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1138029963

Environmental Technology and Innovations

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huynh dung
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ENVIRONMENTAL TECHNOLOGY AND INNOVATIONS

PROCEEDINGS OF THE 1ST INTERNATIONAL CONFERENCE ON ENVIRONMENTAL


TECHNOLOGY AND INNOVATIONS, HO CHI MINH CITY, VIETNAM, 23–25 NOVEMBER 2016

Environmental Technology
and Innovations

Editors
Vladimír Kočí & Tomáš Ruml
University of Chemistry and Technology, Prague, Czech Republic

Phan Dao & Pham Anh Duc


Ton Duc Thang University, Ho Chi Minh City, Vietnam
CRC Press/Balkema is an imprint of the Taylor & Francis Group, an informa business

© 2017 Taylor & Francis Group, London, UK

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Printed and bound in Great Britain by CPI Group (UK) Ltd, Croydon, CR0 4YY

All rights reserved. No part of this publication or the information contained herein may be reproduced,
stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical,
by photocopying, recording or otherwise, without written prior permission from the publisher.

Although all care is taken to ensure integrity and the quality of this publication and the information
herein, no responsibility is assumed by the publishers nor the author for any damage to the property or
persons as a result of operation or use of this publication and/or the information contained herein.

Published by: CRC Press/Balkema


P.O. Box 11320, 2301 EH Leiden, The Netherlands
e-mail: [Link]@[Link]
[Link] – [Link]

ISBN: 978-1-138-02996-5 (Hbk)


ISBN: 978-1-315-37499-4 (eBook PDF)
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Table of contents

Preface ix
Organization xi
Message from Ton Duc Thang University xiii
Introduction xv

Keynote speeches
Sustainable sewage treatment for 21st century 3
J. Bartacek, P. Dolejs, V. Kouba, J. Hejnic & P. Jenicek
Biohydrogen—a green hydrogen 7
C.Y. Lin, C.H. Lay & H.C. Lu
Strategic Environmental Assessment (SEA)—an important tool in marine and coastal
environment management. A case study: SEA for socio-economic master plan for Tonkin
Gulf coastal economic belt, Vietnam 9
T. Le
Metabolomics: A challenging research tool in biotic matrices characterization 17
J. Hajslova, M. Stranska, J. Pulkrabova & T. Ruml
Methodology for screening of HIV inhibitors applicable for in silico designed molecules
and empirical testing of traditional medicinal materials 21
M. Rumlová, V. Spiwok, T. Ruml & R. Hadravová

Environmental engineering
Demonstration of an EFE-BROW model expost application on
brownfields sites 31
B. Vojvodíková, Š. Vilamová, A. Király, K. Chuchrová, M. Piecha & K. Bařinka
Heavy metal contamination of mine area and their uptake by plants (Tailing pond
Sedem Žien, Slovakia) 37
E. Remešicová, A. Király & P. Andráš
Emission factors of criteria pollutants from domestic thermal units 43
F. Skácel & V. Tekáč
Fabrication, characterization, and pervaporation performance of graphene oxide/poly
(vinyl alcohol) nanocomposite membranes for ethanol dehydration 47
H.H. Nguyen & N.P.D. Ngo
Fabrication, characterization and antibacterial activity against Escherichia coli of zinc
oxide/graphene nanocomposite 55
H.H. Nguyen, H.B.S.L. Nguyen, T.T.T. Nguyen & T.T. Nguyen
Application of Box-Behnken design for treatment of tannery wastewater 61
J.C. Beltrán-Prieto, K. Kolomazník & H.B.S.L. Nguyen
Effect of phosphate and nitrogen resources on lipid-rich microalgae cultivation from
textile wastewater 65
J.Y. Wu, S.Y. Wu, J.J. Syu, H.L. Yeh, C.H. Lay, C.Y. Lin & C.C. Chen

v
Correlation of highway traffic and NOx concentration level 71
K. Maneva & F. Skácel
Sorption of heavy metals from aqueous solutions using different types of sorbents 77
M. Chlupáčová, H. Parschová & P. Kůs
Separation of noble gas from helium 83
M. Janák & K. Ciahotný
Study on physicochemical factors influencing sorption capacity in carbonate loop 87
M. Staf, K. Ciahotný, V. Vrbová & L. Jílková
Treatment of pig-waste slurry by a microbial fuel cell using different types of plate electrode 95
M.F. Lai & J.H. Lin
Anaerobic digestion of sludge in municipal wastewater treatment plant—example
of European Solution 99
P. Jenicek, J. Bartacek, J. Kutil & J. Zabranska
Simulation of purification circuits of next generation gas-cooled nuclear reactors 105
T. Hudský, K. Ciahotný & J. Berka
Detection of diethylene glycol by polyaniline coated electrode in a voltammetry system 111
T.K. Tran, H.J. Leu & C.Y. Lin
Removal of ion Pb2+, Zn2+, Cu2+ in aqueous solutions by red mud of Bao Loc Bauxite 119
T.T.O. Truong

Clean energy and sustainability


Single-stage biohythane production via co-immobilized fermentative microorganisms 127
C.Y. Lin, D.T. Ta, C.Y. Chu & T.M.N. Ta
Anaerobic bio-hythane production in a single reactor 133
C.Y. Lin, P.C. Hung & C.H. Lay
Biomass fly ash application for AMD treatment 137
E. Remešicová, A. Király & P. Andráš
Application of staged biomass gasification for combined heat and power production 143
J. Brynda, S. Skoblia, Z. Beňo, M. Pohořelý & J. Moško
Assessment of the possibility of biogas technology development for farmers in
Cu Chi District, Ho Chi Minh City 149
M.T. Dang, T.L.C. Nguyen, M.H. Le & A.D. Pham
An overview of food waste management in Ho Chi Minh City, Vietnam 155
N.B.D. Thi
Pyrolysis technologies and energy recovery from waste in the Czech Republic 161
V. Lapčík
Environmental impact assessment in branch of wind energy in the Czech Republic 169
V. Lapčík & V. Lapčík Jr.
A comparison of catalyst activity for methanation reaction 177
V. Šnajdrová, T. Hlinčík & K. Ciahotný
Evaluation of rice husks qualified for energetic utilization in Vietnam 181
V.M. Duong & F. Skácel

Water resources management


Ecological health monitoring used for river ecosystems in Vietnam: Challenges and prospects 187
A.D. Pham, T.M.L. Nguyen, T.T.H. Nguyen & T.S. Dao
Possibilities for drinking water supply in periods of drought in the Czech Republic 197
M. Kyncl & S. Heviánková

vi
Benthic macroinvertebrates from Dongnai estuaries in Southern Vietnam 203
M.T. Dang, A.D. Pham, T.S. Dao & V. Lapčík
Flow simulation in Sai Gon-Dong Nai river system using TELEMAC 2D 209
Q.D. Dang & T.D. Nguyen
Toxicity of cyanobacterial extract from Cylindrospermopsis raciborskii and potential
solutions for mitigation the cyanobacterial mass development in Xuan Huong Lake,
Da Lat City, Vietnam 213
T.S. Dao, T.P.L. Nguyen & T.K.T. Vo
Zooplankton from Thi Vai River in Southern Vietnam 219
T.T.H. Nguyen, T.M.L. Nguyen, A.D. Pham, D.H. Vuong & V. Lapčík
Spatial distribution of macroinvertebrate assemblages in inland waters of Quang Ngai
Province, Vietnam 225
V.M. Pham, T.T. Nguyen & A.D. Pham
Life cycle assessment of different constructed wetland systems in new Taipei City 231
V.M.T. Nguyen & T.M. Lee

Public health and environment


Comparison of purifying flue gas with selective catalytic and non-catalytic reduction
in waste-to-energy plants with Life Cycle Assessment (LCA) 239
E. Picková & V. Kočí
The effects of reduction conditions on synthesis of graphene by modified hummers
and eco-friendly methods 243
H.H. Nguyen
Assessment of body burden of Czech population to polycyclic aromatic hydrocarbons 251
J. Pulkrabova, D. Lankova, K. Urbancova, A. Svarcova, M. Stupak & J. Hajslova
Estimation of environmental economic for sustainable cultivation of vines in Cu Chi District,
Ho Chi Minh City, Vietnam 255
M.T. Dang, Q.T. Dinh & P.M. Dang
Working posture analysis and design using ergonomics methods and simulation
software in brick production process at Truong Viet Company 263
P.L. Nguyen & D.K. Le
The methods for air pollution emission control from industrial boilers in Ho Chi
Minh City, Vietnam 271
T.L. Phu, Q.V. Nguyen & V. Lapčík
Application of the Analytical Hierarchy Process (AHP) for landslide susceptibility mapping:
A case study in Yen Bai province, Vietnam 275
T. Trinh, D.M. Wu, J.Z. Huang, B.T. Luu, K.H. Nguyen & H.Q. Le
Measures of mitigating the negative impacts of the urbanization and industrialization
to the land resources and environment in Vietnam 283
T.L.C. Nguyen
Identifying hazards at latex workshop of Ben Suc Rubber Factory, Vietnam 289
T.N.S. Tran & A. Bernatík
Building forecast maps of dust dispersion in the Song Hau 1 Thermal Power Plant, Vietnam 297
T.T.H. Nguyen, A.D. Pham, T.V. Nguyen & T.K. Do
Current needs for further developments toward a circular economy—specifically
in the Central European Region 305
V. Kočí
Modern ecological—economic status and sanitary conditions in Vietnam 313
V.H.P. Nguyen & V.I. Chernusov

vii
An overview of forest transition and its environmental impacts in Vietnam 317
V.V. Nguyen, T.T.T. Phan & N.B.D. Thi
Control of noise level and its effects on workers in Hiep Phuoc cement grinding plant,
Holcim Vietnam 321
X.T. Thai & P. Kučera
Proposal of a method for predicting and taking measures against soil slips generating debris
flows in a case study of the 2014 Hiroshima sediment disasters 327
Y. Ooka, H. Umezawa, R. Sawada, A. Tameike, Y. Ishikawa & Q.D. Dang

Author index 333

viii
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Preface

ICETI 2016 (International Conference on Environmental Technology and Innovations) is first conference
on this topic in Vietnam promoted by the following institutions: Ton Duc Thang University (TDTU),
University of Chemistry and Technology, Prague (UCT), VŠB—Technical University of Ostrava (VŠB—
TUO) and Feng Chia University (FCU). This conference brings together engineers, scientists, researchers,
students, managers and other professionals in order to address and discuss emerging environmental issues
dealing with interactions of industrial development and environment.
The main theme of the Conference is actual topics of Environmental Technologies and Innovations.
The Conference provides a forum for presentation and discussion of scientific papers covering theoreti-
cal and experimental research in broad spectrum of environmental engineering and technology. Practical
application of field and industrial scale of environmental innovations are presented on conference, too.
ICETI 2016 is organized for the first time in Ho Chi Minh City, Vietnam. Ho Chi Minh City one of
biggest cities in Vietnam, as well as in the world, lies in the southern part of Vietnam and ranks amongst
the most impressive and modern cities in the world. The city has always played an important part in the
history of the country.
The host of the conference is the Ton Duc Thang University in close cooperation with UCT Prague,
VŠB—TUO from Czech Republic and FCU from Taiwan. The Ton Duc Thang University, as well as
University of Chemistry and Technology Prague, VŠB—Technical University of Ostrava and Feng Chia
University rank among top technical universities in their countries. They focus on research dealing with
environmental protection and sustainable industry practice and play in this context crucial role in devel-
opment of new innovative and long-term sustainable industry and economy in their countries and cor-
responding regions.
The program of the Conference includes around 55 papers from prestigious authors coming from all
over the world including China, Czech Republic, India, Japan, Russian Federation, Slovakia, Taiwan and
Vietnam. Originally, about 75 abstracts were submitted. After the review by the Technical Programme
Committee of full papers, 55 have been accepted and are included in these Proceedings. The work and
effort of the peers involved in the Technical Program Committee in helping the authors to improve their
papers are greatly appreciated.
We would like to thanks authors as well as reviewers for their contributions in this process. The review
process has been conducted electronically through the Conference webpage.
Finally we would like to acknowledge the local organizing committee for their careful planning of the
practical arrangements.

Vladimír Kočí, Tomáš Ruml,


Phan Dao & Pham Anh Duc
Editors

ix
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Organization

HONORARY CHAIRS

Prof. Le Vinh Danh, President of Ton Duc Thang University, Vietnam


Prof. Ivo Vondrák, Rector of VŠB—Technical University of Ostrava, Czech Republic
Prof. Karel Melzoch, Rector of University of Chemistry and Technology, Prague, Czech Republic

CONFERENCE CHAIRMAN

Vladimír Kočí, UCT Prague, Czech Republic

CONFERENCE CO-CHAIRMEN

Tomáš Ruml, UCT Prague, Czech Republic


Radmila Kučerová, VŠB—Technical University of Ostrava, Czech Republic
Alexander Király, VŠB—Technical University of Ostrava, Czech Republic
Chiu-Yue Lin, Feng Chia University, Taiwan & Ton Duc Thang University, Vietnam
Phan Dao, Ton Duc Thang University, Vietnam

ORGANIZING INSTITUTIONS

Faculty of Environment and Labour Safety, Ton Duc Thang University, Vietnam
Faculty of Environmental Technology, UCT Prague, Czech Republic
Faculty of Food and Biochemical Technology, UCT Prague, Czech Republic
Faculty of Mining and Geology, VŠB—Technical University of Ostrava, Czech Republic
Green Energy Development Center, Feng Chia University, Taiwan
European Cooperation Center, Ton Duc Thang University, Vietnam

INTERNATIONAL CONFERENCE COMMITTEE

Vladimír Kočí, UCT Prague, Czech Republic


Tomáš Ruml, UCT Prague, Czech Republic
Pavel Jeníček, UCT Prague, Czech Republic
Jan Bartáček, UCT Prague, Czech Republic
Pavel Šimáček, UCT Prague, Czech Republic
Daniel Maxa, UCT Prague, Czech Republic
Veronika Vrbová, UCT Prague, Czech Republic
Marek Šír, UCT Prague, Czech Republic
Lenka Honetschlagerová, UCT Prague, Czech Republic
Vojtech Dirner, VŠB—Technical University of Ostrava, Czech Republic
Jan Valíček, VŠB—Technical University of Ostrava, Czech Republic
Radmila Kučerová, VŠB—Technical University of Ostrava, Czech Republic
Miroslav Kyncl, VŠB—Technical University of Ostrava, Czech Republic
Juraj Ladomerský, VŠB—Technical University of Ostrava, Czech Republic

xi
Vladimír Lapčík, VŠB—Technical University of Ostrava, Czech Republic
Alexander Király, VŠB—Technical University of Ostrava, Czech Republic
Petr Saha, Tomas Bata University in Zlín, Czech Republic
Karel Kolomazník, Tomas Bata University in Zlín, Czech Republic
Chiu-Yue Lin, Feng Chia University, Taiwan
Nguyen Thi Thu Lan, Ton Duc Thang University, Vietnam
Nguyen Thi Mai Linh, Ton Duc Thang University, Vietnam
Pham Anh Duc, Ton Duc Thang University, Vietnam
Phan Dao, Ton Duc Thang University, Vietnam
Dang Quoc Dung, Ton Duc Thang University, Vietnam
Thi Ngoc Bao Dung, Ton Duc Thang University, Vietnam
Nguyen Vu Hoang Phuong, Ton Duc Thang University, Vietnam
Truong Thi To Oanh, Ton Duc Thang University, Vietnam
Nguyen Huynh B.S. Long, Lac Hong University, Vietnam

LOCAL ORGANIZING COMMITTEE

Nguyen Thoi Trung, Ton Duc Thang University, Vietnam


Trinh Minh Huyen, Ton Duc Thang University, Vietnam
Phan Dao, Ton Duc Thang University, Vietnam
Pham Anh Duc, Ton Duc Thang University, Vietnam
Nguyen Thuy Lan Chi, Ton Duc Thang University, Vietnam

SECRETARY OF THE CONFERENCE

Dang Quoc Dung, Ton Duc Thang University, Vietnam


Nguyen Le Thuy Di, Ton Duc Thang University, Vietnam

SPONSORED BY

Ton Duc Thang University, Vietnam


VŠB—Technical University of Ostrava, Czech Republic
University of Chemistry and Technology, Prague, Czech Republic
Feng Chia University, Taiwan
European Cooperation Center, Vietnam

xii
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Message from Ton Duc Thang University

Welcome to the 1st International Conference on Environmental Technology and Innovations (ICETI 2016),
organized by Ton Duc Thang University in Ho Chi Minh City, Vietnam. This Conference aims at offering
a forum for scientists, researchers, and managers from universities and companies to share their research
findings and experiences in the field. In recognition of its special meaning and broad influence, we con-
sider the organization of this Conference as one of our strategic activities toward developing within three
decades an applied research university.
Ton Duc Thang University (TDTU) has always described itself as a young aspiring and dynamically
growing higher education institution in vibrant Ho Chi Minh City, Vietnam.
TDTU is steadily growing to meet the expanding demand for higher education as well as high-quality
human resources in Vietnam. With sixteen faculties and around 22,000 students, the University is now
ranked among the largest and fastest developing universities in Vietnam in all aspects.
On behalf of TDTU, the host institution of ICETI 2016, I would like to express my sincere apprecia-
tion to our great partners including University of Chemistry and Technology, Prague (Czech Republic),
VŠB—Technical University of Ostrava (Czech Republic) and Feng Chia University (Taiwan), for their
great effort in co-organizing this Conference. I would also like to send my special thanks to the conference
committees, track chairs, reviewers, speakers and authors around the world for their contributions to and
interest in our event.
I believe that you will have an interesting and fruitful conference in Vietnam. I really look forward to
welcoming all of you at our campus and hope that this Conference will start a long-term partnership
between you and our universities.
September 2016

Dr. Nguyen Thoi Trung, Associate Professor


Vice-President, Ton Duc Thang University, Vietnam

xiii
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Introduction

The Conference covers a number of topics within enviromental technology and engineering including
topics dealing with human health as influenced by environment and food quality. The Conference
is especially focused on environmental engineering, clean energy and sustainability, water resources
management, water and food analysis and public health and environment.
There are five very interesting and actual keynote lectures on the program of conference. Jan Bartacek
introduce listeners to sustainable sewage treatment in 21st century, C.Y. Lin prepared actual lecture on
A green hydrogen—biohydrogen, T. Le report about Strategic Environmental Assessment (SEA) as an
important tool in marine and coastal environment management and presents a case study focused on
Socio-Economic Master Plan for Tonkin Gulf Coastal Economic Belt in Vietnam. Jana Hajšlová explain
new term Metabolomics as a challenging research tool in biotic matrices characterization and Tomáš
Ruml presents methodology for screening of HIV inhibitors applicable for in silico designed molecules
and empirical testing of traditional medicinal materials.
Main body of conference program consists of lectures divided into following sessions: Environmental
Engineering; Clean Energy and Sustainability; Water Resources Management and Public health and
Environment. All conference sessions are truly interdisciplinary. Following general topics are discussed in
conference sessions:

I. ENVIRONMENTAL ENGINEERING

• Environmental engineering
• Emerging pollutants
• Air pollution
• Soil contamination and remediation

II. CLEAN ENERGY AND SUSTAINABILITY

• Clean energy and sustainability


• Waste to energy
• Biofuels

III. WATER RESOURCES MANAGEMENT

• Water and wastewater management


• Hydrology and water resources management
• Solid waste management

IV. PUBLIC HEALTH AND ENVIRONMENT

• Public health and the environment


• Ecological, carbon, water and other footprints
• Quality and safety of food production
• Environmental planning, management and policies for cities and regions
• Life Cycle Assessment and environmental data analysis

xv
Keynote speeches
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Sustainable sewage treatment for 21st century

J. Bartacek, P. Dolejs, V. Kouba, J. Hejnic & P. Jenicek


Department of Water Technology and Environmental Engineering, University of Chemistry and Technology,
Prague, Czech Republic

ABSTRACT: In 2015, in total 2.4 billion people still use unimproved sanitation facilities, including
946 million people who still practice open defecation. On the other hand, in most developed countries,
close to 100% of sewage produced is being treated by intensive processes that deliver high quality effluents
while being extremely costly and energy intensive. New sanitation concepts, acceptable both in developed
and developing countries must be proposed to improve this situation. This paper shows some of the
recent developments in sustainable sewage treatment that include resource recovery, less energy intensive
techniques and decentralized solutions.

Keywords: sustainable sanitation, anaerobic digestion, autotrophic nitrogen removal, resource recovery,
sewage treatment

1 INTRODUCTION water (for irrigation, drinking or other purposes)


chemical energy, heat and nutrients (mainly nitro-
In 2015, about 50% of people living in rural areas gen and phosphorus). Recently, researchers focus
and 18% of people in urban areas lack improved on more specific materials such as proteins or bio-
sanitation facilities. I.e. in total 2.4 billion people plastics (Verstraete et al., 2009). Moreover, tech-
(one in three) still use unimproved sanitation facili- nologies that can be utilized on decentralized level
ties, including 946 million people who still practice are being prioritized (Zeeman et al., 2008, Zeeman
open defecation (UN, 2015). This situation, even and Kujawa-Roeleveld, 2011).
though much improved since Millennium Devel- This paper shows some of the recent develop-
opment Goals have been defined in 1990, has ments in sustainable sewage treatment that includes
severe impact on the quality of both human life resource recovery, less energy intensive techniques
and natural environment. Should this situation be and decentralized solutions.
improved, substantial work has to be done.
In most developed countries, close to 100%
of sewage produced is being treated by intensive 2 ANAEROBIC DIGESTION: THE KEY
processes that deliver high quality effluents while PROCESS FOR ENERGY RECOVERY
being extremely costly (UN, 2015). Typically, acti- FROM SEWAGE
vated sludge process is used that is expensive both
in terms of capital costs (large tanks with sophis- Anaerobic biotechnology is the key process for
ticated equipment) and operational costs (energy, recovery of chemical energy from wastewater. This
chemicals). Moreover, its use requires construction process can be implemented in three concepts:
of centralized sewage collection systems, which is (1) traditional centralized concept, (2) centralized
extremely expensive too. Together with ever increas- concept with anaerobic digestion as a core technol-
ing requirements for effluent quality, this causes ogy and (3) decentralized concept.
the situation when sewage treatment established
in developed countries becomes economically and
2.1 Energy recovery in traditional centralized
environmentally unsustainable. Moreover, the price
concept with aerobic treatment
of current sewage treatment technologies prohibits
their application in developing regions. The anaerobic digestion of primary sludge alone
New development in wastewater treatment is or with waste activated sludge is a well-established
driven towards robust technology that requires component of energy recovery from used water in
minimum use of energy and recovers maximum the current centralized systems. In this concept, the
amount of resources from the wastewater. The efficiency of energy recovery largely depends on
most important resources that can be recovered are the efficiency of solids separation in the primary

3
settling tank. Typically, primary sludge contains Various modifications of reactor set-ups have
30–40% of the total COD load and 60–70% of it been used for this purpose (Fig. 2A). Most often,
can be transformed into biogas. With the addition UASB type reactors are currently used in full-scale
of excess activated sludge (20–30% of COD load), (Mahmoud et al., 2004) and they can be combined
which is, however, much less degradable (30–50%), with a membrane unit (Ozgun et al., 2015). The
total biogas production amounts to 20–30% of performance of this technology reported in lit-
total COD load. Considering the fact that the elec- erature varies significantly. While most authors
tric energy yield from biogas is less than 34% of obtained effluent COD concentrations of (depend-
the biogas energy, the electricity-generating poten- ing on process temperature) 50–200 mg/L (Ozgun
tial in used water is less than 15% of the chemical et al., 2015, Gouveia et al., 2015), Shin et al.
energy in the used water COD. (2014) reported much better performance when
The separation of primary sludge can be Granulated Activated Carbon (GAC) was used
enhanced by precipitation with ferric chloride, as biomass carrier in a bioreactor using micro-
alum, polymers or other coagulants. As shown fiber membranes. Shin et al. (2014) obtained up to
in Prague central wastewater treatment plant (the 40% transformation of influent COD into biogas.
Czech Republic), enhanced primary treatment can In addition, Smith et al. (2013) obtained approxi-
remove 55 to 60% of the total suspended solids mately 35% transformation of COD into biogas
(Jenicek et al., 2012) and up to 40% of COD load using a complete-mix AnMBR and submerged,
will then be transformed into methane. It should flat-sheet membrane.
be noted that dosing large quantities of iron (chlo- Because anaerobic digestion of solids is very
ride or sulfide) means additional costs and poten- slow at low temperatures, it is advantageous to
tially introduces external pollution of used water thicken and transfer the solids accumulated in
(inorganic salts). the psychrophilic anaerobic reactor into a second,
The centralized nature of this approach allows smaller, mesophilic reactor where solids can be
for co-digestion of various organic materials
together with sewage sludge. Organic fraction of
municipal solid waste, food waste, high-strength
industrial wastes, glycols from airplane deicing,
manure, etc. may be used for this purpose.

2.2 Energy recovery in centralized concept with


anaerobic digestion as the core technology
The centralized systems of wastewater collection
are well established in current settlements and
may not be fully replaced in the foreseeable future.
Currently, if anaerobic digestion is to be used for
treatment of used water, it must be adapted to the
conditions of typical municipal wastewater (lower
temperature, low COD concentration).

Figure 2. Centralized concept with anaerobic digestion


Figure 1. COD flows in the traditional centralized con- as the core technology used in the main stream (A) or
cept of wastewater treatment (AD is anaerobic digester). after a pre-concentrating step (B).

4
degraded. Although this substrate is usually readily and should be used when new buildings or neigh-
degradable(Mahmoud et al., 2004), an additional borhoods are built.
10–20% of COD can be transformed into meth-
ane. Moreover, co-digestion with other biodegrad-
able solid materials (wastes) collected centrally is 3 POST-TREATMENT OF EFFLUENTS
possible in this reactor. FROM ENERGY RECOVERING
The main constrains of anaerobic diges- SEWAGE TREATMENT
tion at low temperature are low hydrolytic and
methanogenic activity and elevated solubility of If activated sludge process is replaced in the new
methane. Methane losses in the effluent can be sewage treatment concepts, effluent with high
up to 36% (Shin et al., 2014). Another 10–20% nitrogen and phosphorus concentrations must be
percent of COD will be inevitably utilized for further treated before being discharged into envi-
the reduction of sulfate to sulfide and lost in the ronment. Alternatively, the effluent may be directly
effluent (if not utilized as internal substrate for used for irrigation combined with fertilization.
denitrification). For this purpose, especially effluent from Anaero-
Alternatively to the direct use of psychrophilic bic Membrane Bioreactors (AnMBR) is suitable
anaerobic digestion, municipal used water can be (Ozgun et al., 2013).
first pre-concentrated and only the concentrated
stream is then anaerobically digested at mesophilic
3.1 Autotrophic nitrogen removal
temperatures. Bioflocculation (Akanyeti et al.,
2010, Zhang et al., 2013) or Biosorptive activated To complement energy recovery with low-energy
sludge process (Diamantis et al., 2014) can be used nitrogen removal, Partial Nitritation and Anammox
for the separation of 70–80% of total COD load. (PN/A) can reduce the consumption of organic
Sludge separated in this process is highly degrada- carbon for denitrification up to 89%, energy con-
ble (up to 70%) and thus 50% of total COD load sumption for aeration by 50%, and the production
can be transformed into biogas. Alternatively, for- of disposed sludge. PN/A is already established
ward osmosis can be used for pre-concentrating in side-stream of municipal wastewater treatment
used water (Nasr and Sewilam, 2015). plant (Lackner et al., 2014).
The pre-concentration of municipal used water The applicability of single-stage PN/A in the
avoids the problems with dissolved methane at low main stream for moderate temperatures of 19 and
temperatures and minimizes the production of 21°C was recently proved in pilot-scale conditions
sulfide. by Lotti et al. (2015) and (Seuntjens et al., 2016).
These single-stage PN/A report lower activity of
AOB as compared to anammox. Therefore, anam-
2.3 Energy recovery in decentralized concept
mox activity could be fully utilized by separating
If practically possible, decentralization (to a cer- PN/A in two stages (Lotti et al., 2015, Seuntjens
tain level) is very favorable for the use of anaero- et al., 2016, Kouba et al., 2016).
bic digestion, because concentrated streams (black It is well established, that anammox can grow
water, kitchen waste) can be treated separately in both anaerobically pre-treated municipal waste-
from diluted streams (gray water, urine). As shown water (Laureni et al., 2015) and in A-stage efflu-
in Figure 3, around 45% of COD produced in a ent (Lotti et al., 2014). Although the efficiency of
typical household can be transformed into meth- anammox adapted to 25–35°C is severely reduced
ane (de Graaff, 2010). From the energy recovery at main-stream temperatures (Lackner et al.,
point of view, decentralization is very favorable 2015), Hendrickx et al. (2014) enriched high-
activity anammox adapted to 10°C, which shows
that anammox can be optimized to main-stream
conditions.
Although there are still many challenges, the
development of autotrophic nitrogen removal
from main stream sewage is being developed and
it can be predicted that it will become established
technology within several years.

4 CONCLUSIONS

Figure 3. Decentralized concept of energy recovery Sewage treatment techniques for the 21st century
from used water. must maximally recycle resources from sewage and

5
must require minimum energy consumption. At mainstream municipal wastewater. Water Science and
the same moment, these technique must produce Technology, 72, 1358–1363.
high quality effluent with minimum greenhouse Laureni, M., Weissbrodt, D. G., Szivák, I., Robin, O.,
gas emissions. Anaerobic digestion seems to be the Nielsen, J. L., Morgenroth, E. & Joss, A. 2015. Activ-
ity and growth of anammox biomass on aerobically
most preferable core technology for such systems. pre-treated municipal wastewater. Water Research, 80,
In the view of tremendous costs of centralized 325–336.
sewage collection systems, decentralized solutions Lotti, T., Kleerebezem, R., Hu, Z., Kartal, B.,
are ever more preferable. de Kreuk, M. K., Van Erp Taalman Kip, C., Kruit, J.,
Hendrickx, T. L. G. & Van Loosdrecht, M. C. M.
2015. Pilot-scale evaluation of anammox-based main-
ACKNOWLEDGEMENT stream nitrogen removal from municipal wastewater.
Environ Technol, 36, 1167–1177.
This work has been made possible by the finan- Lotti, T., Kleerebezem, R., Van Erp Taalman Kip, C.,
Hendrickx, T. L. G., Kruit, J., Hoekstra, M. & Van
cial support of Czech Technological Agency Loosdrecht, M. C. M. 2014. Anammox Growth on
(TH01021100) and European Comission through Pretreated Municipal Wastewater. Environ Sci Tech-
European Joint Doctorate programme Super-W— nol, 48, 7874–7880.
Resource, Product and Energy Recovery from Mahmoud, N., Zeeman, G., Gijzen, H. & Lettinga, G.
Wastewater (gran agreement No. 676070). 2004. Anaerobic sewage treatment in a one-stage
UASB reactor and a combined UASB-Digester sys-
tem. Water Research, 38, 2347–2357.
REFERENCES Nasr, P. & Sewilam, H. 2015. Forward osmosis: an alter-
native sustainable technology and potential appli-
Akanyeti, I., Temmink, H., Remy, M. & Zwijnenburg, A. cations in water industry. Clean Technologies and
2010. Feasibility of bioflocculation in a high-loaded Environmental Policy.
membrane bioreactor for improved energy recov- Ozgun, H., Gimenez, J. B., Ersahin, M. E., Tao, Y.,
ery from sewage. Water Science and Technology, 61, Spanjers, H. & Van Lier, J. B. 2015. Impact of mem-
1433–1439. brane addition for effluent extraction on the perform-
de Graaff, M. 2010. Resource recovery from black water. ance and sludge characteristics of upflow anaerobic
PhD thesis, Wageningen University. sludge blanket reactors treating municipal wastewater.
Diamantis, V., Eftaxias, A., Bundervoet, B. & Verstraete, W. Journal of Membrane Science, 479, 95–104.
2014. Performance of the biosorptive activated sludge Seuntjens, D., Bundervoet, B., Mollen, H., de Mulder, C.,
(BAS) as pre-treatment to UF for decentralized waste- Wypkema, E., Verliefde, A., Nopens, I., Colsen, J. &
water reuse. Bioresource Technology, 156, 314–321. Vlaeminck, S. 2016. Energy efficient treatment of
Gouveia, J., Plaza, F., Garralon, G., Fdz-Polanco, F. & A-stage effluent: pilot-scale experiences with shortcut
Peña, M. 2015. Long-term operation of a pilot nitrogen removal. Water Science and Technology, 73,
scale anaerobic membrane bioreactor (AnMBR) for 2150–2158.
the treatment of municipal wastewater under psy- Shin, C., Mccarty, P. L., Kim, J. & Bae, J. 2014. Pilot-
chrophilic conditions. Bioresource Technology, 185, scale temperate-climate treatment of domestic waste-
225–233. water with a staged anaerobic fluidized membrane
Hendrickx, T. L. G., Kampman, C., Zeeman, G., bioreactor (SAF-MBR). Bioresource Technology, 159,
Temmink, H., Hu, Z., Kartal, B. & Buisman, C. J. N. 95–103.
2014. High specific activity for anammox bacteria UN. 2015. The Millennium Development Goals Report
enriched from activated sludge at 10°C. Bioresource 2015 [Online]. New York: United Nations.
technol, 163, 214–222. Verstraete, W., Van de Caveye, P. & Diamantis, V. 2009.
Jenicek, P., Bartacek, J., Kutil, J., Zabranska, J. & Maximum use of resources present in domestic “used
Dohanyos, M. 2012. Potentials and limits of anaero- water”. Bioresource Technology, 100, 5537–5545.
bic digestion of sewage sludge: Energy self-sufficient Zeeman, G. & Kujawa-Roeleveld, K. 2011. Resource
municipal wastewater treatment plant? Water Science recovery from source separated domestic waste(water)
and Technology, 66, 1277–1281. streams; full scale results. Water Science and Technol-
Kouba, V., Widiayuningrum, P., Chovancova, L., ogy, 64, 1987–1992.
Jenicek, P. & Bartacek, J. 2016. Applicability of one- Zeeman, G., Kujawa, K., de Mes, T., Hernandez, L.,
stage partial nitritation and anammox in MBBR de Graaff, M., Abu-Ghunmi, L., Mels, A., Meulman, B.,
for anaerobically pre-treated municipal wastewater. Temmink, H., Buisman, C., Van Lier, J. & Lettinga, G.
Journal of Industrial Microbiology & Biotechnology. 2008. Anaerobic treatment as a core technology for
Lackner, S., Gilbert, E. M., Vlaeminck, S. E., Joss, A., energy, nutrients and water recovery from source-
Horn, H. & Van Loosdrecht, M. C. M. 2014. Full- separated domestic waste(water).
scale partial nitritation/anammox experiences—An Zhang, Z., Zhang, J., Zhao, J. & Xia, S. 2013. Effect of
application survey. Water Res, 55, 292–303. short-time aerobic digestion on bioflocculation of
Lackner, S., Welker, S., Gilbert, E. M. & Horn, H. 2015. extracellular polymeric substances from waste acti-
Influence of seasonal temperature fluctuations on two vated sludge. Environmental Science and Pollution
different partial nitritation-anammox reactors treating Research, 1–7.

6
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Biohydrogen—a green hydrogen

C.Y. Lin, C.H. Lay & H.C. Lu


Green Energy Development Center, Feng Chia University, Taichung, Taiwan
Green Energy Technology Group, Faculty of Environmental and Labour Safety, Ton Duc Thang University,
Ho Chi Minh City, Vietnam

ABSTRACT: Biohydrogen is generally produced from organic wastes/wastewaters and its production
fundamentals and technologies had been well developed via lab-scale bioreactors with batch and continu-
ous operations since late 1990’s. A pilot-scale plant of high-rate hydrogen/methane production (HyM-
eTek) and algae cultivation system had been built in the campus of Feng Chia University, Taiwan. This
pilot plant had reactor volumes of 0.5 M3, 2.5 M3 and 0.2 M3 for hydrogen, methane and algae cultivation
units, respectively. The hydrogen and methane reactors were in series and their bio-CO2 gas were stored in
a gas buffer tank (0.1 M3) before being introduced into the algae cultivation reactor. Moreover, a mobile
HyMeTek system treating 30 CMD beverage wastewater had been built and operated. Future prospects
of bio-H2 and bio-CH4 are proposed.

Keywords: biohydrogen, anaerobic fermentation, verification plant

1 INTRODUCTION

Global warming problems enhance the develop-


ments of alternative green and renewable energy
resources. Hydrogen economy is considered as
one of the feasible solutions for this purpose.
Biohydrogen is generally produced from organic
wastes/ wastewaters and is, therefore, consid-
ered as a green hydrogen (Lin and Chang, 1999).
Recently, biohydrogen has been reported to have
the potential gradually to become a major hydro-
gen-generating technology. High-rate biohydro- Figure 1. Field verification plant: (A) 5 m3 Feedstock
gen production technology (hydrogen/methane Tank, (B) 3 m3 Mixing Tank, (C) Control system, (D)
2 m3 H2 Reactor, (E) 2 m3 Mixing Tank, (F) 50 m3 CH4
production, HyMeTek) had been developed via
Reactor.
lab-scale, pilot-plant, field verification plant and
mobile module bioreactors since 2000 in Feng
Chia University, Taiwan. The operation experi-
ences of some of these reactors were summarized.
Future prospects of bio-H2 and bio-CH4 are
proposed.

2 EXPERIMENTAL

The field HyMeTek verification plant had reactor


volumes of 2 M3 and 50 M3 for H2 and CH4 pro-
ductions, respectively (Figure 1). For the mobile Figure 2. Mobile system: (A) 10 m3 Feedstock Tank,
HyMeTek system, it treated 30 CMD beverage (B) 2 m3 H2 Reactor, (C) 4 m3 CH4 Reactor, (D) 4 m3 CH4
wastewater (Figure 2). Reactor, (E) MBR, (F) Control system.

7
Table 1. Bio-hydrogen production from food factory wastewater (field verification plant).

VSS HPR H2 content X HY


(g/L) (m3/m3−d) (%) (%) (mol H2/mol hexose)

2.16 ± 0.93 2.27 ± 0.98 48.6 ± 11.2 84.3 ± 21.4 0.58 ± 0.38

Notes: VSS, volatile suspended solids; HPR, H2 production rate; X, substrate utilization efficiency; HY, H2 yield.

Table 2. Bio-hydrogen and methane production from beverage wastewater (mobile system).

HRT OLR VSS MPR H2 CH4 COD removal MY


(h) (g COD/L−d) (g/L) (m3/m3−d ) (%) (%) (%) (mL CH4/g COD)

12 2.27 ± 0.87 0.511 ± 0.14 0.14 ± 0.03 0.01 ± 0.01 68 ± 17 35.5 ± 19.4 88.1 ± 22.0
8 3.80 ± 1.15 0.61 ± 0.13 0.19 ± 0.03 0.01 ± 0.01 68 ± 10 39.8 ± 20.9 73.4 ± 10.3
4 8.83 ± 2.32 0.52 ± 0.10 0.44 ± 0.01 0.02 ± 0.01 82 ± 13 26.5 ± 12.0 77.9 ± 1.9

Notes: VSS, volatile suspended solids; HPR, H2 production rate; X, substrate utilization efficiency; HY, H2 yield.

3 RESULTS AND DISCUSSION ACKNOWLEDGEMENT

Tables 1 and 2 summarize the performances of Financial supports from Bureau of Energy, Minis-
bio-H2 and CH4 production in field verification try of Economic Affairs, Ministry of Science and
plant and mobile system, respectively. Low bio-H2 Technology (MOST 104-2221-E-035-006-MY3,
production from beverage wastewater was resulted MOST 105-2221-E-035-003), and Feng Chia Uni-
from low influent COD concentration (3.6 g versity, Taiwan and Ton Duc Thang University,
COD/L). The feasibility of using field plant and Vietnam are acknowledged.
mobile system to treat real wastewater feedstock
for bio-H2 and bio-CH4 productions were shown.
However, the feedstock was low in COD concen- REFERENCES
tration and this made low H2 production. To have
a high H2 production performance, higher COD Arimi, M.M., Knodel, J., Kiprop, A., Namango, S.S.,
concentration wastewaters should be used. Zhang, Y., and Geißen, S.U., 2015, Strategies for
Co-production of biohydrogen and methane improvement of biohydrogen production from
has the potential to make anaerobic process cost organic-rich wastewater: A review. Biomass and
Bioenergy 75, 101–118.
effective (Arimi et al., 2015). On the other hand,
Cavinato, C., Fatone, F., Bolzonella, D., and Pavan, P.,
the produced bio-H2 and bio-CH4 could be mixed 2010, Thermophilic anaerobic co-digestion of cat-
to get a green biohythane which should have tle manure with agro-wastes and energy crops: com-
higher combustion efficiency (Porpatham et al., parison of pilot and full scale experience, Bioresource
2007). Hythane is a mixture of H2 and CH4 and Technology, 101(2), 545–550.
both these gases are commercially generated from Lin, C.Y., and Chang, R.C., 1999, Hydrogen production
natural gas and petroleum. Biohythane is an ideal during the anaerobic acidogenic conversion of glu-
and sustainable hythane (Cavinato et al., 2010). cose, Journal of Chemical Technology and Biotech-
nology. 74(6), 498–500.
Porpatham, A.R., and Nagalingam, B., 2007, Effect of
hydrogen addition on the performance of a biogas
4 CONCLUSION fueled spark ignition engine, International Journal of
Hydrogen Energy, 32, 2057–2065.
The HyMeTek technology developed by Feng Chia
University could treat real wastewater feedstock
for bio-H2 and bio-CH4 productions via a mobile
system.

8
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Strategic Environmental Assessment (SEA)—an important tool in


marine and coastal environment management. A case study: SEA for
socio-economic master plan for Tonkin Gulf coastal economic belt,
Vietnam

T. Le
Vietnam Institute for Environmental Science and Development, Vietnam

ABSTRACT: This paper discussed on Strategic Environmental Assessment (SEA) for socio-economic
master plan for Tonkin Gulf Coastal Economic Belt, Vietnam. The results shwed that (i) the level of
coastal and marine environmental pollution would be risen during the Master Plan implementation; (ii)
biological resources will be reduced rapidly because of the extension of industrial parks, urban areas and
tourism zones; (iii) for minimizing the negative impacts on the coastal natural environment, it is necessary
for MPI, provincial People’s Committees, relevant ministries, agencies and investors to reconsider and
adjust various projects in the Master Plan; and (iv) for mitigating the impacts, the SEA report outlines
basic orientations on environmental management and environmental technology which may serve as ref-
erence for MPI and relevant ministries and agencies.

Keywords: Strategic Environmental Assessment (SEA), Tonkin Gulf, master plan, environment

1 INTRODUCTION VESDEC with support for the Swedish SEMLA


Program and Ministry Of Natural Resources and
Vietnam has a long coastal line of over 3,260 km Environment (MONRE) (VESDEC. 2008) may be
lasting through 28 provinces from Quangninh given.
province in the North to Kiengiang province in the
South. The offshore area of Vietnam is over 1.0
mil km2 or over 3.0 times wider than the land area.
2 BRIEF SOCIO-ECONOMIC MASTER
Over 50% of the population living and conducting
PLAN FOR THE TONKIN GULF
economic activities in the coastal provinces. There-
COASTAL ECONOMIC BELT TO YEAR
fore, Vietnam has set up a long—term “sea strat-
2020 AND ITS IMPACTS ON THE
egy” toward 2020 with the target that the GDP
COASTAL ENVIRONMENT
of the coastal region will occupy 53–55% of the
total national GDP (Decree N09/NQ/TW. 2007).
2.1 Brief description of socio-economic master
This development tendency will greatly increase
plan
national economic power but it will also cause
various adverse impacts on the coastal and marine TGCEB includes 2 coastal provinces of Vietnam:
environment. Quangninh province and Haiphong city. The
In the World and in Vietnam many approaches Master Plan for socio-economic development
and measures may be properly used for coastal and of the TGCEB consists of 2 main components:
marine environment management. However, in (1) Development plan for “driving force areas”;
prevention of negative environmental and social and, (2) Development plan for economic sectors.
impacts in the stage of socio—economic planning The aim of the Master Plan is to establish the
Strategic Environmental Assessment (SEA) is a TGCEB to be a dynamic economic region, a “vig-
very effective tool (Barker 2000; Partidario, Labos orous growth pole” attracting a large territory in the
2009; UNNEP 1995). Northern Vietnam; it is also a primary integration
To prove this point of view the follow- area of Vietnam and China with ASEAN coun-
ing summary of a case study of SEA for the tries, at the same time it connects to other coastal
Socio-Economic Master Plan for the Tonkin Gulf provinces to establish a economic belt lasting from
Coastal Economic Belt (TGCEB), implemented by Mongcai in the Northern Vietnam to Hatien in the

9
Southern Vietnam to develop quickly and promote
other inland areas of Vietnam (MPI. 2008).
A number of development objectives are set out,
which are as follows:
i. Establishing a transport system in the eco-
nomic belt especially main coastal axis routes
from Mongcai to Doson in order to link with
the Vietnam-China Economic Corridors and
the Southern China, creating conditions to
widen trade and development cooperation
with China and ASEAN countries effectively
and actively.
ii. Forming and developing a number of main
sectors including marine transport, ship build-
ing, thermo-electricity, mining, mechanics, Figure 2. Map of planned industrial and urban areas.
construction materials production, oil and gas
processing, aquaculture processing … to reach
advanced level in ASEAN. most beautiful bay in the World. Halong Bay is
iii. Assuring economic growth rate is 1.4–1.5 times host to two ecosystems: a tropical, moist, ever-
higher than national GDP growth rate; total green rainforest ecosystem; and a marine and
good circulation through the Economic Belt coastal ecosystem. The bay is home to seven
increases more than 20%/year. By 2020, the endemic species. The many islands that dot
TGCEB will contribute to the whole country the bay are home to a great many other spe-
GDP about 6.5%–7%; GDP per capita achieves cies, including 477 magnoliales, 12 pteris, 20 salt
USD 3,500–4000 (MPI. 2008). marsh flora; and 4 amphibia, 10 re[tilia, 40 aves,
and 4 mammalia. In 2015, 2.5 million domestic
and international tourists visited Halong Bay.
2.2 Main coastal environmental objectives ii. Catba National Park and UNESCO Biosphere
impacted by the implementation of the master Reserve includes a main island, 367 islets and
plan sea surface of 260 km2 (Figure 4) with a great
biodiversity reserve. The fauna on the island
Zooplankton have an intermediate position in the
consists of 279 species, including 53 mammal
various social and environmental objectives would
species from 18 families, and 23 endangered
be affected by implementation of the Master Plan.
and critically endangered species. There are
However, the following ones are most sensitive and
160 bird species, 66 species of reptiles and
most important in term of ecological resources
amphibians, and 274 species of insects from
and socio-economic values:
79 different families. Aquatically, there are 900
i. Halong Bay, included islets and an area of sea fish, 178 species of coral, 7 species of sea
1,553 km2 of sea surface (Figure 3). This is an snakes, 4 species of sea turtles, and 21 species
UNESCO’ Natural Heritage and one of the of seaweed found throughout the archipelago.
iii. A number of natural reserves at the coastal and
inland areas (Figure 5).
iv. A number of tourist centers at cities of Mong-
cai, Halong, Haihong, Doson …

2.3 Potentional impact sources to the coastal and


marine environment
2.3.1 Relating-to-waste impact sources
According to the Master Plan, by the year 2020,
total population in the TGCEB will achieve 3.8
million inhabitants (2.20 times higher than that
in 2010), of which population of Haiphong city
will be 1.4–1.5 million inhabitants, Halong city
will have a population of 0.6 million inhabitants.
Urbanization in 2007 was 59% and it will increase
Figure 1. Map of planned transport systems. to 80% in 2020.

10
Figure 4. Map of natural reserves and natural parks in
the TGCEB.

Figure 5. Map of present forest areas in the TGCEB.

significant pollution sources for the coastal and


Figure 3. Halong Bay (a); Langur (Trachypithecus marine environment. Data on pollution loads are
Poliocephalus) in Catba National Park (b). estimated as follows.
i. By 2020, if the whole area of industries are
Additionally, the TGCEB will have 25 indus- hired, daily wastewater discharge will reach
trial parks with total areas of 22,128.5 ha; in which 636,697 m3, BOD load in wastewaters will reach
9,948.3 ha are for rent. Beside industrial parks, in 108,238 kg. If adding flow of cooling water in
the TGCEB, there are 20 industrial clusters, thou- electric plants, industrial wastewater flow will
sands industrial entities outside industrial parks, be very great if total capacity of electric plants
industrial clusters and almost 100,000 small scale is 6,000 MW, total cooling water discharge will
industries located in commercial zones, residen- reach 10,368,000 m3/day.
tial areas or handy-craft villages with the main Beside industrial parks, in 2020, industrial
branches: building materials, energy, pottery, por- wastewater from industrial clusters, factories,
celain, mechanics, shipbuilding, chemistry, metal- production entities outside industrial parks
lurgy, mechanics. Among them, coal industry is the will increase quickly. Sectors with the biggest
traditional one with the largest scale comparing wastewater flow are food processing (meat,
with other regions in Vietnam. aquatic product, breweries), dyeing, tanning,
Wastes generating by the planned industrial metallurgy and chemistry. Most of these enti-
development, urban development and population ties base in Haiphong city.
growth are main pollution sources. Additionally, ii. By 2020 BOD load estimated from urban
wastes generated from agricultural, animal hus- wastewater will be 190 tons/day; from rural
bandry, medical centers and tourism will also area wastewater will be 47.5 tons/day. BOD

11
content in wastewater before treatment will − Land area occupied for transport projects are
be 347 mg/L, greatly exceeding the permis- estimated as 8,670 ha (86.7 km2).
sible limit of Vietnam Standard for Domestic − Land area occupied for 2 economic zones will be
Wastewater (QCVN: 14/2008/BTNMT). 680.48 km2.
iii. According to the Master Plan, the area of agri- − Land area occupied for industrial parks will be
cultural land in the TGCEB will be reduced; up to 221.285 km2 (in Haiphong city, there will
however, annual productivities of food and be 14 industrial parks with total area of 86.597
vegetable will continually increase in 3–4%. km2; Quangninh province will have 11 industrial
Therefore, types of wastes from agricultural parks with total area of 134.688 km2).
activities and runoff water from fields treated − Land area used for urban areas may be 2 times
by pesticides, fertilizers will be a great water higher than the present area of urban land: the
pollution sources. area of urban zone of Haiphong city may be up
iv. In 2020, the total amounts of hospital solid to 40% of total area of the city or it is double area
wastes in Quangninh will be up to 3,600 of the present urban districts; the urban area of
tons (720 tons of hazardous solid wastes), in Halong city may be also double after 15 years;
Haiphong there will be up to 4,800 tons (960 of area of Mongcai town may be increased in 3
hazardous solid wastes). Medical solid wastes times comparing with current area.
in the whole TGCEB will reach 8,400 tons, − Land area used for tourism zones: it can be
increasing 6 times against 2003. estimated additional growth area to be used
for tourism constructions. It is about 500 km2
According to the Master Plan, the TGCEB will
to obtain 15–16 million tourists/year (2.5 times
attract 15.0 million tourists in 2020, in which, there
higher than present number of tourists).
are 6.5–7.0 million of international tourists, the
total amounts of domestic solid wastes generated
From above mentioned information, it can be
by tourists will be 56,250 tons in 2020 (2.0 times
predicted that from now to 2020, about 2,000 km2
higher than that in 2010). In 2020 discharge of
of agricultural land, forestry land, mountain land,
wastewater by tourists will reach 37.5 million m3
coastal land or about 27% in total natural land area
(2.0 times higher against 2010), if it is assumed that
of 2 provinces will be transferred to land using for
each visitor consumes 200 L water/day.
expanding transport, industrial, urban and tourism
Therefore, with the fast growth rates of
projects. A large coastal land, included saline swamps
population, economic sectors and living stand-
and mangrove area, will be acquired, consequently,
ard, growth rates of wastes from all sources of
coastal ecosystems would be seriously damaged.
industry, domestic activities, animal husbandry,
agriculture and health care in the Tonkin Gulf
Coastal Economic Belt will be very fast in a short 2.4 Tendency of change in the coastal and marine
period of time (10 years). Therefore, the pressure environment
of wastes to the coastal and marine environment,
2.4.1 Preliminary assessment of changing
as well as public health and socio-economy in this
tendency of the coastal and marine
zone will be greatly increased. The main area to
environment
be polluted would be Halong Bay, Baitulong Bay
With expansion of urban areas, development of
and coastal lines of Haiphong and Quangninh
more industrial parks, industrial clusters, eco-
provinces.
nomic zones, commercial zones, new infrastruc-
ture works, from now to 2020, land resources in the
2.3.2 Non-relating-to-waste impact sources TGCEB will be changed rapidly in the direction of
The Master Plan is an ambitious which may cre- transferring costal, agricultural and forestry land
ate significantly change in land use, water use, to construction land.
marine resources, biological resource and coastal About 200,000 ha of land will be transferred to
ecological zone. This non-relating to waste- construction land. Areas where land resources to be
impacts may be even stronger, longer and more greatly changed are Vandon district (Quangninh)
difficult to be mitigated than the relating-to- with 50% of natural land transferred for construc-
waste impacts. tion works; Haiha and Damha district (Quangn-
According to the Plan, a large area of agricul- inh) with about 16.5% of natural land transferred
tural land, forestry land and coastal saline swamps for building Haiha industrial park (12,930 ha);
will be occupied for development projects in trans- Yenhung district (Quangninh) with 19.6% of nat-
port (roads, ports, and airports), industrial parks, ural land changed for establishing Damnhamac
economic zones, commercial areas, urban areas, industrial-service park, Thuynguyen, Kienthuy
tourism areas. Among them the largest area of districts (Haiphong city) with more 5,000 ha to to
land will be used for the following purposes. be occupied expansion of Haiphong city.

12
The transference of agricultural and forestry and the East Sea. The main impacts from external
land, coastal swamps to construction land will factors are listed and defined in the SEA study.
cause following problems:
2.4.4 Impact tendency to the coastal and marine
− Changing terrain, possibly resulting to soil slide
environment due to global climate change
and soil erosion, especially soil in mountain-
The coastal areas of Quangninh province and
ous areas in the coastal districts of Quangninh
Haiphong province will be strongly influenced by
province.
climate change, particularly in case of rise of sea
− Changing ecosystems in coastal zones especially
water level. These impacts include:
mangrove ecosystem if saline swamps is trans-
ferred to construction land. Consequently, area i. Losing a part of rural and urban lands at the
of mangrove forests is reduced, which leads to coastal areas.
decrease of wave breaking ability, causing coastal ii. Losing a large areas of agricultural, aquacul-
erosion and decrease of aquaculture area. ture lands.
− Decreasing area of vegetation cover, especially iii. Influencing on coastal industrial parks and
when expanding urban areas, developing Damha urban areas in 2 provinces: a number of
Economic Zone, Damnhamac Industry—Sevice houses, business centers and industrial facili-
Zone and industrial parks. Reduction of vegeta- ties may be inundated.
tion cover will decrease biological diversity, water iv. Influencing on the transport networks; vari-
storing ability, groundwater resource, and increase ous roads, railways, bridges, harbors and air-
of erosion process, flood intensity and impacts of ports at the coastal areas may be inundated.
climate change. The expansion of roads, harbors, v. Losing a large area of mangrove forests and
urban areas, tourism areas may violate the area of ecosystems involved.
Catba Biosphere Reserve, Halong Bay Heritage, vi. Influencing on coral reefs, seaweed areas and
Natural Conserve areas as Baitulong, Kythuong, ecosystems involved.
Yentu, consequently may cause adverse effect on vii. A number of landscapes, tourism resources
the environment and culture of the region. will be affected.
viii. Floods will happen more often with destruc-
2.4.2 Changing tendency of coastal and marine tion that is more serious.
water quality ix. Drought will be more severe, rainfall change
As predicted in this SEA by 2020, in the TGCEB, resulting to seriously affecting fresh water
the BOD load of wastewaters from industrial parks resources. Consequently, it has influence on
will be increased in 7.3 times, discharge of domestic people, ecosystems, landscape and all eco-
wastewater will be increased in 2.0 times, compar- nomic sectors.
ing with the ones in 2010. If including wastewaters x. A large area of lands in the coast of islands
from industrial clusters, entities outside industrial and some small islands may no longer exist.
parks, and from the sectors of animal husbandry, xi. Climate change may creates conditions for aris-
aquaculture, the discharge of wastewaters and ing some new diseases for people and animals.
load of pollutants discharge into the water and xii. Degradation of soil, water, landscape and
land environment will much higher. infrastructural facilities.
There are not sufficient bases to forecast the
increase in concentrations of pollutants in the
sea and rivers of the TGCEB. However, the areas 3 GENERAL DIRECTION AND SOLUTION
which will be polluted significantly comparing TO PROPERLY MANAGE COASTAL
with ones at present if there is no effective solution AND MARINE ENVIRONMENT IN
to manage and treat waste source. THE PROCESS OF THE MASTER PLAN
IMPLEMENTATION
2.4.3 Changing tendency of the coastal and
marine environment in the TGCEB by As predicted above, if there are not high effec-
external impacts tive measures and solutions in management of
The TGCEB is surrounded by Guangxi province the environment, the Master Plan implementa-
(People’s Republic of China) in the North the tion will cause a number of negative impacts on
Red River Delta provinces (Haiduong, Thaibinh) the coastal and marine environment. Therefore, to
in the West and the East Sea in the East and ensure economic growth targets, integrating with
Southeast. Therefore, the natural environment and protection of the environment toward sustainable
socio-economy of the TGCEB are always affected development, in the period 2020, Ministry of Plan-
by hydrographic, marine, weather factors and eco- ning and Investment (MPI), other ministries, Peo-
nomic activities from the neighboring provinces ple Committees of Quangninh and Haiphong and

13
the owners of projects should implement general actions” of the Master Plan, which should be adjusted
directions and basic solutions as follows: to achieve the targets of sustainable development:
i. Integrating development plan and develop- i. Review scale and area Developing Vandon eco-
ment projects in the whole Economic Belt nomic zone with 551 km2;
into environmental protection, in general, and ii. Reconsider and reject the project of Construc-
into coastal and marine environment manage- tion of Vandon Airport because of the reasons
ment, in particular. of economy and environment;
ii. Checking and adjusting some development iii. Reject project of oil refinery in Haiha indus-
projects in the development plan for the trial park;
TGCEB. The projects, those may cause major iv. Review carefully each industrial park project, giv-
environmental and/ or social impacts and less ing priority to fulfill the existing industrial parks.
economic profit, should be rejected. Do not set up industrial parks in fertile agricul-
iii. Carefully conducting and appraising Envi- tural lands, inside or near natural conserve areas;
ronmental Impact Assessment (EIA) for v. Do not permit the projects located inside
investment projects. Halong Bay, Catba National Park, Baitulong,
iv. Applying appropriate scientific solutions in Yentu Reserve and other natural reserves.
environmental management and protection
of ecologically sensitive areas, especially pro-
tection of Halong Bay, Catba National Park, 3.2 Applying scientific measures to integrated
natural reserves and mangrove ecosystems in environmental management
the region. In order to improve effect for the task of environ-
v. Establishing environmental monitoring sys- mentally synthetic management in the TGCEB, it
tem for the whole region. is necessary to apply some following measures:
vi. Applying technological solutions in coastal
environmental pollution control and environ- − Setting up a database serving coastal and marine
mental risk management. environmental management and reasonable
vii. Strengthening capacity in coastal environ- use of natural resources. In there, beginning
mental management and cooperation in envi- from collecting, handling and storing data/
ronmental management. information about environmental compositions
viii. Promoting public involvement in project in the whole region aiming at building system of
appraisal and environment management. environmental maps for the whole belt;
− Conducting environmental zoning, defining use
Some of the above directions are briefly ability for environmental zones in the TGCEB;
described below. − Developing modeling in integrated coastal envi-
ronmental management in the region;
3.1 Integration of the master plan into coastal − Conducting integrated coastal management;
and marine environmental protection − Applying proper measures for biological resource
conservation and development to enhancing
The most important factor in integrated coastal management for Catba National Park, Baitulong
environmental management in the TGCEB is to Natural park and Halong Bay World Heritage.
carefully consider environmental aspects in the − Conserving and developing mangrove forest ecosys-
Master Economic Development Plan as well as in tem with specific measures of reasonably exploiting
each project in each area or ecological economic mangrove forest resources, reforesting, establishing
zone. mangrove forest conservation area, settling socio-
It is very necessary to carefully review the devel- economic problems in mangrove forest areas.
opment plan for the TGCEB on the point of view − Sustainably conserving and developing coral,
of integrating economic development into environ- protecting ecosystems in coastal and river mouth
mental protection before approval by the GOV. areas.
Based on the predicted environmental impacts − Preventing impacts of climate change.
(Chapter III in SEA Report) created by the plan
implementation by the year 2020 (Chapter I) and
according to the orientation of integration of eco- 3.3 Establishing and operating environmental
nomic development into coastal environmental monitoring system in the TGCEB
protection, strong points and weak points of this
Environmental monitoring system is to achieve 3
plan should be analyzed. Various items of the plan
main objectives:
should be re-checked and adjusted.
With above mentioned assessments, this SEA i. To evaluate the change in environmental qual-
report has preliminarily identified some “development ity, including physical, chemical, biological

14
compositions in scale of the whole area with ii. Biological resources will be reduced rapidly
focuses on areas of highly dense industry, pop- because of the extension of industrial parks,
ulation and natural conservation zones. urban areas and tourism zones. The natural
ii. To assess actual state and forecast environmen- forest areas will be decreased, consequently,
tal pollution due to production activities, life coastal and marine pollution will be increased;
activities through physico-chemical, biological biodiversity will be decreased; coastal erosion
parameters and environmental quality indexes. will be a problem and impacts of climate change
iii. To collect, store data on the change in envi- would be more significant. These impacts are
ronmental compositions, serving to assess expected as significant and large-scale but they
environmental impacts caused by projects, can be mitigated by proper management and
socio-economic development plan and envi- technological measures.
ronmental management; acting as scientific iii. For minimizing the negative impacts on the
foundation in cooperation between provinces coastal natural environment, it is necessary for
in the region with provinces/cities in the Red MPI, provincial People’s Committees, relevant
River Delta and international cooperation ministries, agencies and investors to reconsider
with China in environmental protection in the and adjust various projects in the Master Plan,
whole area. particularly the location, area of industrial
parks, industrial sectors, ports, airport etc.
Among them, environmental compositions need
Some planned projects should be rejected, if
to be monitored are:
they may not high economic benefits but cause
− Water environment (water chemistry, biology major environmental impacts.
and hydrology); iv. For mitigating the impacts (partly, not all),
− Air quality (physico-chemistry and the SEA report outlines basic orientations on
microclimate); environmental management and environmen-
− Soil pollution (physico-chemistry and tal technology which may serve as reference for
microorganism); MPI and relevant ministries and agencies.
− Solid waste (amount and composition);
Summary on negative impacts and solutions to
− Biological diversity (numbers of species, density
mitigate the adverse impacts by the development
and area of habitats).
projects in the Master Plan for the Coastal Tonkin
Frequency, parameters and monitoring sites Gulf Economic Belt is mentioned in SEA report.
of the monitoring systems are identified in SEA
report [5].
REFERENCES

4 CONCLUSIONS AND SUGGESTIONS Barker, A. 2000. SEA—A tool for integration within
coastal planning. Journal of Coastal Research, 22 (4).
From the results of the prediction and evaluation Decree N09/NQ/TW dated 9 February 2007 on Vietnam
of environmental impacts, in cases of lack of effec- Sea Strategy toward 2020. Hanoi.
MPI. 2008. Report on Socio-Economic Master Plan for
tive measures in environmental management it is the Tonkin Gulf Coastal Economic Belt (TGCEB).
possible to give some conclusions: Ministry of Planning and Investment, Hanoi.
i. The level of coastal and marine environmen- Partidario, M.R., Lobos, V. 2009. SEA of the national
tal pollution would be risen during the Master strategy for integrated coastal zone management in
Portugal. Journal of Coastal Research.
Plan implementation. The increased polluted UNNEP. 1995. Guideline for Integrated Management
environment will affect fishery resources, tour- of Coastal and Marine Areas. Regional Sea Report
ism, natural reserves and public health. The N161, Split, Croatia.
main affected areas include bays of Halong, VESDEC. 2008. Report of SEA for the Socio-Economic
Baitulong, coastal areas of Campha, Damha, Master Plan for the Tonkin Gulf Coastal Economic
Haiha, Yenhung, Thuynguyen, Haian, Doson Belt (TGCEB). Prepared for SEMLA/MONRE,
districts and Catba Natural Park. VESDEC, HCMC.

15
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Metabolomics: A challenging research tool in biotic matrices


characterization

J. Hajslova, M. Stranska & J. Pulkrabova


Department of Food Analysis and Nutrition, University of Chemistry and Technology,
Prague, Czech Republic

T. Ruml
Department of Biochemistry and Microbiology, University of Chemistry and Technology,
Prague, Czech Republic

ABSTRACT: In this presentation, metabolomics, a comprehensive study of small molecules, is presented


as an effective tool for biotic matrices research. The metabolomics study workflow including the major
instrumental strategies represented by Nuclear Magnetic Resonance (NMR) and Mass Spectrometry
(MS) are introduced. As an example of metabolomics application, bioprospection of microalgae is briefly
described. In summary, the potential of metabolomics in various application area is outlined.

1 INTRODUCTION

What is metabolomics?
In the recent decade, ‘omics’ based technologies
have become an important research tool in envi-
ronmental, agricultural and food science, as well
as in medicine, pharmacology and many other
disciplines. In Figure 1, the hierarchy of ‘omics’ is
illustrated.
Metabolomics, is defined as a comprehensive
analysis of endogenous and exogenous low molec-
ular weight compounds (up to aprox. 1500 Da) Figure 1. Hierarchy of ‘omics’.
occurring within a cell, tissue, or biofluid of living
organisms at given time point. The plant kingdom, sample should be isolated and recorded without any
thanks to a very large number of genes, is particu- (intended) bias. The targeted approach is mainly
larly biochemically rich in comparison with many used when specific group of metabolites is of inter-
other species. It is estimated that there are around est, in this way ‘metabolic profile’, is obtained.
200,000 metabolites, and somewhere between 7,000 The experimental design of metabolomics study
and 15,000 within an individual plant species; con- is of paramount importance. Therefore, it is essen-
trary to that, in humans, there are thought to be tial to prepare it carefully, the purpose of study has
around 3,000 endogenous or common metabolites. to be considered. In any case, one has to make sure
Worth to notice, that the metabolome is inherently that the sample collected reflect and represent the
very dynamic: small molecules are continuously biology or any other parameter in question. For
absorbed, synthetized, degraded and interact with instance in case of foodstuffs, not only metabo-
other molecules, both within and between biologi- lites present in a raw material of plant or animal
cal systems, and with the external environment. origin, but also secondary products originated
under processing/storage conditions are a part of a
characteristic fingerprint or profile. Similarly, this
Strategies employed in metabolomics-based studies
applies for various additives, residues, contami-
Two main approaches can be used in metabo- nants or even adulterants. The typical workflow of
lomic studies. When employing untargeted (global) metabolomics study is shown in Figure 2.
approach to obtain ‘metabolic fingerprints’, then as A wide range of instrumental techniques has been
many as possible metabolites occurring in respective used for analysis of samples within metabolomics

17
Table 1. Application potential of NMR and Mass
Spectrometry (MS).

Figure 2. Generic metabolomics workflow.


resources and commercialization of new products
studies, among them mass Nuclear Magnetic based on them, has become recently, thanks to
Resonance (NMR) and Mass Spectrometry (MS) developments of modern laboratory technologies,
are clearly best suited, and, in some respect, the a subjects of intensive research.
application potential of these techniques is comple- In the first phase, non-selective extraction
mentary, see Table 1. Regarding the MS, nowadays, avoiding discrimination of any metabolite present
advanced tandem (MS/MS) high resolution time in examined matrix has to be found. In the next
of flight (HR TOF) or orbitrap mass analyzers are phase, unique metabolites are searched in obtained
widely used, thanks to the high selectivity and good extracts or fractions thereof, employing combina-
sensitivity. Various formats of HRMS/MS can be tion of bioactivity testing (an array of cellular and
employed including direct infusion and ambient biochemical tests is commonly used) and structure
MS, nevertheless, hyphenated platforms coupling identification enabled by modern instrumental
on-line either Gas Chromatography (GC) or Liq- technologies.
uid Chromatography (LC) with MS are employed
for characterization of complex matrices.
Case study: microalgae classification
When performing untargeted LC-MS analysis
of large sample set, typically voluminous data are Microalgae represent a group of microscopic pho-
acquired. Advanced chemometric methods have to tosynthetic organisms capable of converting the
be used for their processing. Unsupervised classi- solar energy into biomass. Large-scale biotechno-
fication can be achieved through observing score logical cultivations have begun to develop in the
clustering patterns in the latent space of a single middle of the last century, leading to numerous
Principal Component Analysis (PCA), which is commercial applications. Additionally to uses of
commonly employed in the first phase, as a dimen- microalgae for waste-water treatment, aquacul-
sional reduction technique. Samples clustering in ture sustainability, bio-fuel or feed production,
the measured data can be detected based on linear some strains can be exploited also for an occur-
combinations of their shared features. In the next rence of health-promoting metabolites that can
phase, discriminant models (supervised models) are be used as components of dietary supplements
created based on building the models for the known or cosmetics. Currently, one of the most com-
classes. For example, Linear Discriminant Analysis monly employed microalgae for these purposes
(LDA), Partial Least Discriminant Analysis (PLS- are Spirulina sp., cyanobacteria containing phy-
DA) or Orthogonal Partial Least Discriminant cobiliproteins with many positive health effects
Analysis (OPLS-DA) have often been performed (i.e., antioxidant and anti-inflammatory, hypo-
for statistical models validation in order to find dif- cholesterolemic or even anti-cancer), Chlorella
ferences between the known sample groups. sp., microalgae containing large number of anti-
oxidants and proteins, the other examples are
Dunaliella, Haematococcus and Scenedesmus
Bioprospecting—example of metabolomics
sp., microalgae containing high concentrations
application
of antioxidative carotenoids (e.g., lutein, astax-
Bioprospecting, the process of discovery of anthin, zeaxanthin, lycopene or beta-carotene);
‘new’ bioactive molecules occurring in biological recently, Trachydiscus minutus containing high

18
amounts of ‘healthy’ omega unsaturated fatty 2 SUMMARY
acids, has been subject of investigation.
In our study, a number a large set of microalgae − Metabolomics enables the large-scale study of
has been investigated. The generic extraction pro- small molecules (metabolites) occurring within
cedure we have developed is shown in Figure 3. cells, tissues or organisms. Small molecules
Metabolite fractions were subsequently isolated originated under various conditions in biotic
according to their decreasing polarity (solid resi- matrices (e.g. during food processing) can be
due remained after centrifugation was used for investigated, too.
extraction in step 2 and 3). To monitor extraction − Applications of metabolomics are found within
efficiency, internal standard with Kow value corre- the pharmaceutical, healthcare, agricultural and
sponding to respective fraction was added. food industries, among others. In environmental
The extracts obtained in individual extraction research the impact of various stressors can be
steps were fingerprinted using reversed phase (C18 detected.
silica column) and Ultra-High Performance Liquid − In control laboratories, metabolomics may help
Chromatography (UHPLC) coupled to High Reso- to detect various types of fraud, supposing clas-
lution Mass Spectrometry (HRMS). Specialized sification models constructed on authentic sam-
chemometric software was used for data processing. ples are available.
The results are shown in Figure 4. Clear clustering − There are two main approaches used in metabo-
of tested species based on metabolomics fingerprints lomic studies: untargeted (global) and targeted
was obtained thus documenting then potential of (specific).
this approach to classify biotic samples. Ongoing − Careful planning and design of experiments is
research is focused on identification of individual extremely important in metabolomic studies.
groups of markers. Measurement of bioactivities − Nuclear Magnetic Resonance (NMR) and Mass
associated with individual fractions is also planned. Spectrometry (MS) are two of the most com-
monly used analytical methods in metabolomic
studies.
− Multivariate statistical analysis enables effec-
tive classification of samples and biomarkers
identification.

ACKNOWLEDGEMENTS

The study is supported by the Technology Agency


of the Czech Republic (project No TE01020080).
The “National Program of Sustainability” (NPU I
(LO1215) MSMT-34870/2013) and NAZV (project
No QJ1530272) are also gratefully acknowledged.

Figure 3. Generic extraction procedure for a metabo-


lomic study on algae. REFERENCES

Lankadurai, B.P., Nagato, E.G., Simpson, M.J. 2013.


Environmental metabolomics: an emerging approach
to study organism responses to environmental stres-
sors. Environmental reviews 21: 180–205.
Rubert, J., Zachariasova, M., Hajslova, J. 2015. Advances
in high-resolution mass spectrometry based on metab-
olomics studies for food—a review. Food Additives &
Contaminants: Part A. 32: 1685–1708.
Stranska-Zachariasova, M., Kastanek, P., Dzuman, Z.,
Rubert, J., Godula, M., Hajslova, J. 2016. Bioprospect-
ing of microalgae: Proper extraction followed by high
performance liquid chromatographic–high resolution
mass spectrometric fingerprinting as key tools for suc-
cessful metabolom characterization. J. Chromatogr.
Figure 4. Chemometric analysis (DA-PCA) of algae B 1015–1016: 22–33.
metabolomic fingerprints.

19
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Methodology for screening of HIV inhibitors applicable for in silico


designed molecules and empirical testing of traditional medicinal
materials

M. Rumlová
Faculty of Food and Biochemical Technology, University of Chemistry and Technology, Prague,
Czech Republic
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,
Prague, Czech Republic

V. Spiwok & T. Ruml


Faculty of Food and Biochemical Technology, University of Chemistry and Technology, Prague,
Czech Republic

R. Hadravová
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,
Prague, Czech Republic

ABSTRACT: Nature provides immense variety of biologically active compounds. The beneficial effects
of biological materials for humans are well recognized in traditional medicine. However, most of them are
still poorly characterized despite immense effort of numerous laboratories. This is in some extent caused
also by a quest to identify single compound rather than focusing on synergistic effect of more compounds
present in the material either of plant or animal origin. A need for new inhibitors preferentially of natural
origin is well justified also for viruses. This is especially true for those viruses that copy genomic material
with a low fidelity. This results in continuous emergence of high numbers of drug-resistant viral mutants
including those of HIV. In the search for compounds potentially inhibiting HIV, we have recently devel-
oped a fluorescent high-throughput assay for screening the inhibitors of assembly of the virus (named
FAITH—Fast Assembly Inhibitor Test for HIV) Hadravová et al. (2015). The method was validated using
previously reported assembly inhibitors and was shown to be very sensitive and reliable as it provides
minimum of false results, as confirmed by electron microscopy. We summarize here the principle and
basic protocol of FAITH and we present its application for screening of inhibitors acting in two pos-
sible modes. Both of them are essential for complete retrovirus life cycle and thus their inhibition might
block virus infectivity; by inhibiting either the assembly of immature particle or disassembly of mature
virus core. Based on recently published detailed HIV-1structure, we designed in silico several compounds
presumptively binding to selected interaction interfaces within hexagonal lattice of virus particle. Interest-
ingly, some of the compounds accelerated the assembly, instead of blocking it. This suggests that these
compounds bind with a high affinity without preventing the particle formation and thus might block the
disassembly of the particle rather than its assembly. As the disassembly is another key step in the virus life
cycle, we are currently optimizing the method for screening of the compounds inhibiting the disassembly
of the virus core. The method is now being adapted also for other viral species. Both the assembly and
disassembly screening methods are applicable also for a non-targeted empirical screening of inhibiting
activities of compounds present in biological extracts; preferentially those used in traditional medicine
against viral infections. Extremely interesting would be extracts with combined inhibitory activity against
HIV and microbial pathogens. These would target not only the primary cause of AIDS but also the micro-
organisms causing opportunistic infections in AIDS patients.

Keywords: HIV, inhibitor, screening, assembly, uncoating

21
1 INTRODUCTION to CA. This indicates that the CA domain of Gag
may be a suitable drug target. Despite these posi-
There have been developed numerous methods tive results, no effective inhibitor of HIV assembly
for screening of medicinally relevant activities is currently on the market.
of molecules and their mixtures. In contrast to We and others have demonstrated that the
relatively straightforward testing of inhibitors of assembly of both immature retrovirus-like particle
various prokaryotic and eukaryotic microorgan- and a mature retroviral core occurs in vitro from
isms, testing of antiviral activities is usually more recombinant Gag-derived proteins Campbell &
time consuming, laborious and expensive due to Vogt (1995), Campbell & Rein (1999), Ehrlich et al.
the requirement to cultivate the viruses in mam- (1992), Gross et al. (1997), Gross et al. (2000),
malian host cells before subsequent analysis of Klikova et al. (1995), Rumlová-Kliková et al.
virus replication. Therefore, more simple methods (2000), Hadravová et al. (2012), Bohmová et al.
focusing on discrete steps of virus life cycle are (2010). HIV-1 Gag and its truncated versions form
preferred for a primary screening. These include either tubular structures of a mature-like arrange-
inhibition of nucleic acids polymerases that medi- ment of CA domain Campbell & Vogt (1995),
ate replication of virus genome or inhibition of Ehrlich et al. (1992), Gross et al. (1997), Ganser
other key enzymes required for virus formation, as et al. (1999), Gross et al. (1998), Li et al. (2000),
viral proteases that cleave virus polyprotein pre- von Schwedler et al. (1998), Bharat et al. (2014) or
cursors to the mature proteins of virus particle. spherical immature-like structures von Schwedler
For some viruses, a combination therapy based on et al. (1998), Bharat et al. (2014), Blair et al. 2010).
simultaneous administration of several drugs is Besides some cell-based methods determining
needed. This is especially true for the viruses car- the HIV-1 released from the infected cells and its
rying RNA genome which is replicated by error- ability to infect new cells, several HIV inhibitors
prone RNA polymerases. Resulting virus mutants, screening assays based on the in vitro assembly
capable of replication under selection pressure of HIV-1 Gag were published: the turbidimet-
imposed by the presence of inhibitors, represent ric method for the quantitative determination of
a major threat and may lead to therapy failure. the HIV-1 CA assembly rate Lanman & Prevelige
Therefore current therapeutic approach against (2005) and the immobilized HIV-1 CA assembly
HIV-1 mainly relies on a combination of drugs assay Lemke et al. (2012). However, all the previ-
inhibiting viral enzymes i.e. reverse transcriptase, ously described methods suffered from that fact
protease and integrase. The “Highly Active that they include washing steps, which complicate
Antiretroviral Therapy (HAART)” surely deserves the high-throughput assay. Some also work in high
its name and provides satisfactory results; how- salt i.e. at non-physiological conditions that might
ever there is continuing request for new molecules affect interactions mediating the assembly and
that might help to minimize the tolerance if the binding of the inhibitors.
virus and the appearance of immense amounts of We have recently developed a method over-
drug-resistant mutants. coming these problems Hadravová et al. (2015).
Like in other retroviruses, the life cycle of HIV-1 It is based on in vitro measurement of efficiency
consists of two separated steps. In the first, the of assembly either of spherical or tubular HIV-1
precursor of structural proteins, Gag polyprotein particles consisting from purified truncated
assembles at the plasma membrane to create spher- Gag proteins mimicking either the immature or
ical immature particle that later buds from the mature-like particles, respectively. This method
cell. HIV protease is activated prior to or simul- was validated Hadravová et al. (2015) using pre-
taneously with the process of budding. Specific viously published inhibitors of HIV-1 assembly:
proteolytic cleavage of Gag then yields structural BM2 (Lemke et al., 2012), CAI (Sticht et al.,
proteins matrix MA, Capsid (CA), and Nucleo- 2005), PF-074 (Blair et al., 2010). Among the
Capsid (NC) that re-assemble to form differently major advantages of our method belong: the per-
arranged mature hexagonal lattice of infectious formance of all procedures at physiological condi-
virus. In the mature virus, MA remains bound tions, high sensitivity, fastness and simplicity (no
to the viral lipid envelope, while CA condensates washing steps are needed). The method was used
into a conical core protecting ribonucleoprotein for testing of activity of several in silico designed
complex of NC and the viral genomic RNA. Both inhibitors. Surprisingly, we have found that some
mentioned assembly processes resulting firstly in of the tested compounds facilitated the assembly
creation of the immature particle and then of the rather than blocking it. We are currently develop-
mature core are indispensable steps in the forma- ing the alternative method for screening inhibitors
tion of infectious virus and their blocking would of uncoating of the genomic RNA, which should
inhibit the infectivity. Intensive HIV research effort prevent the early step of the life cycle preceding
resulted in design of several compounds binding the reverse transcription.

22
2 MATERIALS AND METHODS molecules, 8 sodium cations) and its geometry was
optimized. All 2 ns simulations used a harmonic
2.1 Constructs preparation and protein production restraints applied on five selected atoms in each
monomer to mimic their embedding in the capsid.
Construction of expression vectors for HIV-1
The structure after 10, 20, 30 and 40 ns was used as
Gag derived assembly competent domains pro-
a target for docking. The possible binding site was
viding either immature or mature-like particles
chosen by combination of druggability predictions
i.e. ΔMACANCSP2 or CANC, respectively was
(program fpocket), published data on mutations
described previously Hadravová et al. (2015).
destabilizing capsid assembly and visual inspec-
The HIV-1 proteins were also produced and puri-
tion. The pocket was used for virtual screening by
fied E. coli BL21 (DE3) as published previously
program Plants. Maybridge libraries were obtained
Campbell & Vogt (1995), Ulbrich et al. (2006).
from Zinc database. Binding site was defined by
visual inspection of the site as a sphere of diameter
2.2 Assembly 11 Å. ChemPLP scoring function was used. Dock-
ing speed was 1 (highest accuracy). Docking scores
Isolated HIV-1 CANC or ΔMACANCSP2 protein of compounds highly correlated between vir-
in the storage buffer (20 mM Tris-HCl, pH 8.0, tual screenings to structures after 10–40 ns. Top
0.5 M NaCl, 50 μM ZnCl2, 10 mM DTT, 1 mM 20 scoring compounds were selected from each
PMSF) was diluted by the assembly buffer (50 mM virtual screening and partial overlap was found (up
Tris-HCl, pH 8.0, 100 mM NaCl, 1 μM ZnCl2) in to 4 structures were common to two groups; two
96-well plate providing final 300 mM NaCl concen- structures were common to three groups).
tration. After the dilution, the 40-meric OligoNu-
cleotide (ON) was added (Fig. 1B) and the mixture
was incubated for 3 h at room temperature.
3 RESULTS

2.3 Measurement of inhibitory efficiency 3.1 In vitro assembly of HIV-1 particles


The inhibitors were added to the HIV CANC or Retroviral life cycle including that of HIV requires
ΔMACANCSP2 protein and the procedure con- subsequent formation of two types of particles in
tinued as described above. The samples were then the infected cell i.e. immature particles consisting
diluted to the concentration of NaCl 0.3 M, CANC of polyprotein precursors and mature ones con-
protein 18 μM (60 μg/100 μl), and ΔMACANCSP2 taining viral genome inside the core. The interac-
protein 15 μM (60 μg/100 μl), ON was added and tions stabilizing the immature and mature viruses
the incubation was carried on for three hours are very distinct Bharat et al. (2012), Schur et al.
at room temperature. To the reaction mixtures (2015) and blocking either of them would inhibit
(100 μl) in the 96-well plate, were added 20 U/μl of the virus infectivity. Our screening method there-
Exonuclease 1 (NEB) and MgCl2, to a final con- fore targets the assembly of both assembly types
centration of 6.7 mM. Then fluorescence at 517 nm depending on the Gag-derived protein used
was immediately recorded for 120 minutes. The in reaction. The HIV-1 spherical particles are
excitation and emission wavelengths corresponded
to 495 nm and 517 nm, respectively.
Children Children Children
2.4 Transmission Electron Microscopy (TEM)
of assembled particles
The shape of negatively stained (2% phospho-
tungstic acid, pH 7.4) particles was determined
by transmission electron microscopy (JEOL JEM- Children
1200EX operated at 60 kV).

2.5 In silico design of inhibitors


The structure of HIV capsid protein was fitted into
Figure 1. Method principle. A—non-inhibited assem-
the electron density map EMD-2706; 200 minimi- bly, labelled oligonucleotide is protected within the
zation steps and 0.5 ns Molecular Dynamics Flexi- assembled viral particle and is not cleaved by DNAse, no
ble Fitting (MDFF) simulation in vacuum. The fluorescence occurs, B—inhibited assembly, from free,
EMD-2706 was used to restrain the protein. The unprotected labelled oligonucleotide is raised fluoro-
final structure was then solvated (37,974 water phore, which produce positive signal.

23
et al. (2014), Ulbrich et al. (2006). The use of the
in vitro system is justified by the cryo-EM study
that confirmed identical organization of HIV-1
ΔMACANCSP2 spherical particles with the imma-
ture HIV Ulbrich et al. (2006).
The quantification of the assembly yield is based
on the fact that it occurs only when nucleic acid is
incorporated into the resulting particles (Fig. 1).
The residual non-incorporated single-stranded
DNA OligoNucleotide (ON) is then quantified.
For this, we used with a reporter dye—fluorescein
(FAM) attached at the ON 3´ terminus and a
quencher molecule—Black Hole Quencher (BHQ)
attached at another nucleotide (Fig. 1G). The
quencher blocks the fluorescence emission unless
it is released from the reporter due to DNA deg-
radation. The fluorescence is thus recorded only
from free (unprotected) ON prone to exonuclease
degradation. In contrast, the ON molecules incor-
porated into the assembled particles are shielded
by a protein shell against the cleavage and thus
cannot emit any fluorescence. Therefore, the capa-
bility of compounds to block the HIV-1 assembly
can be easily quantified. Importantly, none parti-
cles assembled in the control samples of CANC or
ΔMACANCSP2 proteins lacking the nucleic acid
(data not shown). TEM of negatively stained par-
ticles correlated well with the fluorescence meas-
urements and confirmed the formation of tubular
or spherical structures only in the samples contain-
ing CANC+ON (Fig. 2A) or ΔMACANCSP2+ON
(Fig. 2B), respectively. Either of the proteins does
not assemble and only aggregates in the absence
of ON and only aggregates are observed by TEM
(Fig. 2C).

3.2 Verification of the method


The assay was validated using previously pub-
lished (by Sticht et al., 1998) assembly inhibitors
peptide CAI (Fig. 2C) and inactive peptide deriva-
tive CAIctrl Bharat et al. (2014). The lines in Fig. 3
demonstrate kinetics of degradation of ON by
DNAse in the controls and in the in vitro assem-
Figure 2. TEM analysis of in vitro of assembled HIV-1 bled CANC in presence of the active inhibitor. As
Gag derived domains. A—particles with mature arrange- expected, the addition of the inactive inhibitor to
ment of protein subunit CANC, B—particles with imma- the CANC+ON did not affect the assembly as the
ture arrangement of protein subunit ΔMACANCSP2, emitted fluorescence time curve was almost iden-
C—CANC sample assembled in the presence of CAI tical with that obtained for the control sample
inhibitor or in the absence of ON.
i.e. CANC+ON (Fig. 3; symbols and , respec-
tively). In contrast, an equimolar concentration
of CAI with CANC+ON efficiently inhibited the
assembled in vitro immature-like arrays from trun- formation of the particles triggering a fluores-
cated Gag proteins (ΔMACANCSP2) Gross et al. cence signal comparable to that of free ON control
(2000), while tubular particles (from CANC or CA (Fig. 3, symbols and , respectively). The same
domains of Gag) adopt the mature-like arrange- trend was observed for the model of immature
ment Campbell & Vogt (1995), Ehrlich et al. HIV assembly, i.e. ΔMACANCSP2 protein. TEM
(1992), Gross et al. (1997), Li et al. (2000), Bharat analyses confirmed that CAIctrl did not prevent

24
Children

Children

Children

Children Children
Figure 3. Quantification of in vitro assembly of
HIV-1 CANC.

efficient assembly of the ΔMACANCSP2 or


CANC (data not shown because the particles mor-
phology was identical with those in Fig. 2, pan-
els A and B, respectively). In contrast, the active
CAI inhibitor blocked the assembly and only free
protein and small protein aggregates were present
(Fig 2C).

3.3 Rational design and testing of HIV-1


assembly inhibitors
Using structural data form recently published
detailed analysis of HIV-1 particle (Schur et al.,
2015), we employed in silico methods for dock-
ing small organic molecules into Gag interaction
interfaces interlinking the particle subunits in hex-
agonal lattice. Binding of the molecules into these
interfaces might thus block the interaction forces
essential for the virus assembly.
Visual inspection of the best ranking com-
pounds from screening of Maybridge library and
their binding poses revealed many “frequent hit-
ter” compounds. In order to select well scoring
and pharmacologically relevant compounds, we
visually inspected 20 scoring molecules in each
group (for an example see Fig. 4; compounds:
ZINC01043364: 2-[(5-{[(7-methyl-2,3-dihydro-
1H-inden-4-yl)oxy] methyl}-4-phenyl-4H-1,2,4- Figure 4. Example of predicted binding poses (left:
compound ZINC01043364 docked to the structure after
triazol-3-yl)thio]-1-(4-nitrophenyl)ethan-1-one
10 ns; right: compound ZINC02178970 docked to struc-
and ZINC02178970: 3-[(2-aminophenyl)sulfanyl]- ture after 30 ns).
1-[2-(benzyloxy)phenyl]-3-phenyl-1-propanone:
MFCD00829143). Selected candidate molecules
were purchased and their inhibitory activity was
tested in vitro. Unfortunately, none on the mole- the disassembly of the protein lattice, as the disas-
cules inhibited the assembly. However, surprisingly, sembly (so called uncoating) process is another key
some of the tested molecules exhibited completely event in formation of infectious HIV. The disinte-
opposite effect, i.e. they facilitated (accelerated) gration of the particle occurs twice in the HIV life
the assembly. This indicates that the molecules cycle. Firstly, during the virus maturation when the
enhanced mutual affinity of the Gag molecules in CA domain of Gag in the spherical immature par-
the virus protein lattice but did not interfere with ticle is liberated to rearrange into conical core of
the assembly process. Therefore, we are currently the mature virus. Secondly, the uncoating, occurs
developing the assay for testing the ability of the when the virus core releases viral genome for reverse
compounds to stabilize the particle and thus inhibit transcription. Thus compounds blocking either of

25
these steps would represent another class of potent for docking of the molecules was the strength of
inhibitors of HIV. their interaction with selected interfaces it is very
likely that their interactions might stabilize the
structure and thus not only facilitate the assembly
4 DISCUSSION but also hold the compact particle and this way
prevent the process of disassembly. Therefore our
We have explained above the reasons for the con- current effort is aims at optimization of the screen-
tinuing search for new HIV-1 inhibitors. The major ing assay focusing on the inhibitors of disassem-
problem in AIDS therapy is frequent occurrence bly and also on characterization of the molecules
of drug resistant strains. However, up to date, in respect of blocking the uncoating of the virus.
there is no assembly inhibitor available on the
market. Quite the opposite is true for easily moni-
tored inhibitors of HIV enzymes, i.e. reverse tran- ACKNOWLEDGEMENTS
scriptase, protease and integrase. In our opinion,
an effective high throughput screening method This work was supported by the Ministry of Edu-
might help to identify effective compounds inhibit- cation NPU I projects LO 1302, LO 1601 and LO
ing processes of assembly and uncoating of parti- 1304.
cles at various stages of the HIV life cycle.
One of published high-throughput screening
methods Lanman & Prevelige (2005) includes tur- REFERENCES
bidimetric determination of the kinetics of the
HIV-1 CA assembly. The main drawback of this Bharat T.A.M., Castillo Menendez L.R., Hagen W.J.H.,
method is that it requires high (non-physiological) Lux V., Igonet S., Schorb M., Schur F.K.M., Kräusslich
ionic strength that could affect CA interactions H.G., Briggs J.A.G. 2014. Cryo-electron microscopy
and thus limit appropriateness of the assay. There of tubular arrays of HIV-1 Gag resolves structures
essential for immature virus assembly. Proceedings of
is available also a protocol for HTS of HIV-1 the National Academy of Sciences.
assembly inhibitors at physiological NaCl con- Bharat T.A., Davey N.E., Ulbrich P., Riches J.D.,
centration Lemke et al. (2005) that monitors the de MA., Rumlova M., Sachse C., Ruml T., Briggs J.A.
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However, this method suffers with a risk of false 487:385–389.
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The principal novelty of our method is that the Bohmová K., Hadravová R., Štokrová J., Tůma R.,
mere binding of the protein to the nucleic acid is Ruml T., Pichová I., Rumlová M. 2010. Effect of
does not protect ON against nucleases. This was Dimerizing Domains and Basic Residues on In Vitro
demonstrated by using the CAI inhibitor that effi- and In Vivo Assembly of Mason-Pfizer Monkey
ciently blocks the assembly but not the interactions Virus and Human Immunodeficiency Virus. J. Virol.
of ON with NC as proved by an electrophoresis 84:1977–1988.
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the method can be applied for the screening of two S.D. 2003. Structural organization of authentic, mature
HIV-1 virions and cores. EMBO J. 22:1707–1715.
principally different types of HIV assembly inhibi- Campbell S., Rein A. 1999. In vitro assembly properties
tors: i) those blocking protein-protein interac- of human immunodeficiency virus type 1 Gag protein
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interactions (between ON and NC). The modified Campbell S., Vogt V.M. 1995. Self-Assembly In-Vitro of
method will allow also testing the disassembly Purified Ca-Nc Proteins from Rous-Sarcoma Virus
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nation of anti HIV compounds. of recombinant human immunodeficiency virus type 1
capsid protein in vitro. J Virol. 66:4874–4883.
We demonstrate the applicability of the method Ganser B.K., Li S., Klishko V.Y., Finch J.T., Sundquist
for testing in silico designed molecules that were W.I. 1999. Assembly and analysis of conical models
fitted into the high resolution structure of HIV-1. for the HIV-1 core. Science. 283:80–83.
The result of the in vitro verification of activity of Gross I., Hohenberg H., Huckhagel C., Krausslich
the hits was unexpected, as the compounds rather H.G. 1998. N-terminal extension of human immu-
accelerated the assembly. However, as the criterion nodeficiency virus capsid protein converts the in vitro

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assembly phenotype from tubular to spherical parti- bind the same site within the N-terminal domain of
cles. Journal of Virology. 72:4798–4810. the viral CA protein. J Virol. 86:6643–6655.
Gross I., Hohenberg H., Krausslich H.G. 1997. In vitro Li S., Hill C.P., Sundquist W.I., Finch J.T. 2000. Image
assembly properties of purified bacterially expressed reconstructions of helical assemblies of the HIV-1 CA
capsid proteins of human immunodeficiency virus. protein. Nature. 407:409–413.
Eur J Biochem. 249:592–600. Rumlová-Kliková M., Hunter E., Nermut M.V.,
Gross I., Hohenberg H., Wilk T., Wiegers K., Pichová I., Ruml T. 2000. Analysis of Mason-Pfizer
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27
Environmental engineering
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Demonstration of an EFE-BROW model expost application


on brownfields sites

B. Vojvodíková, Š. Vilamová, A. Király & K. Chuchrová


VŠB—Technical University of Ostrava, Ostrava, Czech Republic

M. Piecha
Ministry of Industry and Trade, Prague, Czech Republic

K. Bařinka
Česká zbrojovka a.s., Uherský Brod, Czech Republic

ABSTRACT: This article is focused on the demonstration of the EFE-BROW assessment model
application to locations that were previously abandoned and unused—called brownfields, and today they
serve as industrial zones. The EFE-BROW model is targeted at the evaluation of development potential
for utilization of brownfield areas for commercial use, ideally of industrial zone type. Namely the ex post
application—which means application on sites that are no longer brownfields is a meaningful way to
verify the assessment method of the EFE-BROW model.

1 INTRODUCTION impassable conditions for success are correctly and


realistically set priorities of regional development.
Brownfields—abandoned, unused or underused Most brownfield areas—particularly in Eastern
areas that are losing or already have lost their are Europe require a definite degree of support from
part of the history of most cities. The reasons for public authorities (Smelík, 2015). Determining the
their emergence are different but in the past 20 realistic requirements for the scope, size, finan-
years, as stated by Ferber (2006), they are very cial limits and expected number of revitalized
often associated with the production restructur- brownfields, which are to be supported is one of
ing, with structural changes. Brownfields can not the crucial steps in getting the best possible ben-
be understood simply as the problem of the site efits for society in terms of the subsequent effects
itself, but it is necessary to perceive its negative in exchange for public funds investment. Bergatt-
effects on the environment, as stated in (Petriková, Jackson & Votoček. (2003). The EFE-BROW
2011). Votoček (2011) in his work describes the model is a tool supporting this crucial step.
gradual expansion of this negative phenomenon
from the industrial areas to their surroundings,
often accompanied with appearance of related 2 EFE-BROW MODEL INTRODUCTION
social brownfields.
Several authors have previously stated (for The aim of the EFE-BROW (effective brownfield)
example, Oliver (2003)) that there is no fixed defini- mode is to carry out an assessment of potential
tion of brownfields anchored in the valid EU laws. options for the future use of brownfield lands for
But addressing of this problem has already been commercial purposes. The model is designed to not
adopted by many countries, including the countries making difference between the commercial use of
of Eastern Europe, as Osman (2015) mentions. For B2B and B2C. B2B is the abbreviation of “Business
this article, and in general for creation of the EFE- to Business” (merchant → merchant), which means
BROW model the definition of brownfields was business relationship and communication between
chosen as it was published in (Ferber & Grimski, merchant subjects without any direct impact on
2002), which one the same authors used in prepar- the final consumer. B2C—“business to customer”
ing the outputs of the CABERNET network. refers to business relations between merchants
Finding ways on how to properly proceed and and end customers. Especially use in industry and
initiate all the stakeholders is a challenging activity logistics is considered for commercial use. Areas
as described by Rizzo (2015) but one of the are not assessed here from the viewpoint of effec-

31
tive utilization for development housing projects, The criteria of the second degree are not exclud-
but allows for assessment for administration, IT ing, but just warning criteria—if any of the listed
companies and so on. situations is detected, the overall assessment cannot
Explanation what brownfield areas are and how continue without the assessment of specific use.
they are defined was described in the introduc- Second level criteria:
tory part of this article. The EFE-BROW model
− infrastructure—water resource availability,
is designed for use in Czech regions namely the
− limits of the territory utilization—percentage of
Moravian-Silesian Region and the Usti Region in
utilization,
Czech Republic.
− utilization of surrounding areas.
These two regions have many features in com-
mon especially their industrial history and related In the evaluation part the site, which has passed
present problems. Currently they deal with a large first and second criteria (ie. there is no circum-
amount of locations that are brownfields, are stance that would cause the land has significant
unused underused, abandoned. They are a bur- barrier) is evaluated in terms of potential opportu-
den to the location, town and region. Both regions nities for commercial exploitation.
have over 800 such sites registered. Because these Table 1 lists all parts—the characteristics that
regions need support, and it is not realistic that are evaluated. Furthermore, the table shows the
the aid could be directed to all necessary areas, it
is necessary to pay attention to those sites which
are commercially attractive and can bring new Table 1. Assessment criteria in EFE-BROW model.
uses, new employment opportunities and the asso-
Population weight 3,8
ciated development of the regions in a relatively
increase PO1 10
short time (in the regeneration of brownfield we
decrease by 0% up to 0,5% PO2 8,7
are speaking about years).
decrease by > 0,5% up to 0,8% PO3 6,8
decrease by > 0,8% up to 1% PO4 5,2
decrease by > 1% up to 1,2% PO5 3,7
2.1 Description of the EFE-BROW model
decrease by more than 1,5% PO6 3,0
The EFE-BROW model is divided into two parts; Senior citizens (age 65 or more) weight 3,7
into the criterial part (first and second level crite- less than 0,5% PV1 10
ria) and into the evaluation part. Criterial part— up to 1,0% PV2 8,3
especially the first level criteria are closely tied to up to 1,5% PV3 7,0
the two regions and their application to another up to 2% PV4 5,0
region would require revision. The second level more than 2 PV5 3,3
criteria are closely related to Czech legislation and
their application outside Czech Republic would be Unemployment rate weight 4,7
difficult. less than 3.5% NZ1 9,7
up to 5,5% NZ2 10
The evaluation part is, however, universally con-
up to 7,5% NZ3 9,8
ceived and its application is more general, although
up to 9,5% NZ4 9,2
some thresholds for individual evaluation indica-
more than 9,5% NZ5 8,2
tors again reflect the situation in Czech Republic.
Scope of the article does not allow for a detailed Railway weight 6,8
description of individual criteria, their assessment on the site ZE1 8,6
methods, or their threshold values. Here only the cri- in the immediate vicinity ZE2 10
terion names are listed and in the application section in up to 0,5 km distance ZE3 8
of this article at least some values will be shown as a in distance over 0,5 km ZE4 5,5
part of model’s application to a specific location. Road weight 9,5
First level criteria are exclusionary criteria— the site is accessible by a road SI1 10,0
ie. when the site has certain criterion values, it is suitable for trucks.
excluded from further assessment. the site is accessible by a road SI2 6,3
First level criteria—listed in the order in which suitable for vans only
they are assessed—by their importance: the site is accessible by a road SI3 7,8
suitable for small cars only.
− ownership,
− area with risk of subsidence (as an impact of Highway weight 10,7
previous mining activities), highway or expressway OS1 10
− floodplains, 1st class road OS2 9,0
− urban plan function of the area. (Continued)

32
Table 1. (Continued). maximum number of points for each item. Also
weights of the individual characteristics are men-
Population weight 3,8 tioned in the table.
2nd class road OS3 5,8 Preparation of this part of the model was possi-
3rd class road OS4 3,5 ble to be divide into three stages. The first stage was
Higher class road distance weight 7,0 the definition of individual characteristics to be
2000 m VS1 10 evaluated. In the second stage, the individual char-
4000 m VS2 8,2 acteristics were divided into items—as can be seen
5000 m VS3 6,8 in table 1 And in the third stage, the panel of experts
more VS4 4,2 evaluated the items in terms of the significance of
Common water supply weight 13,7 each item within the characteristic by assigning a
no water system in the VO1 3,0 point value from 1–10 scale. The panel of experts
municipality also assigned a weight to each of the characteris-
water system available in VO2 10 tics. The points scale and weights were subsequently
distance recalculated. Scope of the article does not allow to
up to 100 m describe in detail the way how the recalculation was
water system available in VO3 8,0 carried out. In total, the evaluation can assign a
distance maximum of 1000 points (Kozel, 2015).
up to 500 m
up to 1 km VO4 5,5
water system available in VO5 3,8 3 EX POST EVALUATION
distance
over 1 km In order to get status of locality suitable for busi-
Sewers weight 9,5 ness the boundary was set to 800 points. Evalu-
no sewer system in the KA1 4,2 ation was conducted using application of the
municipality assessment to few already revitalized locations,
sewer system available in KA2 10,0 based on their characteristics valid when the revi-
distance talization just started. This article focuses on sites
up to 500 m in the Moravian Silesian region. Below are three
sewer system available KA3 8,0 selected sample localities which used to be indus-
in distance up to 1000 m trial brownfields and which have found a new utili-
sewer system available in KA4 6,3 zation as an industrial zone.
distance These three localities used to host various kinds
up to 2 km of industrial production. All three of them under-
sewer system available in distance KA5 5,0 went revitalization and as of today they are fully or
over 2 km at least partially utilized. Two of them are located in
Environmental protection weight 10,5 Ostrava, the third one is located in Horni Sucha.
Natura 2000 OP1 1,0 The localities are:
National park OP2 1,2 − Nad Porubkou site,—urban area of Ostrava—
CHKO (protected landscape area) OP3 2,0 Poruba—size 14 ha,
natural reserve OP4 2,0
− CEMOS site—urban area of Ostrava Kunčičky—
no protection OP5 10
size 13.5 ha,
Utilizable area weight 11,3 − Coal mine Frantisek—urban area of Horní
90% or more VY1 10 Suchá.—size 15 ha.
70% or more VY2 8,2
50% or more VY3 5,8
50% or more VY4 3,0 3.1 Brief history and description of evaluated
Buildings weight 8,8
sites
no buildings OB1 10 Nad Porubkou site is located in the municipal dis-
buildings requiring small OB2 7,8 trict of Ostrava Poruba. Ostrava is the third largest
reconstruction city in Czech Republic and it is a centre and capital
buildings in need of bigger OB3 3,0 of Moravian Silesian region. The first study on the
reconstruction due to technical possible new use of the area began to emerge in
shape 2001 and 2002. In 2003 the Poruba council received
buildings to be demolished OB4 5,2 a grant of about 23 million crowns from the State
100,0 Environmental Fund for the elimination of illegal
dumps, self-seeded trees and soil decontamination.

33
Projekt called The regeneration of Nad Porubkou
site was chosen by CzechInvest agency as a pilot
project for the redevelopment of former industrial
sites. Transport-service networks and utilities were
built on the site. The whole zone preparation costs
were about 60 million crowns, most of the funding
the council received from European Union funds
and grants from the Treasury. The first investor
utilized the site in 2007. (ČTK, 2007)
Out of 14 hectares of the industrial zone, in
total 13 hectares are occupied now. Potential inves-
tors are sought mainly by administration of the
Ostrava-Poruba municipal district. (Statutármí
město Ostrava, 2015)
CEMOS site, today Business Park
Ostrava—Kunčičky
Figure 2. Industrial zone František in 2012 (Photo: B.
Another example of brownfield reuse is a Vojvodiková).
former area of CEMOS Inc. industrial com-
pany, which is located in the eastern part of the
Ostrava—Kunčičky municipal district between struction of the administrative building for about
Lihovarská and Vratimovská streets. The new con- CZK 20 million was carried out from 2006 to 2007
struction has started in 2013. (Moravskoslezsko, with the help of subsidies from the Operational
2014). Currently there is the first of seven planned Programme Industry and Business. In 2007–2008
production, logistics, warehouse or wholesale halls a new production hall. Construction cost approxi-
in use. And few more are under construction close mately CZK 40 mil., of which 20.6 milions CZK
to completion. An important role in the revitaliza- were provided from EU structural funds, 6.8 mil-
tion of this brownfield site played the use of the ions CZK from the State budget (Operational Pro-
JESSICA financial instrument. In 2016, there are gramme Industry and Business) and 12.6 millions
local headquarters of several major companies— CZK were taken from the Horni Sucha municipal-
Figure. 1. ity budget. In 2010, the industrial zone was offi-
The municipality Horni Sucha is located in cially opened. At present it hosts about 20 business
Ostrava—Karvina agglomeration, about 12 km far subjects. See Figure. 2
from Ostrava—the regional capital. It extends on
the area of about 10 km2 and has a population of
4,500. The area of interest is the area of the former 4 APPLICATION TO THE THREE
Frantisek mine, which is located on the northern SELECTED SITES
boundary of the village and which is approxi-
mately 15 ha in size. The transfer of ownership The assessment was done by individual steps of the
to the village was made in February 2005. Recon- model. It was an ex-post evaluation, i.e. the sites
were evaluated which have already been successful,
but the date which the assessment was related to
varied according to the start date of revitalization
implementation. For the Nad Porubkou area the
assessment was done over the state as of 2007, for
CEMOS site the state as of 2013, and for the mine
Frantisek site as of 2006.

First level criteria


Application of the questions can see in Table 2.
Good answer, indicates positive situation of sites,
can see in last column in Table 2.
Out of the second level criteria only the avail-
ability of drinking water is important, as there was
no problem indicated in the total utilizability of
the site and the surrounding areas of the sites do
not represent any problem or barrier for the new
Figure 1. Business Park Ostrava—Kunčičky autumn use of the sites. That’s why those other criteria are
2015 (Photo: P. Vavrinová). not detailed here. In the third step of the ex post

34
Table 2. Application first step of EFE-BROW model to selected localities.

Nad Porubkou CEMOS František Positive answer

Is the owner known? Yes Yes Yes Yes


Is there a risk of negative effect related to No Yes Yes Yes
(former) mining activities?
Is the area in construction group 1 or 2? – No No No
(Standard ČSN 73 0039 )
Is the are designated for housing or agricul- No No No No
tural use in the urban plan?
Floodplains? No No No No

Table 3. Application of third step of EFE-BROW model.

Nad Porubkou CEMOSs František

Population 33,35 26,1 38,3


Senior citizens 36,7 36,7 36,7
Unemployment rate 3,9 38,3 38,3
Railway 37,6 37,6 54,7
Road 95 95 95
Highway 106,7 106,7 96,0
Higher class road distance 57,4 57,4 70
Common water supply 109,3 109,3 109,3
Sewers 95,0 76,0 59,9
Environmental protection 105 105 105
Utilizable area 92,9 92,9 92,9
Buildings 45,9 47,1 57,4
SUM 828,7 828,0 853,5

application the evaluation by individual character- their thresholds set in relation to the present situa-
istics was carried out. Characteristics of individual tion in these regions.
sites are listed in Table 3. Application of ex post evaluation of brown-
The values achieved after including points fields presented in this paper demonstrates the
for items and multiplied by the weight of each applicability of the model in its target field and
characteristic. it can contribute to the efficient selection of sites
All three sites have reached the points score with higher priority of reuse so that the support of
greater than 800. i.e. values that are believed to brownfield regeneration and using them for com-
mark a site suitable for business purposes. mercial production would achieve maximal effi-
ciency of investments made.

5 CONCLUSIONS
ACKNOWLEDGEMENT
Assessment of the model EFE-BROW was con-
ducted using ex post evaluation—the sites were The article was supported by a specific university
retrospectively evaluated that had been success- research by Ministry of Education, Youth and
fully revitalized to use their territory for business. Sports of the Czech Republic No. SP2016/29 Crea-
EFE-BROW model is dominantly designed for use tion of a system for market analysis of industrial
in Moravian Silesias and Usti regions and for the enterprises.
needs of Czech Republic. Its applicability outside
the territory of the Czech Republic would meet a
problem with some specifics such as the standards REFERENCES
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36
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Heavy metal contamination of mine area and their uptake by plants


(Tailing pond Sedem Žien, Slovakia)

E. Remešicová & A. Király


Faculty of Mining and Geology, Institute of Environmental Engineering, VŠB—Technical University of Ostrava,
Ostrava, Czech Republic

P. Andráš
Faculty of Mining and Geology, Institute of Environmental Engineering, VŠB—Technical University of Ostrava,
Ostrava, Czech Republic
Faculty of Natural Sciences, Matej Bel University, Banská Bystrica, Slovakia

ABSTRACT: This article reports an environmental study concerning tailing pond Sedem Žien in
Central Slovakia. Heavy metal concentrations (Fe, Mn, Pb, Co, Cr, Cu, Ni, Zn) were measured in waters,
soils and plants of the tailing pond. Two drainage waters percolating tailing pond sediments were ana-
lysed (red coloured drainage and transparent drainage). Colour of the red drainage was caused by high
Fe content (9.63 mg.l−1) and the predominant metal in the transparent drainage was Pb (3.77 mg.l−1). Soils
contain high concentrations of all of the analysed metals, mainly Fe, Mn, Zn, Pb and Cu. Calculated Bio-
Concentration Factor (BCF) <1 showed that both of the analysed species (Pinus sylvestris, Quercus robur)
are excluders and are not suitable for phytoremediation purposes. The biggest uptake of heavy metals by
plants was observed in the soils with lowest pH value. Translocation factor reached the highest values for
Mn (up to 27.545).

1 INTRODUCTION and thereby limit the plant and animal lives.


Acidification of surface waters causes loss of
Studied area Sedem Žien tailing pond is character- bicarbonate needed for the photosynthesis. Large
ized by high abundance of sulphide minerals whose influxes of hydrogen ions disrupt the natural flow
oxidation causes the lowering of pH, releasing of of the neutralizing system and the bicarbonate is
heavy metals and Acid Mine Drainage (AMD) converted to carbonic acid and carbon dioxide.
production. Acidification depletes the soil of Ca On the contrary heavy metals become due to the
and Mg, mobilizes metals and reduces sorption low pH value and increasing mobility in aquatic
abilities of the humus horizon causing the gradual environment available to organisms. Acidic envi-
destruction (Šottník, 2005, Andráš et al., 2015b). ronment also contributes to the methylation of
The produced AMD may have chemical, physi- metals, by which is metal transformed to a toxic
cal, biological and ecological effect on the environ- form (Cuypers et al., 2000). Since the roots are
ment. The resulting effect on the ecosystem can the place of the nutrients uptake, they become
be reflected in the elimination of species, food the most frequent place for bioaccumulation of
chain simplifying and ecological stability reduc- heavy metals. The heavy metals may affect the
tion. Among the chemical consequences of the structural properties of the root, morphology of
acid mine drainage are an increase of acidity, the the root system or the length of the root. Entry
disappearance of bicarbonate buffer system and of metals to plants is further reflected in the food
increase of soluble metals concentration. The gen- chains and the metal is spread in the ecosystem
eration of reactive metals and other components (Cuypers et al., 2000; Younger & Wolkersdorfer,
consuming oxygen have a strong influence on the 2004). The ability of some plants to absorb and
biota. Impacts on ecosystems depend on charac- accumulate heavy metals makes them significant
teristics of AMD, neutralisation potential of the in terms of environmental pollution indication
ecosystem and on the climatic factors of the envi- (Buszewski et al., 2000). Plants that are able to
ronment (Akcil & Koldas, 2006). accumulate high amounts of xenobiotics are
Heavy metals, metalloids and acidic environ- used in the process of phytoremediation (Prasad,
ment increase the toxicity of the environment 2003).

37
2 MATERIAL AND METHODS

2.1 Study area


The tailing pond Sedem Žien is located in the
district Banská Štiavnica in the southern part of
Central Slovakia. In the past, Banská Štiavnica
was significant in terms of the Au, Ag and Pb-Zn
mining. The dominant minerals of the deposit are
quartz, carbonates, sphalerite, galena, pyrite, chal-
copyrite, hematite, gold, argenite and stephanite
(Koděra, 1963). Waste mud formed after treatment
of sulphide ores had been deposited on Sedem Žien
tailing pond since 1963 until 1994. The tailing pond
is 44 m high with an area of approximately 22 ha.
The dam of the pond consists of mine waste rocks
and local soils (Masarovičová et al., 2007). Sedem
Žien tailing pond meets technical and legislative
requirements for categorisation in the group of Figure 1. Sampling sites (P1—the plain under the tail-
permanent environmental burdens (Masarovičová ing pond; P2—the second terrace of the pond´s dam;
et al., 2007; [Link], 2015). P3—the fourth terrace of the pond´s dam; P4—the top
Soil and water samples have been collected for plain of the tailings pond; W1—red coloured mine drain-
the characteristics of contamination of the stud- age; W2—transparent mine drainage).
ied area. Soil samples were collected on the four
sites of the tailing pond: P1—the plain beneath
24 hours and milled. 0.25 g of the soil samples were
the tailings pond Sedem Žien; P2—the second ter-
weighted into the cuvette and reacted with 4 ml of
race of the pond´s dam; P3—the fourth terrace of
65% HNO3. The decomposition of the material was
the pond´s dam; P4—the top plain of the pond.
carried out in Milestone ultraclave under the pres-
There were two sampling sites for the water sam-
sure 40 bar in a bath composed of 330 ml of H2O,
ples: water sample 1 (W1)—red coloured drainage
30 ml of 30% H2O2 and 2 ml of 98% H2SO4. The
percolating Sedem Žien tailing pond; water sample
same procedure was followed during the decompo-
2 (W2)—transparent drainage percolating tailing
sition of plants from samples with weight of 0.3 g.
pond. Two plant species (Pinus sylvestris and Quer-
Soil samples were then filtered for removal of pre-
cus robur) were sampled in the tailing pond with
cipitated silicates. Concentrations of metals (Fe,
aim to determine bioaccumulation of heavy met-
Mn, Pb, Co, Cr, Cu, Ni, Zn) were measured in all
als. Plants have been collected from four sites of
samples using an absorption spectrometer VAR-
the pond, identic with soil sampling sites (P1—P4).
IAN 280FS AA. The decomposition of the of the
Since there was only one species growing at the site
biological material was performed with use of dry
P4, Pinus sylvestris was the only collected species
matter of the plants which was in leaves of Quercus
from the top plain of the pond.
robur around 90% and in the branches and roots
of Quercus robur about 80% of the total weight.
The dry mater in needles of Pinus sylvestris was
2.2 Experimental
50–70% of the weight and in branches and roots
Analyses of the waters and soils of the tailing pond 80–90%. Analyses of metals in water samples were
were firstly realised to determine contamination of realised by atomic absorption spectrometry using
the studied area. The pH value of the two mine Fast Sequential Atomic Adsorption Spectrometer
drainages was measured directly on the sampling Varian AA240 FS.
site. The pH value of the soil samples was meas- BioConcentration Factor (BCF) and Translo-
ured in a suspension of 5 g of soil sample in 25 ml cation Factor (TF) were calculated from the con-
of distilled water after 1 hour of mixing in mag- centrations of heavy metals in plants and soils.
netic stirrer. Heavy metals in water samples were Bioconcentration factor represents the ratio of the
measured by atomic absorption spectrometry using concentration of heavy metals in shoot tissue of
Fast Sequential Atomic Adsorption Spectrometer plants to the concentration of metals in the soil.
Varian AA240 FS. The decomposition of the soil Calculation of BCF for Pinus sp. and Quercus sp.
samples was needed before atomic absorption was based on the content of heavy metals in the
analysis. The soil samples as well as separated par- soil and in the leaves and needles. According to
ticular parts of the collected plants (the leaves/nee- Baker (1981) there are following categories of the
dles, branches and roots) were dried at 100 °C for plants:

38
Table 1. pH and heavy metals of water samples.

Fe Mn Pb Zn Cu Cr Ni Co

Sample pH mg.l −1
μg.l −1

W1 7.6 9.6 4.4 73 1720 140 <D.L <D.L <D.L


W2 8.8 0.8 0.0 3773 400 160 0.3 <D.L <D.L

− Excluders (BCF <1, metals are immobilised in Table 2. Average values of pH and concentrations of
the root system). heavy metals in the soil of the analysed area.
− Indicators (BCF = 1, the content of metals in
Fe Mn Pb Zn Cu Cr Ni Co
plants reflects the content of metals in the exter-
nal environment). Site pH [Link]−1 [Link]−1
− Accumulators (BCF> 1, metals in these plants
are actively concentrated in shoot tissues, espe- P1 6.7 155 5.7 4889 14199 1435 46.3 42.1 47.7
cially in leaves and the vacuoles. This group P2 5.1 183 10.1 5846 9675 2048 67.5 38.5 51.4
includes the hyper accumulators, in which the P3 4.1 197 15.8 3710 6365 1866 48.2 39.7 60.4
concentration of metals in above-ground parts P4 6.4 148 3.4 466 1051 157 50.6 46.4 65.1
of the 100- to 1000-times higher than the con-
centration of metals in the soil and the roots
(Andráš et al., 2015a). To determine the accu- the soil, but despite the high content of Fe in
mulation of metal in the particular plant parts the soil Quercus robur accumulated less than 1%
the translocation factor is calculated. The trans- of the content. Zn values accumulated in the
location factor is the ratio of the metal in the plant correspond to 14–19% of the zinc in the
shoot tissues to metal in the roots (Singh et al., soil. On the second terrace of the pond´s dam
2010). the difference between uptake by Pinus sylvestris
and Quercus robur can be observed. While Pinus
sylvestris accumulated less than 2% of all metals
3 RESULTS present in the soil, Quercus robur accumulated
up to 9% of these metals. A common indicator
Water and soil analyses showed high concentra- is the fact that both plants accumulated in the
tions of the metals present in the ores mined in largest ratio Mn and Zn. The plain beneath the
the study area (mainly Fe, Zn, Pb). The red col- tailing pond showed to be the area with the low-
oured tailing drainage water (W1) contains a large est metals uptake, although the highest uptake
amount of Fe, Zn and Mn and the second drainage of Mn and Zn persists.
water percolating the tailing pond (W2) contains Bioaccumulation of the metals in the plants was
high concentrations of Pb (3773 μg.l−1; Tab. 1). for all accumulated metals (Cu, Pb, Fe, Zn, Mn)
Soils of the tailing pond show high concentrations dependent on the pH value. Uptake of metals was
of Fe, Mn, Zn, Pb and Cu. The area with the low- increasing with the decrease of the pH (Fig. 2).
est concentrated metals was the top plain of the Concentrations of the rest of the analysed
tailing pond (Tab. 2). metals (Cr, Ni, Co) were under the detection
The only hardwood species growing at the limit of the spectrometer. BCF calculation
top plain of the tailing pond—Pinus sylvestris implemented as a calculation of element con-
contained very low concentrations of the met- tent in leaves/needles vs. content in soil showed
als in comparison with the amount of metals in that BCF < 1 for all of the analysed metals. The
the soil between the roots. The soil contained highest BCF values were described for Mn in
mainly Fe, Mn, Zn and Pb. The largest propor- Quercus robur on the 2nd and 4th terrace of the
tion of metal uptake was observed for Zn, when pond. Translocation factor indicates that Fe, Pb
Pinus sylvestris contained more than 15% of the and Cu (in most cases also Zn) accumulate pref-
amount of metals contained in the soil. Another erentially in the roots. Exception is Mn, which
metal with the second highest uptake was Mn. passes into the leaves/needles. TF highest val-
On the fourth terrace of the pond´s dam were ues for Pinus sylvestris and Quercus robur have
by Pinus sylvestris the most accumulated met- been described from the fourth terrace, where
als Mn, Zn, Pb and Cu. The same results were the land had the lowest pH. TF values for Mn in
achieved with Quercus robur, which accumulated Quercus robur reached values up to TF = 27.545
more than 27–38% of Mn compared to Mn in (Tab. 3).

39
4 DISCUSSION

Results of this study confirmed the influence of


the sulphide ores mining on the studied area. Soils
of the tailing pond are characterised by elevated
concentrations of heavy metals. This phenomenon
is conditioned as by geological structure of the
area so by mining activities which facilitated the
weathering of rocks and the subsequent release of
hazardous elements into the environment (Ďurža,
2007). The soils from the pond´s dam had lower
pH (4.1, 5.1) than soils from the top plain of the
tailing and from the plain beneath the tailing.
The pH value of the top plain (6.7) is probably
due to application of limestone layer during rec-
lamation. The limit concentrations of Pb, Zn, Cu
and Cr for agricultural land given by the Act No.
220/2004 Coll. were exceeded in all of the analysed
soils. Entry and accumulation of metals in various
parts of the plant are affected by numerous factors.
An important factor is soil-ecological conditions,
including pH and Eh of the soil, moisture, tem-
perature, soil type, the content and form of met-
Figure 2. Dependence of metals uptake on pH of the als in the soil, the content of humus components
soil. in soil, presence of clay minerals, cation exchange

Table 3. BioConcentration Factor (BCF) and Translocation Factor (TF) calculated for Pinus sylvestris and Quercus
robur.

BCF

Plant Site Fe Mn Pb Zn Cu Cr Ni Co

[Link] P1 0.001 0.011 0.003 0.012 0.003 0.011 0.019 0.01


[Link] 0.001 0.012 0.005 0.009 0.001 0.016 0.014 0.014
Q. robur 0.002 0.037 0.004 0.007 0.006 0.015 0.02 0.015
[Link] P2 0.002 0.015 0.002 0.013 0.003 0.007 0.016 0.02
Q. robur 0.001 0.194 0.001 0.071 0.008 0.015 0.02 *
[Link] P3 0.003 0.02 0.01 0.006 0.003 0.01 0.018 0.02
[Link] 0.002 0.088 0.006 0.038 0.004 0.019 0.029 *
Q. robur 0.001 0.179 0.005 0.043 0.008 0.017 0.015 0.01
Q. robur 0.002 0.284 0.005 0.026 0.011 0.017 0.015 0.01
[Link] P4 0.001 0.047 0.002 0.072 0.000 0.014 0.015 0.011
TF
[Link] P1 0.192 0.75 0.301 0.976 0.251 − − −
[Link] 0.852 2.00 1.109 1.153 0.252 − − −
Q. robur 0.87 4.25 0.38 0.679 0.681 − − −
[Link] P2 0.326 1.429 0.182 0.72 0.123 − − −
Q. robur 0.119 14.182 0.025 0.909 0.099 − − −
[Link] P3 0.095 4.00 0.292 0.564 0.071 − − −
[Link] 0.121 1.25 0.275 0.473 0.044 − − −
Q. robur 0.153 5.457 0.246 1.301 0.17 − − −
Q. robur 0.75 27.545 0.463 0.215 0.677 − − −
[Link] P4 0.034 1.455 0.037 2.387 0 − − −

Explanations: For the metals which concentrations were under the Detection Limit (<D.L.) was calculated with the
value 0.7. TF calculations for Cr, Ni and Co were not possible to realise (concentrations of these metals in leaves/nee-
dles as well as concentrations in roots were under the detection limit). * Co concentrations in the soil were under the
detection limit.

40
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T., Van Hees, M., Wannijn, J., et al., 2008. Effects of agement. Mine water and the environment. Springer.
uranium and phosphate concentrations on oxidative 23(1): 2–80 p.

42
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Emission factors of criteria pollutants from domestic thermal units

F. Skácel & V. Tekáč


University of Chemistry and Technology, Prague, Czech Republic

ABSTRACT: Domestic Thermal Units (DTU) combusting various solid and/or fluid fuels are signifi-
cant source of air pollution. Their contributions to the air quality should be taken into account. Criteria
pollutants emission factors are quite high and exceed those of huge fireplaces. Emission factors of CO,
SO2, NO2, TOC, SPM and POP’s are given for different fuels and appliances.

1 INTRODUCTION realistic user behavior. The experimental results


are compared with the reference values determined
Residential combustion in Domestic Thermal using equal methods in huge power plant firing
Units (DTU) is a major source of air pollutants brow coal in Czech Republic and typical domestic
with potential health hazard (Lavric et al. 2004; natural gas firing boiler used in Czech Republic.
Ostro et al. 2006; Naeher et al. 2007; Bølling et al.
2009; Bari et al. 2010; Pastorello et al. 2011; Win
et al. 2012). Its impacts in local air quality are 2 MATERIAL AND METHODS
confirmed in numerous studies by different meth-
ods such as emission inventories, air quality data Technology and characteristics of four tested
analysis and modeling, and source receptor mod- appliances are summarized in Table 1.
eling. However, the real operations of domestic Eight types of solid fuel (spruce wood pellets,
solid fuel appliances are generally not considered pellets made from agriculture wastes and spruce
in those evaluations. The test methods for quality sawdust and shavings, wheat and oat corn, brown
labels primarily focus on emissions during opera- coal briquettes, coal I from Czech Republic, coal
tion on full load and national Emission Factors II from Poland) were used for the feeding of man-
(EF) for DTU are generated from measurements ual and automatized appliances; these types were
primarily during stationary operation in optimal selected for their large market penetration and for
conditions. a comparison (corn fuel).
Emissions caused by incomplete combustion The main characteristics of tested fuels were
are mainly a result of combustion conditions such determined using methods based on the inter-
as inadequate mixing of combustion air and fuel in national standard methods EN 15407:2011 for
the combustion chamber, an overall lack of avail- elemental analysis (C, H, N), ISO 587:1997 for
able oxygen, too low over all combustion tempera- chlorine content, EN 14918:2012 for net calorific
tures, non-homogeneous temperature distribution value, EN 15414:2011 for moisture and ash con-
in the combustion chamber (cold zones), as well tent and EN 15980:2004 for sulfur content.
as too short residence times, they thus depend on Aiming to be representative of the average user
operational practices that could differ significantly behavior, the “real life” cycle has been defined as
between appliances and firing staff. follows and was subsequently reproduced in labo-
The present work aimed to determine average ratory for manual operated appliances:
EFs for combustion devices, types of fuel and fir-
ing behavior typical of Czech Republic and many − the ignition phase consisted of the load of a
European countries. The work assessed the EFs of small amount of solid fuel (0.5 kg) keeping the
manual appliances burning different types of solid air regulation valve completely open throughout
fuels, investigating the influence of the fuel type the phase;
and burning cycle on the emissions in order to sup- − after 20 min from the ignition an amount of fuel
port the new policy frameworks needed to lower equal to the nominal fuel load (defined by the
the DTU emissions. Differently from the standard manufacturer) was added and the air valve was
emission testing methods, user habits were simu- partially closed;
lated in a schematic way in the laboratory employ- − after 1 hour a second load was added;
ing different combustion cycles that represent a − after another hour a final full load was added.

43
Table 1. Description of the tested appliances.

Appliance/nominal heat output


[kW] Fuel Air regulation Heat transfer

Stove/6.3 Wood briquettes Natural draft Natural


convection
Coal I
Boiler DOR 24/24 Wood briquettes Manual Water
Coal II
Brown coal briquettes
Automatized boiler A25/25 Wood pellets Automatic Water
Pellets (agriculture wastes)
Wheat corn
Oat corn
Gas boiler G27/27 Natural gas Automatic Water
Power plant*/135 × 103 Brown coal Automatic Steam

* Fluid bed furnace equipped by a “dry” desulfurization unit.

The duration of each load was limited to a max- (cooled probe technique) which is composed of a
imum of 60 min; the fire has been stoked if neces- titanium sampling probe heated to 150°C, a com-
sary not more than once in the time between one bined quartz fiber filter and PolyUrethane Foam
load and the following. (PUF) filter to collect the particulate matter, a
For automatic a [appliances the combustion cooling system at 4°C that condenses the con-
cycle used starts after 1 hour of appliance opera- densable gaseous species and PUF to fix the gas
tion and lasts for 1 hour at nominal heat output. phase. The filters and the PUF were extracted,
In order to obtain a realistic evaluation of treated and analyzed together with the condensate
ambient emissions and to measure the conden- and rinsing solution by HRGC/MS using method
sable particles produced by tested heating sys- based on EN 1948-2:2006, EN 1948-3:5006, and
tems, the emissions sampling was performed in EN 1948-4:2010. A sampling standard addition
a stack fulfilling requirements of EN 15259. The of 13C isotope marked standards was used for the
appliances for solid fuels were placed on a scale extraction efficiency assessment.
to measure the weight variation during the test A calibrated Prandtl tube type S in combina-
period. The fuel consumption was continuously tion with the pressure transducers specifically to
monitored. The scale has a resolution of 10 g and the installed stack was used in order to be able to
therefore the uncertainty of the weight measure- measure the flue gas flow in the stack during all
ment for the total fuel consumed during the test phases of combustion test. The actual density of
was less than 1_. the flue gas was calculated using composition tem-
A set of thermocouples was located in and just perature and static pressure characteristics of the
after the combustion chamber to measure the flue flue gas in a measuring plane according to EN ISO
gas temperature. The thermal output of teste appli- 16911-1:2015.
ances was measured using heat transfer circuit. The EFs in a sampling period may be estimated
The exhaust gases were extracted from the test- from average pollutant concentration and average
ing stack by means of heated probe at 180°C, to flue gas volume flowrate in relation to the amount
be distributed to the following flue gas analyzers: of fuel consumed (e.g. g/kgdry fuel) or in relation to
a flame ionization detector (Microfid, ABB); mul- the energy input to the combustion process (e.g.
ticomponent flue gas analyzer for monitoring of g/MJ). While the method may work quite well with
NO/NOx, SO2, CO, CO2 and O2 (Horiba PG250, stable combustion process, assuming constant flue
Horiba), and Ultrakust (Bartec) for water vapor gas flow rate, deviations from the average emission
monitoring. factor calculated in this way may occur in batch
For each test of solid fuels total PM emissions combustion installations with variations among
were measured according to EN 13284-1:2004 different combustion phases.
using in-stack filtration technique. Prebaked (3h at
800°C), preweighed 47 mm quartz fiber filters were
used for all tests. 3 RESULTS AND DISCUSSION
PAH and PCDD/PCDF were measured accord-
ing to the EN 1948-1:2006. Both pollutant sets The summary of the average EFs for tested
were collected with the same sampling system appliances is shown in Table 2 for gaseous

44
Table 2. Emission factors (kg/MWh) of gaseous pollutants related to effective energy output.

Appliance Fuel CO SO2 NO2 TOC CH4

Stove Wood briquettes 40.9 0.1 0.9 23.1 8.2


Coal I 16.4 2.2 0.7 7.8 2.7
Boiler DOR 24 Wood briquettes 10.7 0.1 0.4 0.8 0.6
Coal II 10.0 0.6 0.5 5.8 1.1
Brown coal briquettes 26.5 0.8 1.0 8.7 5.6
Automatized Wood pellets 0.48 0.05 0.42 0.05 0.02
boiler A25
Pellets (agriculture 3.1 0.38 2.7 0.2
wastes)
Wheat corn 2.0 0.50 3.1 0.3
Oat corn 2.9 0.22 1.8 0.1
Gas boiler G27 Natural gas 0.03 0.01 0.16 −
Power plant Brown coal 0.49 1.32 0.89 0.01 0.01

Table 3. Emission factors (μg/MWh) of condensed phase pollutants related to effective energy output.

PM PAH PCCD/F PCB

Appliance Fuel (g/MWh) (μg/MWh)

Stove Wood briquettes 1000 97 0.66 66


Coal I 2200 444 1.48 122.8
Boiler DOR 24 Wood briquettes 200 57 0.11 24.7
Coal II 2300 535 5.32 174.7
Brown coal briquettes 1400 505 0.08 30.4
Automatized Wood pellets 380 57 0.11 24.7
boiler A25
Pellets (agriculture 410 105 1.89 47
wastes)
Wheat corn 810 43 0.23 20.8
Oat corn 230 37 0.18 18.4
Power plant Brown coal 72 0.001 0.012 74.9

pollutants and in Table 3 for condensed phase 4 CONCLUSIONS


pollutants. Average CO emissions relative to the
solid fuel types and manually operated appli- The impact of the parameters outlined in this study
ances are in the same order with a maximum (e.g. fuel type, appliance type, combustion mode)
difference of four times between spruce wood on actual emissions suggests that the emissions in
briquettes presenting the lowest and coal I the the batch working process are strictly related to the
highest EF value. EFs for automatically oper- combustion mode and the treatment of solid fuel
ated DTU and huge power plant are of different rather than the fuel type, because the general emis-
orders of magnitude. Emissions result for SO2, sion performance of the manually operated appli-
NO2, TOC, CH4, PM and POPs are similar for ances is observed not to differ notably between
DTU firing solid fuels. All pollutant EFs for different types of commercially available fuel.
gas burner and huge power plant are signifi- It is known that the design of a heating appli-
cantly lower. ance (i.e. primary and secondary air supply)
Regarding the automatic appliances, better pel- directly influences the emission characteristics,
let quality (i.e. lower ash content) corresponds to however the reported results indicate that SO2 and
lower incomplete combustion product emissions NO2 emissions from the advanced appliance are
(i.e. CO and TOC) and higher NO2 emissions due similar or higher than the traditional appliances,
to higher combustion temperatures. and are only slightly lower for PM and PAH. This

45
finding highlights the importance of the real-world Naeher, L.P., Brauer, M., Lipsett, M., Zelikoff, J.T.,
emission factors in the evaluation of the environ- Simpson, C.D., Koenig, J.Q., Smith, K.R. 2007,
mental performance of the heating appliances. Woodsmoke health effects—a review, Inhalation Toxi-
cology 19, 67–106.
Ostro, B., Broadwin, R., Green, S., Feng, W.Y., Lipsett, M.
2006, Fine particulate air pollution and mortality in
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Environmental Health Perspectives 114(1), 29–33.
Bari, M., Baumbach, G., Kuch, B., Scheffknecht, G. Pastorello, C., Caserini, S., Galante, S., Dilara, P.,
2010, Particle-phase concentrations of polycyclic aro- Galletti, F. 2011, Importance of activity data for
matic hydrocarbons in ambient air of rural residential improving the residential wood combustion emission
areas in southern Germany, Air Quality, Atmosphere & inventory at regional level, Atmospheric Environment
Health 3(2), 103–116. 45, 2869–2876.
Bølling, A.K., Pagels, J., Yttri, K.E., Barregard, L., Win, K.M., Persson, T., Bales, C. 2012, Particles and gas-
Sallsten, G., Schwarze, P.E., Boman, C. 2009, Health eous emissions from realistic operation of residential
effects of residential wood smoke particles: the impor- wood pellet heating systems, Atmospheric Environ-
tance of combustion conditions and physicochemical ment 59, 320–327.
particle properties, Part. Fibre Toxicol. 6, 29–48.
Lavric, E.D., Konnov, A., De Ruyck, J. 2004, Dioxin lev-
els in wood combustion—a review, Biomass Bioenergy
26, 114–145.

46
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Fabrication, characterization, and pervaporation performance


of graphene oxide/poly(vinyl alcohol) nanocomposite membranes
for ethanol dehydration

H.H. Nguyen
Key Laboratory of Chemical Engineering and Petroleum Processing, Vietnam National University,
Ho Chi Minh City, Vietnam
Faculty of Chemical Engineering, Ho Chi Minh City University of Technology, Vietnam National University,
Ho Chi Minh City, Vietnam

N.P.D. Ngo
Faculty of Chemical Engineering, Ho Chi Minh City University of Technology, Vietnam National University,
Ho Chi Minh City, Vietnam

ABSTRACT: Graphene Oxide/Poly(Vinyl Alcohol) (GO/PVA) nanocomposite membranes were fabri-


cated by solution-casting method. The effect of GO content on the PerVaporation (PV) performance of
nanocomposite membranes was investigated with additive loading of 0.1 ÷ 0.5 wt% respect to the weight
of PVA. The membrane characterizations were performed by atomic force microscopy, transmission elec-
tron microscope, Fourier-transform infrared spectroscopy, X-ray diffraction, tensile testing, differential
scanning calorimetry, swelling degree, and water contact angle. The characterization and pervaporation
results indicated that thermal stability, swelling degree, and separation performance of GO/PVA mem-
brane were improved compared to neat PVA by adding 0.3 wt% GO (0.3GO/PVA). This nanocomposite
membrane exhibited an acceptable selectivity of 34.9, an equivalent permeate flux of 0.12 kg/m2h, and a
good pervaporation separation index of 4.12 kg/m2h for dehydration of 80 wt% ethanol solution at feed
flow rate of 60 L/h, feed temperature of 50°C, and vacuum pressure of −100 kPa.

Keywords: Graphene oxide, poly(vinyl alcohol), nanocomposite, membrane, pervaporation, ethanol,


dehydration.

1 INTRODUCTION needs multiple evaporation of the entire mixture,


PV consumes energy only for permeate evaporation.
PerVaporation (PV) is an important membrane PV generally also doesn’t need any extra reagents as
process for the separation of azeotropic mixtures, azeotropic and extractive distillation, extraction or
close-boiling systems, isomeric or heat-sensitive other methods employing extra chemicals… . Thus,
compounds. The popular applications of PV proc- PV process also doesn’t need subsequent recovery
ess are dehydration of alcohols and other organic of these chemicals which complicate the separation
solvents (Kaminski, 2008; Frolkova & Raeva, of technology (Barker, 2014). Accordingly, PV has
2010). This technique has advantages such as sim- been considered as a potential separation technol-
plicity, no separating agents or chemicals required, ogy for ethanol dehydration.
save energy, and minimal environmental impact. The challenges in PV have been the search for
Herein, instead of the physicochemical properties suitable membranes with good separating proper-
of components being separated and those of the ties. Herein, membrane separation working principle
mixture, the separation efficiency in PV is mainly is based on using hydrophilic membranes to dehy-
based on the membrane properties and process drate ethanol. In the most materials used in dehy-
conditions. This allows azeotropic mixtures to be dration of ethanol by PV, Poly(Viny Alcohol) (PVA)
separated more readily in PV than in the case of membranes have proved to be an ideal polymer for
conventional distillations. Moreover, in PV proc- fabricating hydrophilic membranes because of their
ess, the mixture to be separated doesn’t need to be polar, low cost, and good membrane-forming prop-
boiled and it is, hence, possible to utilize low-grade erties in dehydration of ethanol by PV. However,
heat. As being distinct from distillation, which PVA membranes often perform poorly in PV due to

47
sulfuric acid (98 wt%), sodium nitrate (99 wt%),
and hydrogen peroxide (30 wt%) were purchased
from Xilong Chemical, China. Graphite (particle
size: <50 μm, density: 20 ÷ 30 g/100 mL) was pur-
chased from Sigma Aldrich, Germany. Potassium
permanganate (>99.5 wt%) and ethanol (96 vol%)
were purchased from ViNa Chemsol, Vietnam.
Figure 1. Structural model of GO.

2.2 Nanocomposite membrane preparation


the swelling in water and the decline of the stabil-
Graphite Oxide (GiO) was synthesized by chemi-
ity at high temperature, results in both an increase
cal oxidation modified Hummers’ method (Hieu
in solubility and diffusivity of ethanol, and conse-
et al, 2013). At first, 0.5 g of GiO was mixed with
quently lowers the permselectivity. In this respect,
500 mL of deionized water and sonicated for 12 h
enhancement the PV performance has been achieved
to exfoliate into GO. The obtained GO was centrif-
by adding inorganic nanoparticles as clays, zeolites,
ugated to remove the aqueous solution. And then,
fullerenol, silica, titania, or other nanofillers into the
wet GO was finally washed with deionized water
polymer matrix to form nanocomposite membranes
until pH = 6, and dried at 60°C for 24 h.
to improve swelling property of PVA. Such nano-
Nanocomposite membranes were prepared as
composite membranes have both forming properties
follows: 0.05 g of GO was mixed with 500 mL of
of the polymer and physicochemical stability of the
deionized water and sonicated for 24 h to obtain
inorganic particles ([Link] et al, 2009; Ankudey &
GO suspension. The nanocomposite membranes
Zainudeen, 2014; Penkova et al, 2014; Bruggen &
were fabricated by solution-casting method. Dried
[Link], 2015; Ravindra et al, 2015).
PVA (1.0 g) was dissolved in 100 mL deionized
Interestingly, several strategies reported for the
water and heated at 90°C to form aqueous PVA
fabrication of Graphene Oxide (GO)-based PVA
solution. Then, the PVA solution was mixed with
nanocomposites with improved mechanical, ther-
certain amounts of GO suspension to be obtained
mal properties, and water resistance (Wang et al,
by GO/PVA ratio of 0.3 wt% with respect to the
2013). Graphene oxide is product of oxidation and
weight of PVA. The mixture was stirred for 1 h and
exfoliation of graphite (Gi). The structure of GO
sonicated for 45 minutes. The obtained homogene-
contains functional groups such as: epoxy (–O–),
ous solutions were casted in petry disk and dried
hydroxyl (–O–H), cacboxyl (–COOH) and cacbo-
at room temperature for 24 h to form membranes.
nyl (–C = O), as shown in Figure 1 (Compton &
After that, membranes continued to be dried at
Nguyen, 2010). GO can be well dispersed at the indi-
100°C in 3 h to constant weight. The nanocompos-
vidual-sheet level in aqueous solution because of
ite was denoted 0.3GO/PVA, corresponding to the
its numerous oxygen-containing functional groups.
0.3 wt% GO content.
Therefore, the appearance of GO will restricted the
The effect of GO contents on the PV perform-
movement of PVA chains, which leads to increase
ance of membranes were investigated using a vari-
the mechanical properties and reduce swelling.
ety of GO of 0.1 ÷ 0.5 wt%. A series of GO/PVA
Moreover, as two-dimensional nanomaterials, GO
nanocomposite membranes was named as 0.1GO/
sheets nanoparticles might promise as molecular
PVA, 0.2GO/PVA, 0.3GO/PVA, 0.4GO/PVA, and
sieve-like shields to prevent the permeation of large
0.5GO/PVA, corresponding to the loading content
molecules throughout the membrane, contribute to
of GO.
increase the selectivity when they disperse into PVA
matrix chains (Bao et al, 2011).
Accordingly, in this study, PVA nanocomposite 2.3 Characterization
membranes with different fillers (GO) were fabri- Atomic Force Microscopy (AFM) measurements
cated by solution-casting method (Hieu et al, 2016). were performed on an AFM Nanotech Electronica
The effect of GO contents on PV performance as by casting powder dispersion onto freshly cleaved
well as morphology, structure, and properties of mica substrates and drying under ambient condi-
the nanocomposite membranes were investigated. tion. Transmission Electron Microscope (TEM)
images were taken by JEM-1400 machine with an
accelerating voltage of 100 kV. Fourier-Transform
2 MATERIALS AND METHOD Infrared spectroscopy (FTIR) spectra were obtained
in the range of wavenumber from 4000 to 500 cm−1
2.1 Materials during 64 scans on Alpha–E Brucker (Bruker
PVA (molecular weight and the degree of saponi- Optik GmbH, Ettlingen, Germany) spectrom-
fication were 80,000 and >98%, respectively), eter. X-Ray Diffraction (XRD) patterns were

48
obtained by Advanced X8, Bruker (German) with and measured the concentration by a refractom-
λ = 0.154 nm, step of 4°/minute from 5° to 35°. eter to determine the selectivity.
Tensile testing were performed with AND RTC The PV membrane performance is expressed in
1210 A (Tensilon, Japan) with the membranes were terms of permeate flux (J-kg/m2h), selectivity (α),
cut into approximately 5 × 60 mm, and carried out and pervaporation separation index (PSI-kg/m2h)
under initial tensile length of 40 mm, and drawing (Barker, 2014; Bruggen & [Link], 2015):
speed of 50 mm/min. Differential Scanning Calor-
imetry (DSC) was performed with DSC-1 (Mettler 1 ΔW
Tolado, America) differential scanning calorimeter. J= (2)
A Δt
Water contact angles measurements were assessed
by an OCA20 contact angle meter equipped with yH2O yC2 H5OH
α= (3)
an image capturing system. Static contact angles xH2O xC2 H5OH
were measured by the sessile drop method. Swell-
ing degrees (S) were carried out by immersing in PSI
S J − )
J( (4)
deionized water at room temperature at least 48 h
to reach absorption equilibrium, and were calcu- where ΔW (kg) is the weight of permeate during
lated as follows: the experimental time Δt (h), A (m2) is the effec-
tive membrane area; x and y are the mass fraction
WS WD of either water or ethanol in the feed and the per-
S= × 100% (1) meate, respectively. The PSI is originally defined
WD
to measure the separation ability of a membrane,
the higher PSI value is the better separation ability.
where WS and WD are the weight of swollen and
In case of PSI = 0, membrane has no selectivity
dry membrane, respectively.
(α = 1) or no pemeation (J = 0).
All measurements were carried out at 25°C and
relative humidity of 30%.
3 RESULTS AND DISCUSSION
2.4 Pervaporation experiments
3.1 Characterization
The PV system was used in this study as illustrated
in Figure 2. The PV dehydration of ethanol was 3.1.1 Morphology of GO and dispersion of GO in
carried out as follows: 1 L of 80 wt% ethanol feed PVA membrane
solution was heated up to 50°C and circulated AFM image and height profile for GO as shown
through the membrane module from the feed tank. in Figure 3. AFM result confirmed that GO
Membrane was placed on a stainless steel screen nanosheets were successfully synthesized which the
support in the module with effective membrane average thickness of the obtained GO layers were
area of 28.3 cm2. During the experiments, the pres- found to be 0.913 nm. This result is in agreement
sure at the downstream side was kept at −100 kPa with previous studies (Bao et al, 2011; Hieu &
by a vacuum pump. The permeate vapor was con- Long, 2013; Hieu et al, 2016).
densed in cold trap at −20°C. For each experiment, In order to evaluate the dispersion of GO in the
the operating time was 2 h to ensure that a steady PVA matrix, the ultrathin sections of nanocom-
state was reached. The collected permeate in cold posite membrane was observed via Figure 4 which
trap was weighted to calculate the permeate flux

Figure 2. Schematic diagram of PV system. 1. Feed


tank, 2. Metering pump, 3. Membrane module, 4. Mem-
brane, 5. Cold trap, 6. Vacuum pump. Figure 3. AFM image and height profile of GO.

49
shows the TEM image of 0.3GO/PVA. Apparently, the presence of hydrogen bonding interactions
a homogeneous dispersion and alignment of GO between oxygen-containing functional groups of
in PVA that obtained dark lines with the average GO and the hydroxyl groups on PVA molecular
thickness of 29 ÷ 39 nm. Nevertheless, a little bit chains, and the forming of free hydroxyl groups
amounts of GO sheets tended to restack together (Bao et al, 2011; Shuai et al, 2015).
by Val der Waals forces. XRD is an effective method to characterize
crystalline properties of materials. As shown in the
3.1.2 Interaction of GO and PVA in membrane Figure 6, the peak of neat PVA appeared at 2θ ≈
Figure 5 shows FTIR spectra of GO, PVA, and 19.6°. However, the XRD pattern of 0.3GO/PVA
0.3GO/PVA. It can be seen that the absorptions nanocomposite membrane only showed the PVA
at 3550 cm−1 ÷ 3200 cm−1, 2840 cm−1 ÷ 3000 cm−1, diffraction peak. XRD results demonstrated a
and 1145 cm−1 are typical to the presence of –O–H, well-dispersing of the GO nanosheets into the PVA
–CH2– (symmetric and asymmetric) and –C–O matrix. Hereby, the broad peak in GO disappeared
groups, respectively, of PVA matrix (Mansur et al, in the nanocomposite membrane, suggesting the
2008; Hossain et al, 2014). Compared to neat PVA disorder and loss of structure regularity of GO at
and GO, the spectrum of GO/PVA exhibited the 2θ = 9 ÷ 11°. Moreover, after adding GO into PVA,
enhancement of the –C = O stretching peak at the intensity of the diffraction of PVA decreased.
1741 cm−1 and the increase in the –O–H and –C–O Such effect was ascribed to stronger interfacial
stretching vibration, which can be identified as interactions between GO and PVA matrix through
the hydrogen bonds. These interactions probably
restricted the capability of the matrix chains to
form large crystalline domains and led to decline
crystallinity of the GO/PVA (Zhao et al, 2010;
Zhou et al, 2010).

3.1.3 Tensile testing


The tensile strength Tb and elongation at break Eb
of PVA and nanocomposite membranes are sum-
marized in Table 1. The decrease in Tb of composite
membrane was observed. The decreasing in Tb

Figure 4. TEM image of 0.3GO/PVA membrane.


Children

Children
Children
Children
Children Children

Children Children Face Tough Issues


Children
Figure 6. XRD patterns of GO, PVA, 0.3GO/PVA.
Children
Table 1. Tensile strength Tb and elongation at break Eb
of PVA and 0.3GO/PVA.

Children Face Tough Issues Samples Tb (MPa) Eb (%)

Children
Children PVA 176.5 4.5
0.3GO/PVA 166.5 4.3
Figure 5. FTIR spectra of GO, PVA, and 0.3GO/PVA.

50
confirms the fact that crystallinity is directly related hence Tg is expected to be affected (Bao et al, 2011;
to the mechanical strength of polymer, i.e. polymer Bruggen and Luis, 2015; Hieu et al, 2016).
become stronger and harder with increasing crys-
tallinity (Gupta et al, 2011). This is the reason why 3.1.5 Swelling degree
neat PVA exhibited a more strength than that of Swelling of any polymer membranes in a solvent
0.3GO/PVA. depends upon the diffusion coefficient of the sol-
Further, due to the stronger interfacial inter- vent, the relaxation rate of the amorphous regions
action between GO and PVA matrix through the of polymer chains and its degree of crystallinity.
hydrogen bonds which restricted the movement of The swelling properties of PVA and nanocompos-
PVA chains, the sample of 0.3GO/PVA was becom- ite membrane is shown in Table 3.
ing stiffer and less flexible (Bao et al, 2011; Bedaghi The presence of a large number of the hydroxyl
et al, 2014). This led to the reducing trend of Eb. groups in PVA results in strong hydrogen bonding
(both intermolecular and intramolecular types),
3.1.4 Thermal properties which affects the swelling of PVA in water. This is
From the DSC curves as shown in Figure 7, it can owing to the relaxation of the amorphous zones.
be observed that the glass-transition temperature As represented in Table 3, neat PVA membrane
Tg was 90°C. This result was greater than that of showed a high degree of swelling with an average
neat PVA membrane, indicating the improvement value of 88%. For the 0.3GO/PVA membrane, the
of thermal property of GO/PVA membrane (Bao swelling degree was greatly suppressed. This could
et al, 2011; Bedaghi et al, 2014). For any neat poly- be explained by incorporation of GO nanosheets
mers as PVA, the stiffness is mainly due to the with PVA chains, which reduced the water perme-
formation of hydrogen bonds among hydroxyl ability (Abdeen, 2011; Bao et al, 2011; Xie et al,
groups of different PVA chains. As soon as foreign 2011; Bedaghi et al, 2014).
materials as GO sheets fillers are introduced to the
polymer, they could interfere with the hydrogen- 3.1.6 Water contact angle
bond formation. This resulted in a decrease in Water contact angle results as shown in Table 4.
the hydrogen-bond interaction, which may reduce Overall, the membranes were hydrophilic.
the stiffness of the chains. However, at the same Accordingly, neat PVA showed the highest
time, the incorporation are occurring due to act- hydrophilic, with a water contact angle of 51.6°.
ing as a nucleating agents of fillers with the chains; On the other hand, with the presence of GO, the
membrane contact angle was enhanced, indicat-
ing the less hydrophilic of the membrane surface.
This is due to the forming of hydrogen bonding
Issues interactions between oxygen-containing functional
groups of GO and the hydroxyl groups on PVA
chains after adding GO sheets. The contact angle
Issues data were similar to previous studies (Xie et al,
Issues 2011; Penkova et al, 2014).

3.2 Pervaporation performance of membranes


Issues
Effects of different filler loading level on per-
vaporation performance of ethanol dehydration

Table 3. Swelling degree of PVA and 0.3GO/PVA.

Samples S (%)
Children Face Tough Issues
Issues PVA 88
0.3GO/PVA 63
Figure 7. DSC curves of PVA and 0.3GO/PVA.

Table 2. Glass transition temperature (Tg) of PVA and Table 4. Water contact angles of PVA and 0.3GO/
0.3GO/PVA. PVA.

Samples Tg (°C) Samples Water contact angle (°)

PVA 85 PVA 51.6


0.3GO/PVA 90 0.3GO/PVA 66.2

51
through membrane are depicted in Figures 8 Table 5. Comparison of PV performance of the present
and 9. Generally, neat PVA membrane showed a membranes with literature for dehydration of 80 wt%
selectivity, α = 21.4 and a relative permeate flux, ethanol feed solution.
J = 0.10 kg/m2h. And after adding the GO fillers
Membranes J (kg/m2h) α References
with contents of 0.1 ÷ 0.3 wt%, nanocomposite
membranes produced higher selectivity but lower Zeolite 0.025 ÷ 0.035 45 ÷ 50 Ankudey &
permeate flux than that of neat PVA. However, the clay/PVA Zainudeen,
phenomenon showed in contrast when the filler 2014
contents were over 0.3 wt% of GO. 1–5 wt% 0.080 ÷ 0.13 36 ÷ 46 Penkova et al,
In particular, by adding GO into PVA matrix Fullerenol/PVA 2014
at a low loading level (≤0.3 wt%), GO nanosheets 0.3GO/PVA 0.12 34.9 Present work
were well-dispersed into and obtained stable struc-
ture with PVA chains. It was apparent that the 2011; Kang et al, 2014). The PSI results indicated
selectivity of GO/PVA membrane increased and that GO content of 0.3 wt% exhibited the high-
its permeate flux decreased. This can be explained est performance of ethanol dehydration with the
due to a role of GO nanosheets (2D material) were equivalent selectivity of 34.9 and permeate flux of
considered as molecular sieves that helped to reject 0.12 kg/m2h.
large particles such as ethanol. Whereas, at GO Result of present work are compared with
loading level of over 0.3 wt%, GO interacted to published data in literature as shown in Table 5.
PVA stronger and caused destroying crystallinity Evidently, the performance of GO/PVA nanocom-
regions of PVA. Thus, permeate flux enhanced but posite membrane was improved in the selectivity
selectivity dropped (Zhou et al, 2010; Peng et al, and permeate flux.

4 CONCLUSIONS

GO/PVA nanocomposite membranes were pre-


pared by solution-casting method. The effects of
GO contents on characteristics and PV perform-
ance of membranes were investigated with GO
loading of 0.1 ÷ 0.5 wt%. AFM result indicated
that the successfully synthesized GO with the aver-
age thickness of 0.913 nm. TEM image revealed
GO dispersed into PVA matrix to the lines with
the average thickness range of 29 ÷ 39 nm. FTIR
spectra confirmed that the cross-linking between
Children Face Tough Issues PVA and MA decreased the crystallinity of nano-
composite membrane, which was also observed via
Figure 8. Effect of GO loading contents on J and α. XRD analysis. Additionally, DSC, swelling degree,
and water contact angle analyses also presented
that the characteristics of GO/PVA nanocompos-
ite membrane were improved in comparison to neat
PVA. PV testing results on dehydration of 80 wt%
ethanol solution demonstrated a good perform-
ance of the nanocomposite membrane by adding
0.3 wt% GO with an acceptable selectivity of 34.9,
an equivalent permeate flux of 0.12 kg/m2h, and a
good PSI of 4.12 kg/m2h at the operating condi-
tion as feed flow rate of 60 L/h, feed temperature
of 50°C, and vacuum pressure of −100 kPa.

REFERENCES

Children Face Tough Issues Abdeen, Z. 2011. Swelling and Reswelling Characteristic
of Cross-Linked Poly(vinyl alcohol)/Chitosan Hydro-
gel Film. Journal of Dispersion Science and Technology
Figure 9. Effect of GO loading contents on PSI. 32: 1337–1344.

52
Ankudey, E.G. & Zainudeen, M.N. 2014. Pervaporative Kang, Q. et al. 2014. Hydrophylic membranes to replace
Separation of Ethanol-Water Mixture using Compos- molecular sieves in dewatering the bio-ethanol/water
ite Membranes with Hydrophilic Zeolite fillers made azeotropic mixture. Separation and Purification Tech-
from Ghanaian Clay deposits. International Journal of nology 136: 144–149.
Scientific & Engineering Research 5: 358–363. Mansur, H.S. et al. 2008. FTIR spectroscopy characteri-
Baker, R.W. 2014. Membrane technology and applications, zation of poly(vinyl alcohol) hydrogel with different
Second Edition. England: John Willey & Sons. hydrolysis degree and chemically crosslinked with glu-
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investigation of property and mechanism. J. Mater. Patachia, S. et al. 2009. Chapter 2: Pervaporation proc-
Chem. 21: 13942–13950. esses in Poly(Vinyl Alcohol) PVA-Based Polymer
Bedaghi, H. et al. 2014. Synthesis and Characterization Membranes, New York: Nova Science Publishers.
of Poly(vinyl alcohol)/Sulfonated Graphene Oxide Penkova, A.V. et al. 2014. Transport properties of
Nanocomposite Membranes for Use in PEMFCs. cross-linked fullerenol-PVA membranes. Carbon 76:
Industrial and Engineering Chemistry Research 53: 446–450.
16621–16632. Peng, F.B. et al. 2011. Tuning the molecular structure,
Bruggen, B.V. & Luis, P. 2015. Pervaporation. In: separation performance and interfacial properties of
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tion. UK: Academic Press. ite membranes. Journal of Membrane Science 368:
Compton, O.C. & Nguyen, S.B.T. 2010. Graphene Oxide, 26–33.
Highly Reduced Graphene Oxide, And Graphene: Ravindra, S. et al. 2015. Performance enhancement of
Versatile Building Blocks For Carbon-Based Materi- the poly(vinyl alcohol) (PVA) by activated natural clay
als. Small Nano 6: 711–723. clinoptilolite for pervaporation separation of aque-
Frolkova, A.K. & Raeva, V.M. 2010. Bioethanol Dehy- ous-organic mixtures. Desalination and Water Treat-
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Chemical Engineering 44: 545–556. Shuai, C.J. et al. 2015. Graphene oxide reinforced poly(vinyl
Gupta, S. et al. 2011. Evolution of PVA gels prepared alcohol): nanocomposite scaffords for tissue engineer-
without crosslinking agents as a cell adhensive sur- ing applications. RSC advances 5: 25416–25423.
face. Journal of Materials Science: Materials in Medi- Wang, N.X. et al. 2013. Poly(vinyl alcohol)-graphene oxit
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ethanol. Chemical Engineering Journal 135: 95–102. ogy 71: 1266–1270.

53
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Fabrication, characterization and antibacterial activity against


Escherichia coli of zinc oxide/graphene nanocomposite

H.H. Nguyen
Key Laboratory of Chemical Engineering and Petroleum Processing, Faculty of Chemical Engineering,
Ho Chi Minh City University of Technology, Vietnam National University, Ho Chi Minh City, Vietnam

H.B.S.L. Nguyen, T.T.T. Nguyen & T.T. Nguyen


Faculty of Chemical and Environmental Engineering, Lac Hong University, Dong Nai, Vietnam

ABSTRACT: In this study, graphene (Ge) and zinc oxide (ZnO)/Ge nanocomposite were prepared by
the modified Hummers’ and coprecipitation methods, respectively. The structural and morphological
properties of ZnO, grapheme, and ZnO/Ge were performed by using X-ray diffraction, Fourier transform
infrared spectroscopy, transmission electron microscopy, Brunauer–Emmett–Teller method, and Raman
spectroscopy. The characterized results showed ZnO nanoparticles with a mean size of 12 nm were syn-
thesized and randomly decorated on the surfaces and edges of Ge sheets and high specific surface area of
zinc oxide/Ge was 50 m2/g. The antibacterial activities of ZnO, Ge and ZnO/Ge nanocomposite against
Escherichia coli were observed. The tested results revealed that the antibacterial activity of the ZnO/Ge
nanocomposite at low loading 0.04 mg/L is higher than that of ZnO or Ge on this bacteria.

Keywords: Zinc oxide, graphene, nanocomposite, antibacterial activity, Escherichia coli

1 INTRODUCTION oxide (ZnO), gold (Au), calcium oxide (CaO), silica


(SiO2), copper oxide (CuO) and magnesium oxide
Bacterial infectious diseases are serious health (MgO) have been reported to possess antimicrobial
problem that has drawn the public attention activity (Azam et al, 2012; Besinis et al, 2014; Chen
in worldwide as a human health threat, which et al, 2013; Emani-Karvani et al, 2011; Pal et al,
extends to economic and social complications. 2007; Usman et al, 2013; Zarei et al, 2014). More-
Increased outbreaks and infections of pathogenic over, the aqueous fullerene nanoparticles (nC60)
strains, bacterial antibiotic resistance, emergence and Carbon NanoTubes (CNT) have showed anti-
of new bacterial mutations, lack of suitable vac- microbial activity.
cine in underdeveloped countries and hospital Graphene (Ge) is a two-dimensional (2D) mate-
associated infections are global health hazard to rial, formed of a lattice of hexagonally arranged
human. Accordingly, without new antibacterial carbon atoms. The term Ge is typically applied to
agents, routine medical procedures and opera- a single layer of graphite, although common refer-
tions could soon become impossible. An antibac- ences also exist to bilayer or trilayer graphene. It
terial property is required in wound dressings to have high electron conductivity, mobility of charge
inhibit bacteria proliferation and damage to tissue carriers and high surface area (Delina et al, 2008;
under wound dressings (Janpeth et al, 2016). Most Kang et al, 2008; Zhang et al, 2012). These fasci-
infection-causing bacteria are resistant to at least nating properties render graphene, as a sheet of
one of the antibiotics that are generally used to sp2 hybridized carbon, suitable for many promis-
eradicate the infection (Akiyama et al, 1998). This ing applications such as sensors, energy conversion
problem encourages the researchers to study the devices and catalysts. Importantly, the properties of
new agents which can effectively inhibit microbial Ge vary significantly to the bulk material graphite,
growth (Dizaj et al, 2015). Various nanometer- particularly in terms of electron mobility and these
sized antibacterial agents such as metal and metal significant feature differences have driven research
oxide nano-particles have been evaluated by in fields as diverse as electronics, materials, secu-
researchers in recent years. Several types of metal rity, water and health (Xiang et al, 2012; Cong et al,
and metal oxide nanoparticles such as silver (Ag), 2012). Much of the focus of Ge research has been in
silver oxide (Ag2O), titanium dioxide (TiO2), zinc high value added electronics where miniaturization

55
is a key driver. However to date, the bulk of the In this work, the ZnO/Ge nanocomposite was
material that is produced is geared toward research fabricated and characterization by X-Ray Diffrac-
applications or in composites production. The tion (XRD), Fourier Transform InfraRed spectros-
use of Ge as the load bearing component in com- copy (FTIR), Transmission Electron Microscopy
posites is highly beneficial (Geim, 2009). Recent (TEM), Brunauer–Emmett–Teller method (BET),
studies have also shown that Ge could also be and Raman spectroscopy. The well diffusion
used in water purification applications (Geim & method was used to evaluate the antibacterial
Novoselov, 2007). Other potential applications activity against gram negative bacteria Escherichia
of Ge include in sensor technology, electronics, coli ([Link]) of this material.
hybrid photovoltaic devices, bio devices, compos-
ites, drug delivery systems, and catalysts due to its
unique properties. A thorough understanding of 2 EXPERIMENTS AND METHODS
the interaction with biological material is essen-
tial prior to the uptake and utilization of Ge on a 2.1 Materials
wide scale, particularly if there is significant poten-
tial for it to find its way into the environment and Graphite (particle size: <50 μm, density: 20–30 g/
human body. Potential biomedical applications for 100 ml) was purchased from Sigma Aldrich,
Ge have been suggested. The low surface energy of Germany. Sulfuric acid (98 wt%), hydrogen per-
Ge makes it an attractive substrate for the delivery oxide (30 wt%), and potassium permanganate
of hydrophobic drugs. Furthermore, the unique (>99.5 wt%) were purchased from Duc Giang
structure could allow it can be used as a contrast Detergent Chemical JSC (Vietnam). Zinc acetate
agent in biomedical imaging. The influence of par- (99 wt%), sodium nitrate (NaNO3) (99 wt%), and
ticle size is important in biomedical application. ethylene glycol were purchased from Xilong Chem-
Hence there is a strong push for understanding the ical (China). Microbial Cultures: [Link] strain was
interaction of Ge with cells and bacteria. Bacterial purchased from Research Institute of Biotechnol-
interaction with surfaces is ubiquitous in nature. ogy and Environment (RIBE) – Nong Lam Uni-
There are also countless examples where biofilm versity (Vietnam); nutrient broth and nutrient agar
formation leads to significant environmental and were purchased from Titan Biotech Ltd. (India).
health problems. For instance in a marine environ- All solutions were prepared with double-distilled
ment, biofilm formation on ship hulls can lead to water.
corrosion and increased drag as bacteria coloniza-
tion can lead to subsequent attachment of other
2.2 Preparation of graphene oxide
organisms such as barnacles. Whilst this can result
in a substantial economic cost, the health prob- Graphene oxide was prepared from graphite fine
lems arising from bacteria attachment to medical powder based on the modified Hummers’ method
implants can be fatal if not properly dealt with in (Wang et al, 2009). According to this method, 1 g
timely fashion (Stankovich et al, 2006). of graphite and 0.5 g of sodium nitrate were mixed
Nano-sized ZnO exhibits varying morpholo- together and added in 60 mL concentrated sulfuric
gies and shows significant antibacterial activity acid under constant stirring at temperature of less
over a wide spectrum of bacterial species explored than 5°C. For the first oxidation, 3 g of KMnO4
by a large body of researchers (Buzea et al, 2007; was added gradually to the above solution while
Brayner et al, 2006; Emami-Karvani et al, 2011; Li & maintaining the temperature at less than 20°C.
Kaner, 2008; Jones et al, 2008; Jalal et al, 2010; Then, the mixture was heated to 35°C and soni-
Notley et al, 2013; Seil et al, 2012). ZnO is cur- cated in an ultrasound bath (500 W) for 2 h. For
rently being investigated as an antibacterial agent the second oxidation, 3 g of KMnO4 were added
in both microscale and nanoscale formulations. to the mixture followed by a sonication at 35°C
ZnO exhibits significant antimicrobial activi- for 4 h. Then, 400 mL of distilled water was added
ties when particle size is reduced to the nanom- and the solution placed at room temperature. In
eter range, then nano-sized ZnO can interact with order to ensure the completion of the reaction with
bacterial surface or with the bacterial core where KMnO4, the suspension was further treated with
it enters inside the cell and subsequently exhib- 30 wt% hydrogen peroxide solution until light yel-
its distinct bactericidal mechanism (Padmavathy low color appeared. After that, the mixture was cen-
et al, 2008). The interactions between these unique trifuged, washed with distilled water until pH = 6
materials and bacteria are mostly toxic, which have and dried at 80°C to obtain graphite oxide. The
been exploited for antimicrobial applications such obtained graphite oxide was dispersed in distilled
as in food industry. However, the easy aggrega- water to achieve a concentration of 0.5 mg/mL
tion of ZnO hinders their antibacterial activity H2O. Subsequently, the graphite oxide suspension
(Raghupathi et al, 2011). was exfoliated by sonicating for 12 h to obtain

56
graphene oxide. Finally, graphene oxide was were taken and made into cultures. Fresh overnight
centrifuged and dried at room temperature. cultures of inoculum (100 μL) of each cultures
were spread on to nutrient agar dish’s surface
evenly in four different Petri dishes respectively,
2.3 Preparation of ZnO/Ge nanocomposites
the wells were casted by porer (8 mm diameter).
The graphene oxide 30 mg was dissolved in 100 ml Control dish consists of distilled water and anti-
of ethylene glycol by ultrasonic treatment for 4 h biotic drugs. The square dishes were incubated at
under ambient condition to give a brown disper- room temperature for 19–24 h. Activity was clearly
sion. Further 0.87 g of zinc acetate dissolved in visible from 19–24 h on the dishes. Zone of inhi-
80 ml of ethylene glycol and stirred to obtained bition was measured and the sample of the ZnO/
brown dispersion. Subsequently, 4 g of NaOH Ge showing maximum antimicrobial activity was
dissolved in 20 mL of deionized water then the noted.
mixture was stirred for 60 min and transferred to
250 mL glass bottle and tightly sealed with teflon
cap then kept the glass bottle in hot air oven for 3 RESULTS AND DISCUSSION
10 h at 100ºC. After completion of process, sam-
ple was cooled down to room temperature. The 3.1 Characterization
obtained few layered ZnO/Ge in material was cen-
trifuged and washed several times with water and 3.1.1 XRD analysis
ethanol thoroughly. The synthesized few layered Figure 2 displays XRD patterns of ZnO, Ge, and
ZnO/Ge material was dried in oven at 300ºC for ZnO/Ge. It can be seen that the feature diffraction
24 h. Schematic diagram and chemical formula of peak of exfoliated Ge at 43° (001) is observed. It
preparation few layered graphene sheets decorated further shows the excellent crystal structures of
by ZnO nanoparticles shown in Figure 1. ZnO nanoparticles even in the nanocomposite with
graphene. The peaks at 31.9°, 34.5°, 36.3°, 47.5°,
56.9°, 62.7°, and 68.0° correspond to (100), (002),
2.4 Characterization (101), (102), (110), (200), and (201) planes of ZnO,
XRD patterns were observed on a Bruker indicating crystal structure (Wang et al, 2014). The
D8 Advanced powder diffractometer system using diffraction peaks of as synthesized ZnO/Ge nano-
Cu-Kα radiation. FTIR spectra were recorded composite can be ascribed to the well crystallized
in the 4000–400 cm−1 range with a Bruker FTIR ZnO of the (100) diffraction peak of ZnO.
Alpha–E spectrometer. TEM image was obtained This XRD result indicated that the existence of
using a JEOL JEM 1010 microscope at an accel- ZnO nanoparticles in nanocomposite. The results
eration voltage of 100 kV. The surface area of the are consistent with studies published previously
nanocomposite was measured by nitrogen adsorp- (Lua et al, 2011; Wang et al, 2011).
tion/desorption using a NOVA 2200e surface area
analyzer. Raman spectra were recorded using 3.1.2 FTIR spectra
LabRam micro-Raman spectrometer with an exci- The FTIR spectra of ZnO, Ge, and ZnO/Ge as
tation wavelength of 632 nm (He–Ne laser). shown in Figure 3. The peaks of ZnO and O-H

2.5 Well diffusion method


According to this method (Bykkama et al, 2015), Issues
the sterilized nutrient agar was poured (20 ml/dish)
onto the Petri dishes and left for a while till the
agar gets solidified. Two pathogenic strains E. coli
Issues

Issues Issues
Issues

Children
Children
Face Tough
Face Tough
IssuesIssues
Figure 1. Formation mechanism of few layered graph-
ene sheets decorated by ZnO nano particles (Li et al,
2016). Figure 2. XRD patterns of ZnO, Ge, and ZnO/Ge.

57
are observed on the ZnO spectrum at 436 cm−1 and has been integrated and consistent with research
3452 cm−1, respectively. The C = C was observed at published previously (Ferrari et al, 2000). D band
1552 cm−1. The ZnO/Ge spectrum showed identical originates from the edge defect and the disordered
peaks of Ge, but a new broad peak was observed at structure of Ge, whereas the G band represents the
442 cm−1 which attributed to ZnO vibration (Kang ordered sp2 bond structure. This can be attributed
et al, 2016). These vibrations indicated that ZnO to an obvious decrease in the size of the in plane
nanoparticles were anchored to the Ge sheets. sp2 domains owing to the reduction reaction lead-
ing to the removal of the oxygen functional group
3.1.3 Raman spectra in Ge and the interaction be-tween ZnO nanopar-
Raman spectroscopy is a nondestructive and most ticles and the Ge sheets in the liquid phase based
widely used technique to characterize graphitic ultrasonic-assisted synthesis system.
materials, in particular to determine ordered and
disordered crystal structures of ZnO/Ge nano-
composite. The Raman spectra of graphite, Ge,
and ZnO/Ge were shown in Figure 4. Two charac-
teristic peak broad D band and a measure of dis-
order degree and average size of the sp2 domains
in graphite materials. This result showed that Ge

Issues

Issues Figure 5. TEM images of ZnO/Ge nanocomposite.

Table 1. The BET specific surface areas of ZnO and


ZnO/Ge nanocomposites.

Samples BET area, m2 g−1

ZnO 16.798
G-ZnO-20 47 [37]
G-ZnO-30 57 [37]
ZnO/Ge 50.36
Children Face Tough Issues
Figure 3. FTIR spectra of ZnO, Ge, and ZnO/Ge.

Issues

Issues
Issues Issues
Issues

Children Face Tough Issues


Figure 6. Zone of inhibition formation against E. coli
Figure 4. Raman spectra of graphite, Ge, and ZnO/Ge. of Ge (a), ZnO (b), and ZnO/Ge (c).

58
Table 2. The antibacterial activity (zone of inhibition) against E. coli at different concentrations of antibacterial
agents.

Organism Zone of inhibition (mm) at different concentrations of antibacterial agents (μL)

E. coli ZnO Ge ZnO/Ge

20 μL 40 μL 60 μL 20 μL 40 μL 60 μL 20 μL 40 μL 60 μL
0.8 1.2 2 0.5 0.8 1.2 9 10 11.6

3.1.4 TEM images ZnO/Ge is a promising candidate for application


The TEM image of the ZnO/Ge nanocomposite in antibacterial medicine.
confirms ZnO nanoparticles are uniformly deco-
rated on Ge sheets. A fine size distribution of
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60
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Application of Box-Behnken design for treatment of tannery


wastewater

J.C. Beltrán-Prieto & K. Kolomazník


Tomas Bata University in Zlín, Zlín, Czech Republic

H.B.S.L. Nguyen
Lac Hong University, Dong Nai, Vietnam

ABSTRACT: This paper suggests a methodology for the adsorption of chromium from tannery
wastewater as an ecological alternative to the contamination and toxic problems associated with this
industry. The effect of mixtures of quarry stone and silica gel or activated carbon, particle size and pH were
analyzed using a Box-Behnken design to evaluate and optimize the adsorption of chromium up to 88%.

1 INTRODUCTION They reported that the adsorption of Cr(III)


was proportional to the surface area of the acti-
The process of skin preservation, also known as vated carbon containing calcium. In the treatment
tanning, has traditionally been considered as a of wastewater containing metals, the pH of the
non-environmental friendly activity. This is caused solution is one of the most common parameters
mainly because of the effluents that are discharged under study. Malkoc and Acar (Malkoc & Acar.
to the environment during the skin transformation 2005) reported that on Fagus orientalis L, the
process into leather. This fluid contains chromium adsorption of Cr(VI) resulted to be optimal at pH
and can cause serious problems to the environment. 1. However, the adsorption of Cr(III) on pyrophyl-
Metals that are present in industrial wastewater lite was reported to be favored while increasing pH
are toxic in some of their valence states (El Nemr (up to 5) (Talidi at al. 2005).
2007). Moreover, they are particularly problematic Compounds like CaCO3, SiO2, Al2O3, and MgO
due to the fact that they are not biodegradable and are able to assist in the filtration and sorption of
can be accumulated in living tissues (Nessim 2011). toxic metals. As they are contained in high con-
Chromium (VI) reacts with biological material and centration in minerals like quarry stone, these min-
produce reactive oxygen species. Therefore, it is erals have the potential to be used in the removal
considered to be carcinogenic and strong mutagen of chromium from wastewater. Natural quarry
as it causes DNA damage and gene mutation. The stone is widely used in construction and building
toxic effects are produced by prolonged contact industry. However, the application for heavy metal
of solid or liquid chromium compounds even in adsorption is extremely scarce. This is important
small quantities (Bennet 2013, Beyersmann 2002, particularly from the economical point of view,
Dirican & Türkez 2012). since the use of low-cost and efficient adsorbents
Several studies have been performed to examine is one of the key elements for successful industrial
the separation of chromium from aqueous solu- applicability.
tions or effluents. For example, Talidi et al. In general, when a process is controlled by sev-
reported a 98% chromium removal from aqueous eral variables, an analysis is performed by changing
solutions using natural pyrophyllite with alumin- one variable ad keeping the rest constant. However,
ium as adsorbent (Talidi at al. 2005). Research on this procedure requires a large number of experi-
the adsorption process of Cr(III) as dithizonate ments and a great deal of time. One alternative to
chelate using chromosorb 108 resin demonstrated remove the limitations from classical methods is to
an adsorption capacity of the sorbent of 4 mg/g use experimental design. Response Surface Meth-
(Tuzen & Soylak 2006). The utilization of acti- odology (RSM) comprises a group of statistical
vated carbon from sugar industrial waste for the techniques for empirical model building in which
treatment of tannery wastewater was proposed by a experimental design is performed to modify the
Fahim et al. (Fahim et al. 2006). factors under study at the same time, leading to a

61
better understanding of the interactions between Table 1. Coded and natural levels of the design factors.
factors. The analysis and design of experiments by
RSM try to relate a response to either an output Design factors Coded levels
variable, with levels of a parameter, or an input var-
−1 0 1
iable that affects the response. Despite the efforts
A:particle size (μm) 1410 1895 2380
made by several groups to separate chromium
B: pH 4 6 8
from tannery wastewater, little has been done to
C: ratio 0.3 0.5 0.7
optimize the process of chromium recovery.
The main objective of this study was to evaluate
the feasibility of the adsorption of chromium from
efficiency. Considering the results from the first set
tannery wastewater using mixtures of activated car-
of experiments, a second experimental design was
bon, quarry stones, and silica gel by Box-Behnken
proposed. Conditions of pH, ratio and mesh sieve
design and optimization through response surface
near to the relative maximum obtained were tested
modeling.
in a secondary experimental design for optimiza-
tion purposes.
The coded and natural levels as well as the range
2 METHODOLOGY of selected independent variables are presented in
Table 1. Values for particle size were limited to the
2.1 Instrument available mesh size.
Wastewater was collected from a local tannery.
The water was filtered and the concentration of
3 RESULTS AND DISCUSSION
Cr2O3, fatty and oil content, pH, Chemical Oxygen
Demand (COD), and conductivity was calculated.
3.1 Characterization of wastewater
All chemicals used were reagent-grade chemicals
from Fermont and Merck. Quarry stones were Table 2 shows the characterization of the waste-
obtained from building waste. The samples were water. The concentration of chromium oxide was
triturated, automatically crushed, and the parti- taken into account for the evaluation of chromium
cles were passed through different mesh sieves in a adsorption. Results are similar to those found in
range of 1410–2380 μm particle size. literature. For example, Munz et al. [4] found values
The concentration of chromium from waste- of 3690 mg L−1 for COD, pH values of 5.8–7.5 and
water was estimated as chromium oxide (Cr2O3) conductivity between 6.3–12.1 μS/cm. Differences
and measured as g Cr2O3⋅L−1. Chromium oxide can be attributed to the initial raw material and the
content was measured from Cr(III) oxidation to particular concentration of chemicals in the proc-
Cr(VI) with perchloric and sulfuric acid; pH and ess. Moreover, higher values of conductivity are
conductivity were measured using a digital pH also related to the concentration of NaCl in the
meter Orion 420 A and CRISON micro CM2202, effluent. Normally, this salt is added to the animal
respectively. Fatty and oil content was calculated skin in the conservation and pickling stages.
by Soxhlet extraction. COD was determined
using colorimetric method (DR100 colorimeter in
3.2 Optimization of chromium adsorption
HACH cuvettes, digestion solution was prepared
in the presence of potassium bicarbonate and sul- The results of the chromium adsorption using
furic acid) quarry stone and activated carbon are presented
in Figure 1 showing the contours of estimated
response surface at proportion of quarry stone
2.2 Chromium removal experiments
equal to 0.3. It is clearly seen that the increment in
The influence of three different parameters, pH and lowering of particle size favors adsorption
namely size particle, pH, and proportion of quarry of chromium. 83% of Cr2O3 was retained at pH of
stone in the adsorbent (with activated carbon or 8, particle size of 1895 μm and quarry stone pro-
silica gel) was studied by means of Box-Behnken portion of 0.3. In the present study it was found
design. 10 g of prepared mixtures of quarry stone that the chromium started to precipitate at pH
and silica gel or activated carbon were collocated higher than 8, thereby reducing the adsorption. At
in a glass column of 10 x 150 mm. lower pH, the H+ is competitive to the metal and
Sample solutions (30 ml) were adjusted to differ- can cause a reduction in the adsorption, however
ent pH values by adding 1% NaOH to the effluent acid values can also benefit the separation proc-
to reach a pH of 4–9. After, the sample was added ess due to metal hydrolysis and increment in the
to the column with the adsorbent. The water fil- formation of charged metal complexes, which can
tered was analyzed to account for the adsorption also benefit the adsorption process.

62
Table 2. Characterization of wastewater recollected. Table 3. Percentage if chromium adsorption for the
second experimental design.
Parameter Value
Particle size (μm) Ratio of adsorbants % Adsorption
pH 3.6
Cr2O3 (mg⋅L−1) 6826 1895 0.25 84.6
Conductivity (μS⋅cm−1) 10.1 1895 0.2 85.03
COD (mg O2⋅L−1) 3267 1895 0.15 85.5
Fatty and oil (mg⋅L−1) 4118 1895 0.1 86.1
1895 0.05 87
1410 0.25 84.2
1410 0.2 85.07
1410 0.15 86.08
1410 0.1 87.1
1410 0.05 87.8

Table 4. Characterization of treated wastewater.

Issues Parameter Value


Issues Issues Issues pH 7.7
Issues Cr2O3 (mg⋅L−1) 819
Conductivity (μS⋅cm−1) 23.5
Figure 1. Contours of estimated response surface for
COD (mg O2⋅L−1) 2345
chromium adsorption from wastewater using quarry
stone and activated carbon (ratio 0.3:0.7). Fatty and oil (mg⋅L−1) 388.1

After the evaluation of these results, a second


experimental design was proposed closer to the
region with higher adsorption using quarry stone
and activated carbon as adsorbents. The values of
pH remained constant at 8. The results were ana-
lyzed using Statgraphics Centurion XVI version
16.1.11 and are presented on Table 3. From the
Issues new experimental design proposed, the adsorption
Issues Issues Issues of chromium into the support increased to 88 by
decreasing the particle size to 1410 and using a mix-
Issues ture of quarry stone:activated carbon (0.1:0.9).
Figure 2. Contours of estimated response surface for The adsorption capacity of the quarry stone
chromium adsorption from wastewater using quarry can be related to the content of clay minerals, car-
stone and silica gel (ratio 0.7:0.3). bonate, iron oxide and high porosity. The charac-
terization of the treated wastewater was realized,
as shown in Table 4. Chromium concentration
The response surface contours in the vicinity of remained was 12% from the initial concentration.
the optimum value for chromium oxide adsorption Conductivity increased mainly due to the addition
at quarry stone: silica gel ratio of 0.7:0.3 is pre- of NaOH but COD and content of fatty and oil
sented in Figure 2. Solutions with a pH of 6 and decreased significantly. The solution of chromium
particle size of 2380 μm showed 84% chromium that was filtered through the column was centri-
adsorption from wastewater. The pH can influ- fuged at 100 rpm for 5 min followed by water evap-
ence the behavior of the support. For example, oration to obtain a chromium salt.
when the pH reach values lower than the point of
zero charge, the adsorbent surface becomes posi-
tively charged being more suitable for adsorption 4 CONCLUSIONS
of anions, while adsorption of cations is favored
at higher pH. At this ratio, increasing the size of This study presents a novel approach for the
the particle at lower pH enhanced the separation removal of chromium from tannery wastewater by
of chromium, but at higher pH the variation in using quarry stone and activated carbon as adsorb-
particle size does not affect considerably. ent material. Quarry stone was obtained from

63
waste building material and after an activation Beyersmann, D. 2002. Effects of carcinogenic metals on
process the surface has the capacity to remove effi- gene expression. Toxicology Letters 127(1–3): 63–68.
ciently chromium when it is combined with other Dirican, E., & Türkez, H. 2012. Thymbra spicata L.
adsorbent materials. An optimization process by modulates chromium (III) chloride-induced genetic
and oxidative damage in vitro. Fresenius Environmen-
means of Box-Behnken design was performed to tal Bulletin 21(6): 1480–1485.
find optimum conditions of pH (8), quarry stone: El Nemr, A. 2007. Pomegranate husk as an adsorbent
activated carbon gel ratio (0.5:95), and particle size in the removal of toxic chromium from wastewater.
(1410 μm) for chromium adsorption. Chemistry and Ecology 23(5): 409–425.
Fahim, N. F., Barsoum, B. N., Eid, A. E., & Khalil, M. S.
2006. Removal of chromium(III) from tannery waste-
ACKNOWLEDGMENT water using activated carbon from sugar industrial
waste. Journal of Hazardous Materials 136(2): 303–9.
This work was supported by the Ministry of Malkoc, E., & Acar, F. N. 2005. A comparison of adsorp-
tion kinetics: Cr(VI) removal from aqueous solutions.
Education, Youth and Sports of the Czech Republic Fresenius Environmental Bulletin 14(6): 509–513.
within the National Sustainability Programme Nessim, R. B., Bassiouny, A. R., Zaki, H. R.,
project No. LO1303 (MSMT-7778/2014) and by the Moawad, M. N., & Kandeel, K. M. 2011. Biosorption
European Regional Development Fund under the of lead and cadmium using marine algae. Chemistry
project CEBIA-Tech No. CZ.1.05/2.1.00/03.0089 and Ecology 27(6): 579–594.
and also by Lac Hong University, Dongnai, Talidi, A., Chakir, A., Kacemi, K. E., Benbrahim, A.,
Vietnam. Alaoui, A., & Sirvent, C. P. 2005. Chromium(III)
removal from aqueous solutions by adsorption onto
pyrophyllite and pyrophyllite-al. Fresenius Environ-
mental Bulletin 14(10): 947–953.
REFERENCES Tuzen, M., & Soylak, M. 2006. Chromium speciation in
environmental samples by solid phase extraction on
Bennett, R. M., Cordero, P. R. F., Bautista, G. S., & Chromosorb 108. Journal of Hazardous Materials
Dedeles, G. R. 2013. Reduction of hexavalent chro- 129(1–3): 266–73.
mium using fungi and bacteria isolated from contami-
nated soil and water samples. Chemistry and Ecology
29(4): 320–328.

64
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Effect of phosphate and nitrogen resources on lipid-rich microalgae


cultivation from textile wastewater

J.Y. Wu, S.Y. Wu, J.J. Syu & H.L. Yeh


Department of BioIndustry Technology, Da-Yeh University, Changhwa, Taiwan

C.H. Lay & C.Y. Lin


Green Energy Development Center, Master Program of Green Energy Science and Technology, Feng Chia
University, Taichung, Taiwan

C.C. Chen
Department of Landscape Architecture, Chung Chou University of Science and Technology, Changhwa, Taiwan

ABSTRACT: The organic materials and nitrogen and phosphate nutrients in the industrial wastewater
could be utilized for algal growth. The effects of pH and concentrations of Textile Wastewater (TW) as
well as phosphorus and nitrogen sources on microalgae growth and lipid accumulation using TW cultiva-
tion was investigated. Our previous results show that higher COD removal efficiency and the total Fatty
Acid Methyl Easters (FAMEs) content were obtained while the microalgae G22 was cultivated on initial
pH 10 with aeration. This study aims to investigate the effects of adding K2HPO4 and could nitrogen
sources on pollutant removal efficiency and FAMEs accumulation using microalgae from TW. The results
show phosphate and nitrogen sources addition could enhance NH4+-N, COD and color removal efficien-
cies (>60%). Adding (NH4)2SO4 as the nitrogen source with aeration conditions, total FAMEs content
could reach >22% in microalgae G22.

1 INTRODUCTION microalgae is about 80% of the yield of the parent


crop oil given; (3) the water usage per unit weight
Microalgae may prove an alternative to terrestrial biomass and per energy unit during microalgae
crops because they have higher photosynthetic effi- cultivation is lower than that required to grow
ciencies, higher yields and growth rates, and fewer maize at an equivalent weight of corn grain and
requirements for cultivation land and they can be eightfold less than rape cultivation on fertilized
grown in saline waters and in arid and barren land land; (4) Microalgae cultivation is currently done
areas (Lakaniemi et al., 2011). Microalgae biomass at coastal locations in open ponds and interior
can be converted to energy and fuel such as elec- locations in desert climate using nutrient supple-
tricity, ethanol, hydrogen, methane and bio-oil etc mented seawater where evaporative losses domi-
through biochemical and thermochemical conver- nate; (5) All of these components are generally
sions because it has considerable advantages, such found in treated or untreated livestock wastewater,
as environmental sustainability, lower greenhouse and they can be recycled to conserve resources as
gases emission and wastewater treatment ben- well as reduce algal culture medium cost; (6) using
efit (Lakaniemi et al., 2012). Biodiesel production microalgae to clean up flue gas via photosynthesis
from microalgae has been expected to replace the is considered a promising CO2 mitigation process
petroleum-based energy sources owing to its high for flue gas; (7) optimizing the cultivation condi-
areal productivity and lipid contents due to the tions could enlarge the lipid content in microalgae
higher energy yield: 7–31 times higher than palm biomass; (8) algae cultivation does not need herbi-
and several tens–several hundred times than other cides herbicides or pesticides; (9) microalgae valu-
oily plants such as corn, soybean, canola, jatropha, ables products like fatty acids, pigments and stable
coconut and oil palm (Cho et al., 2013). There are isotope biochemical and the residual algal biomass
many advantages for using algae to produce bioen- after oil extraction may be used as feed or fertilizer,
ergy, such as (1) microalgae grow extremely rapidly or fermented to produce ethanol or methane; (10)
and many are exceedingly rich in oil (15–77% dry the clean energy-hydrogen (H2) could be metabo-
weight); (2) actual biodiesel yield per hectare of lized by microalgae (Ghirardi et al., 2000; Spolaore

65
et al., 2006; Chisti, 2007; Dismukes et al., 2008; wastewater to produce biodiesel. Microalgae adopt
Cantrell et al., 2008; Rodolfi et al., 2009; Yen et al., various routes of metabolism for their growth and
2015; Skorupskaite et al., 2015). Therefore, using survival viz., autotrophic, heterotrophic and mix-
microalgae to produce biodiesel for the transporta- otrophic modes. Some microalgae can grow heter-
tion fuel is a high potential renewable source. otrophically by utilizing only organic compounds
Low-cost feedstock production plays an important as both carbon and energy source and mixotrophi-
role in the production of biofuels from algae com- cally using both organic compounds and CO2 as
mercialization. Using the addition of organic car- energy source. Microalgae growth is also affected
bon, such as sugar alcohols, sugar and algae growth by many cultivation parameters, such as pH, tem-
medium expands the cultivation cost for microalgae perature, nutrient sources and so on. Therefore, this
biomass. Recently, attention has been taken into study aims to develop a technology which could
account for the search of cheap products microalgae remove the pollutant in the textile wastewater and
culture media components (Skorupskaite et al., cumulate the lipid in the algae simultaneously and
2015). Mixotrophic culture is a viable alternative investigate the cultivation pH and aeration on lipid
strategy to improve the effective use of light or elimi- accumulation and wastewater removal.
nate cell requirements as well as reducing the cost
of microalgae biomass production. Mixotrophic
growth can reduce energy costs by relatively low 2 MATERIALS AND METHODS
requirement of light intensities and consequently
(Lin and Wu, 2015). Many types of wastewaters 2.1 Microalgae collection and identification of
including dairy wastewater (Woertz et al., 2009), algal strains
municipal wastewater (Komolafe et al., 2014), saline
wastewater (Babatsouli et al., 2015), brewery waste- The microalgae samples were collected from sea-
water (Mata et a., 2014) and so on had been used water around Taiwan, stored in sterile centrifugal
to investigate the biofuel production potential with tubes, and sent to the laboratory within 3 d for algal
mixotrophic culture because wastewater is not only cell isolation. Walne medium plates were prepared
a supplier of major nutrients such as nitrogen and using full-strength seawater, containing 18 g/L of
phosphorus but also a source of organic carbon. agar and 1 g/L of glucose. After inoculation, the
Textile is an important traditional industry in plates were cultured at 30oC for 2–7 d. Single colo-
the world. The effluent from textile processes con- nies composed of spherical cells atypical of either
taining organic materials, dyes and other nutri- yeast, fungi, or bacteria were extracted and care-
ents could contribute significantly to pollute the fully transferred to a new plate. Furthermore, the
environment. These effluents are highly variable isolated microalgae with 49 species were cultivated
in composition with relatively low Biochemical in the sterilized textile wastewater as the medium
Oxygen Demand (BOD) and high chemical oxy- to investigate the potential lipid-rich microalgae
gen demand (COD) contents and are typically which could utilize textile wastewater.
characterized by: (1) strong colour due to residual
dyes, (2) recalcitrance due to the presence of com- 2.2 Textile wastewater
pounds such as dyes, surfactants and sizing agents,
(3) high salinity (up to 100 g /m3 NaCl) and (iv) Textile wastewater was collected from the buffer
high temperature and highly variable pH (Mantza- tank before wastewater treatment process in a tex-
vinos and Psillakis, 2014). These factors not only tile manufactory in central Taiwan and directly
affect the water clarity, but also the solubility of used to cultivate the 49 species microalgae to inves-
gases, which would cause toxicity to aquatic plants tigate the wastewater inhibition on microalgae
and animals, leading to serious global environmen- growth according to the wet biomass estimations
tal problems. The traditional treatment processes using spectrophotometer were done in terms of
for textile wastewater usually combined physical, Density (D) at an OD of 650 nm. Characteris-
chemical and activity sludge methods and it had tic of raw textile wastewater is COD 2330 mg/L,
high cost during operation. Biological treatments pH 11.82, NH4+-N 27.84 mg/L and colorization
are a relatively inexpensive way to remove dyes ADMI 900.
from wastewater. Several microorganisms, such as
bacteria, fungi, and microalgae, have been tested
2.3 Experiment design
for their ability to accumulate heavy metals and
dyes (Taştan et al., 2010). Therefore, the algae cul- Thirty seven species that can grow using the textile
tivation was considered to be a unit in a wastewa- wastewater (dilution rate of 0–80%) were selected to
ter treatment process. In order to increase the cost study the effects of cultivation pH (7, 8, 9, 10, 11)
efficiency in the algal wastewater treatment proc- with and without aeration for extra carbon source
ess, lipid-rich algae could be grown using these adding in our previous study (Lay et al., 2014). The

66
Table 1. Experimental design on optimization of cultivation condition for microalgae G22.

Cultivation condition Effects of K2HPO4 Effects of various nitrogen


concentration source

Textile wastewater 1465 1990


(mg COD/L)
Extra phosphate source K2HPO4 0, 4, 8, 12, 16, 20 mg/L K2HPO4 4 mg/L
Extra nitrogen source non 1 mg/L of peptone, urea,
yeast extract, NH4NO3,
(NH4)2SO4
Initial pH 10 10
Cultivation temperature (oC) Room temperature Room temperature
Light/dark cycle (h/h) 24/0 24/0
Light source (lux) 7523 8125

extra K2HPO4 (2–20 mg/L) and various nitrogen extraction step. After the samples were mixed using
sources (peptone, urea, yeast extract, NH4 NO3 and a vortex mixer for 1 min, they were ultrasonicated
(NH4)2SO4) were added for optimizing the cultiva- for 3 h and centrifuged at 3000 rpm for 10 min. The
tion condition. The glass tube with a working vol- solid phases were separated carefully using What-
ume of 20 mL at 30 °C by using an exponentially man No. 1 filter paper, and the solids were washed
growing seed culture, and 4300 lux of light intensity using 5 mL of chloroform. After this process, 9 mL
was adopted. Aeration was achieved by sparging air of sterilized water was added to a solvent phase, and
enriched with 10% CO2 at 2 vvm. During microalgal the solvent was mixed using a vortex mixer. The sol-
growth, the liquid sample was collected from the vent phase was centrifuged at 3000 rpm for 10 min,
serum bottle with respect to time to determine micro- and the chloroform layer was collected. The weight
algal biomass concentration, pH, residual sugar con- of the lipids was measured after removing the sol-
centration, colorization, NH3-N concentration and vent by using a nitrogen blowing concentrator; the
lipid content of the microalgal biomass. The detail lipid content was then calculated.
cultivations in this study is shown in Table 1.
2.6 Fatty methyl esters and fatty acid analysis
2.4 Analytical method
To observe the saponification/esterification reac-
Biomass was determined by measuring the OD tions, each of the samples were mixed with 2 mL
of each sample at 680 nm (OD680). The dry cell of NaOH–methanol solution and disrupted using
weights of the diluted samples were then detected a sonicator, heated in a 100 °C water bath for
and measured for plotting the standard curve. 10 min, and cooled to room temperature. The sam-
The amounts of total sugar were estimated by the ples were then mixed with 2 mL of HCl in methanol
phenol–sulfuric acid assay method of Dubois et al. and 1 mL of boron trifluoride solution (Sigma–
(Dubois et al., 1956) using glucose standard cali- Aldrich, St. Louis, MO, USA), heated again in
bration curves, respectively. The analytical proce- a 90 °C water bath for 15 min, and then cooled
dures of Standard Methods were used to determine again. Next, 3 mL of a saturated NaCl aqueous
pH, COD, NH3-N concentration and colorization solution and 4 mL of n-hexane were added, and
(APHA, 1995). the samples were mixed thoroughly. The upper liq-
uid layer was transferred to a 4-mL amber glass
vial, sealed using Parafilm®, and stored at −20 °C
2.5 Total lipid extraction
until analysis was performed.
The total lipid content (dry weight) was measured by The fatty methyl ester (FAME) samples were
employing a modified version of the method used analyzed using a gas chromatography machine
by Bligh and Dyer (Bligh and Dyer, 1959). After (YL6100 GC, Young Lin, Korea) equipped with a
the cultivation was complete, the culture medium Carbowax column (fused silica, 30 m × 0.25 mm,
was centrifuged at 9000 rpm and 4 °C for 2 min; Quadrex, U.S.A.) and a flame ionization detec-
the cell pellets were then collected for freeze drying. tor according to appropriate reference standards
The samples were pulverized after drying by using a (Sigma, Louisiana, USA). The injector tempera-
homogenizer, and were extracted using a chloroform– ture was set at 220 °C, the column temperature was
methanol mixture (1:2 v/v). Approximately 15 mL of raised from 50 °C to 150 °C in increments of 15 °C/
solvents was used for 50 mg of dried samples in each min, and then from 150 °C to 250 °C in increments

67
of 5 °C/min. Methyl esters prepared from fatty
acids, including C16:0, C16:1, C18:0, C18:1, C18:2,
C18:3, and C20:0, as well as a FAME standard
mixture, were all purchased from Sigma–Aldrich
and used as the standards for identifying fatty
acids in the samples. These fatty acids were quan-
tified according to their peak area relative to the
C17:0 fatty acid internal standard, and expressed
as a percentage of total fatty acid content.

3 RESULTS AND DISCUSSION

3.1 Effects of concentration of K2HPO4


Microalgae biofuel, which fixes carbon dioxide
and uptakes nitrogen and phosphorous through Issues
the treatment of wastewaters, constitutes a poten-
Figure 1. Pollutant removal efficiency and total FAME
tial application in the short term (Quiroz Arita content of microalgae G22 (a) with aeration and (b)
et al., 2015). The concentration of extra addition without aeration at K2HPO4 concentrations after 7 days
of K2HPO4 was optimized on microalgae cultiva- cultivation.
tion using textile wastewater and the effect on lipid
accumulation and pollutant removal efficiency was
investigated in this study.
The NH4+-N and COD removal efficiencies were
increased with the cultivation time on microalgae
G22 both with and without aeration. After 7 days
cultivation, the NH4+-N and COD concentrations
were decreased to 0.52 mg/L and 800 mg/L respec-
tively (Data not shown). Moreover, the coloriza-
tion was obviously removed at the second day
during the cultivation. The biomass content of
microalgae G22 could reach high amount (1.1 g/L)
under aeration condition and without extra phos-
phate addition (K2HPO4 0 mg/L).
While microalgae G22 was cultivation both with
and without aeration, the colorization and NH4+-N
removal efficiencies could reach 70% and 60%
respectively. The colorization removal efficiency
was much higher than 57% using white-rot fungus
Bjerkanderaadusta to treat the textile wastewater
Issues
Issues Issues
Issues
(Anastasi et al., 2010). Issues
The highest COD removal efficiency (ca 80%)
was obtained with the cultivation condition of Figure 2. Color removal, NH4+-N removal, COD
without aeration and K2HPO4 addition (0 mg/L) removal and total FAME content of microalgae G22 (a)
(Figure 1). Peak FAMEs content of 24% was with aeration and (b) without aeration at various nitro-
occurred at adding K2HPO4 4 mg/L and with aera- gen resources after 7 days cultivation.
tion. This value is much higher than FAMEs con-
tent of 4.4% without phosphate addition (K2HPO4
limiting nutrients, such as nitrogen and phospho-
40 mg/L). Khozin-Goldberg and Cohen (2006)
rous, in the wastewater media (Quiroz Arita et al.,
reported that phosphate limitation caused signifi-
2015). Nitrogen source limitation is an important
cant changes in the fatty acid and lipid composi-
operation strategy for enhancing the lipid con-
tion of Monodus subterraneus.
tent in microalgae (Ho et al., 2012). Five types of
nitrogen sources (peptone, urea, yeast extract, NH4
NO3 and (NH4)2SO4) was studied the effects of the
3.2 Effects of nitrogen resources
growth and lipid accumulation on selected micro-
To grow microalgae in wastewater has taken into algae as well as pollutant removal efficiency to
consideration the measurement of the growth-rate build the low-cost operation strategy in this study.

68
Figure 2 reveals that these five nitrogen sources Biochemistry and Physiology. Vol 37(8), pp. 911–917,
with aeration could improve the NH4+-N removal 1959.
efficiency to 80%, which was higher than 50∼80% Cantrell K.B., Ducey, T., Ro, K.S., and Hunt, P.G., “Live-
without aeration. The COD removal efficiency stock waste-to-bioenergy generation opportunities”.
Bioresource Technology. Vol 99, pp. 7941–7953, 2008.
could reach higher than 75% both with and Chisti Y., “Biodiesel from microalgae”. Biotechnology
without aeration. Moreover, using yeast extract Advances. Vol 25, pp. 294–306, 2007.
as nitrogen source could increase the coloriza- Cho S., Lee, N., Park, S., Yu, J., Luong, T.T., Oh, Y.-K.,
tion removal efficiency to 26%. While microalgae and Lee, T., “Microalgae cultivation for bioenergy pro-
G22 utilized the (NH4)2SO4 as nitrogen source, duction using wastewaters from a municipal WWTP
the total FAMEs content of 22% was obtained. as nutritional sources”. Bioresource Technology. Vol
The main compounds of FAMEs were C16:1 and 131, pp. 515–520, 2013.
C18:2 (Fig. 2). Xiong et al. (2008) also reveals Clayton T.D., Byrne, R.H., Breland, J.A., Feely, R.A.,
that adding yeast extract 1 g/L could enlarge the Millero, F.J., Campbell, D.M., Murphy, P.P., and
Lamb, M.F., “The role of pH measurements in mod-
microalgae growth ability but it can’t help the lipid ern oceanic CO2-system characterizations: Precision
accumulation. and thermodynamic consistency”. Deep Sea Research
Part II: Topical Studies in Oceanography. Vol 42,
pp. 411–429, 1995.
4 CONCLUSIONS Dismukes G.C., Carrieri, D., Bennette, N., Ananyev,
G.M., and Posewitz, M.C., “Aquatic phototrophs:
efficient alternatives to land-based crops for biofuels”.
Chlorella sp. G22 isolated from the beach in Taiwan Current Opinion in Biotechnology. Vol 19, pp. 235–240,
could utilize textile wastewater to grow and cumu- 2008.
late the lipid in the biomass. Microalgae G22 could Dubois M., Gilles, K., Hamilton, J., Rebers, P., and
remove the pollutant such as colorization, NH4+-N Smith, F., “Colorimetric method for determination of
and COD. The results show that adding extra phos- sugars and related substances”. Anal Chem. Vol 28,
phate and nitrogen sources could enhance NH4+-N, pp. 350–356, 1956.
COD and color removal efficiencies (>60%) while Ghirardi M.L., Zhang, L., Lee, J.W., Flynn, T., Seibert,
Chlorella G22 was cultivated at pH 10 and raw tex- M., Greenbaum, E., and Melis, A., “Microalgae: a
tile wastewater with and without aeration. Adding green source of renewable H2”. Trends in Biotechnol-
ogy. Vol 18, pp. 506–511, 2000.
(NH4)2SO4 as the extra nitrogen source with aera- Ho S.-H., Chen, C.-Y., and Chang, J.-S., “Effect of light
tion conditions, total FAMEs content could reach intensity and nitrogen starvation on CO2 fixation
>22% in microalgae G22 biomass. and lipid/carbohydrate production of an indigenous
microalga Scenedesmus obliquus CNW-N”. Biore-
source Technology. Vol 113, pp. 244–252, 2012.
Khozin-Goldberg I., and Z. Cohen, “The effect of phos-
ACKNOWLEDGEMENTS phate starvation on the lipid and fatty acid compo-
sition of the fresh water eustigmatophyte Monodus
The authors gratefully acknowledge the financial subterraneus”. Phytochemistry. Vol 67, pp. 696–701,
supports of Ministry of Science and Technology 2006.
(NSC 102–2218-E-035 -010) and Feng Chia Uni- Komolafe O., Velasquez Orta, S.B., Monje-Ramirez, I.,
versity, Taiwan. Noguez, I.Y., Harvey, A.P., and Orta Ledesma, M.T.,
“Biodiesel production from indigenous microalgae
grown in wastewater”. Bioresource Technology. Vol
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and Puhakka, J., “Biogenic hydrogen and methane
Anastasi A., Spina, F., Prigione, V., Tigini, V. Giansanti, P., production from Chlorella vulgaris and Dunaliella
and G.C. Varese, “Scale-up of a bioprocess for textile tertiolecta biomass”. Biotechnology for Biofuels. Vol
wastewater treatment using Bjerkandera adustaOrigi- 4, p. 34, 2011.
nal”. Bioresource Technology, Vol 101, pp. 3067–3075, Lakaniemi A.-M., Tuovinen, O., and Puhakka, J., “Pro-
2010. duction of Electricity and Butanol from Microalgal
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Association, 1995. Lin T.-S., and Wu, J.-Y., “Effect of carbon sources on
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70
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Correlation of highway traffic and NOx concentration level

K. Maneva & F. Skácel


Department of Gaseous and Solid Fuels and Air Protection, University of Chemistry and Technology,
Prague, Czech Republic

ABSTRACT: The main objective of this work was the validation of the correlation between nitrogen
oxides level across highway and the traffic intensity. The purpose of the work was to provide measure-
ments of the overall NOx concentration in a location where high traffic fluxes occurs. A representative
sampling site (short tunnel) was chosen without meteorological disturbances. Measurements were per-
formed during the period of 2013 to 2015 in Zelený most (short tunnel), located in Pardubice region,
in Czech Republic. Time series of measured NOx concentrations were used while simultaneously traffic
activity counting was performed. Regarding the traffic counting, the passing vehicles were divided in
different categories. The experimental work yielded reliable results of the mutual correlation of NOx con-
centration level and vehicles activity with statistical evidence. Emission factors from emission model for
road transport were applied.

1 INTRODUCTION main source of high NO2 concentration in the air is


mobile activities. Average NO2 concentration level
In the last decades with growing human popula- depend on meteorological conditions and wind
tion and their activity the atmospheric abundance direction but most dominantly on the distance of
of many emitted pollutants continues to increase. the measurement site from highways [11, 13].
Due to this problem, air pollution became one of
the main topics of environmental protection. The
characteristics of air pollution are different in dif- 2 EXPERIMENT
ferent areas and depend on the differences in mete-
orological conditions and human activities [1, 2]. The focus of this work is to measure the overall
In urban areas due to anthropogenic-stationary, NOx level in a location where high traffic is main-
industrial processes and mobile activity the level of tained. Motorways and roads are among the most
air pollution is higher [3]. polluted areas, suitable for measurements. For NOx
Nitrogen oxides are part of the primary pol- measurements is important to find a remarkable
lutants originating from traffic exhaust systems sampling site where can be obtained highly time-
[4]. Nitrogen oxides NOx express the total sum of resolved measurement of NOx concentration and
nitric oxide NO and nitrogen dioxide NO2 [5, 6]. traffic activity counting.
Nitrogen oxides are dominantly produced during
high temperature combustion from the exhaust
2.1 Sampling site
systems as nitric oxide [4, 7, 8]. However, NO dur-
ing a short period is oxidized to NO2 [7–9]. Nitrogen oxides emission was measured in Zelený
In atmospheric chemistry nitrogen oxides have most (short tunnel). The bridge is located on high-
a very important role. Included in many chemical way D11 in Pardubice region, eastern of Prague,
reactions in the atmosphere, NOx are precursors in Czech Republic. In this section of D11 highway
of the tropospheric ozone formation, photochemi- high traffic intensity occurs. The advantage of
cal smog and acid rain [4]. Emitted NOx in the tunnel measurements is the tunnel structure char-
atmosphere can cause serious harmful effects on acteristics that limit air circulation and therefore
the environment and human health [10]. In areas meteorological effects can be eliminated.
that are more populated, industrialized and where
intensive traffic occurs, NOx concentration level is
2.2 Measuring system and data processing
higher. Nitrogen dioxide is more toxic then nitric
oxide [11]. As a result of the fast transformation The measurements of NOx concentration were
of NO to NO2, the most harmful influence can performed using the Horiba APNA-360 Nitrogen
be attributed to the presence of the later [12]. The Oxide Analyzer. The Nitrogen Oxide Analyzer is

71
mass of a pollutant per driven distance (g/km).
This model is used to describe the average emis-
sion rate of a pollutant (NOx) corresponding to
a specific activity of an emission source such as
vehicles [19, 20].
The advantage of HBEFA program is the vari-
able case preposition with different driving cycles.
This data base dispose with pollutants emission for
all adequate categories of vehicles: passenger cars,
heavy and light commercial vehicles, motorcycles,
urban buses etc. HBEFA presents many optional
parameters for the traffic scenario including usual
driving conditions with different speed limits and
route gradients [17–19, 21].

3 RESULTS AND DISCUSSIONS


Figure 1. Semi-circular tunnel used for the ambient air
sampling. The work was based on short-term daily measure-
ments carried out in different week days at different
hours during the course of the day and at various
based on chemiluminiscence principle using multi- meteorological conditions. The measurements were
flow modulation method that makes possible syn- performed during the years 2013 to 2015.
chronic and separate measurements of NO, NO2 The sampling point was chosen to be situated at
and NOx [14]. The analyzer was calibrated by an 2 m above the ground level. That is the point where
accredited calibration laboratory in Czech Repub- the highest NOx mass concentration was detected.
lic. The analyzed air was drawn to the analyzer All the results and discussions in this section are
through a probe positioned in the middle of the described for one day measurement-Tuesday, Feb-
highway and PTFE (polytetrafluoroethylene) sam- ruary 17, 2015.
pling tube. In Figure 2 the mass concentration progress
For tunnel measurements is very convenient to during the measurement for the analyzed com-
use a statistical data processing. Analysis of vari- pounds i.e. NO, NO2, NOx is shown. Additionally,
ance ANOVA is a statistical method that is usually in order to compare the differences in NOx concen-
applied to compare the equality of more than two tration on road and in the near surrounding air,
population means [15]. ANOVA technique appli- the background mass concentration of NOx was
cation determines whether the variance between determined. The resulting values were almost sta-
samples is due to random errors or due to system- ble and the mean mass concentration of NO, NO2
atic treatment effects [16]. and NOx were 19.3 μg/m3, 41.5 μg/m3, 78.8 μg/m3,
respectively.
2.3 Emission factors for tunnel measurements
To obtain emission factors from the tunnel meas- Issues Issues
urements HBEFA 3.1 model was used. Handbook
Emission Factors for Road Transport (HBEFA)
is the most adjusted road traffic emission model
used in Austria, Germany, Switzerland, Norway
and France. HBEFA 3.1 is a data system with col-
lection of older and new measurements collected
in an improved model that dispose of all existing
data usage. Emission factors are used to inform
the contribution of road traffic emission and vehi-
cle emission. Emission Factors (EFs) can be used
for more than one vehicle category i.e. for whole
vehicle fleet [17, 18]. EFs depend on many param-
eters such as vehicle categories and characteris-
tics, emission control technology implementation,
Issues
operating conditions and fuel specification. Emis- Figure 2. Time course of the concentration progress for
sion factors for road traffic express the emitted the monitored compounds (February 17, 2015).

72
During another part of the measurement vehicle tracks + buses and the total number of motor vehi-
counting was performed. The motor vehicles were cles is depicted.
divided in two different categories: passenger cars To define the reliability of the results and to
and trucks + buses. The total number of vehicles examine if the correlation between the measured
for both categories was in 9 minute intervals calcu- data is linear, ANOVA analyses of variance was
lated. In Figure 4 the various traffic activities dur- used. The ANOVA analyses compares whether the
ing the day measurement are depicted. controlled factor has an important effect [16], in
addition whether the number of passing vehicles
3.1 Correlation effect the NOx mass concentration growth. With
analyses of variance is confirmed a strong linear
The aim of this section was to characterize the correlation between NOx emission and the traffic
impact of the traffic intensity on NOx concentra- intensity.
tion level measured in the short tunnel. Vehicle
counting and NOx mass concentration measure-
ment were simultaneously obtained. The meas- 3.2 HBEFA 3.1 calculation
urement was carried on for four hours. The actual In order to apply emission factors for particular
hourly concentration limit of NOx at standard research, the measurement has to contain collected
conditions is 200 μg/m3 [22]. Only one value was data of the chosen vehicle category and details
below the hourly NOx limit. adaptable to real driving scenario. In addition,
In Figure 3, 5 and 6 the correlation of NOx mass all collected information have to be incorporated
concentration and the number of passing vehicles, with the emission models. The tunnel road case
corresponded with the selection of parameters in
HBEFA 3.1. Therefore, this program was applied
and the measured values and modelled emission
factors by HBEFA 3.1 were compared.
In Figure 8 the correlation of the measured NOx
mass dependence and the number of passing vehi-
cles is depicted. In the same figure the values of the
measured NOx mass and the values of the calcu-
lated NOx mass for the different EFs are presented.
Additionally, in Figure 7 the NOx mass correlation
with the passing tracks and buses is depicted.
The emission factors were calculated for the
specific traffic case, constructed according to the
measurement location, vehicle category, speed
limit, road inclination gradient etc. The years 2005,
Issues 2010 and 2015 were selected as years chosen for the
Figure 3. Total number of all vehicle categories during
realization of the traffic compositions.
measurement time in 9 minute intervals (February 17, The measured NOx mass values are below
2015). the NOx mass values calculated by the HBEFA

Issues Issues
Figure 4. Correlation of NOx mass concentration Figure 5. Correlation of NOx mass concentration
dependence and number of passing passenger vehicles dependence and number of passing trucks and buses
(February 17, 2015). (February 17, 2015).

73
Face Tough

Face Tough Face Tough


Figure 6. Correlation of NOx mass concentration Figure 8. Correlation of the NOx mass dependence and
dependence and number of passing of the both catego- number of passing trucks and buses (February 17,2015).
ries (February 17, 2015).

Face Tough the structure of that fleet in HBEFA related more


likely to year 2010.

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NOx. Atmospheric Environment, 2000. 34(12–14):
pp. 2063–2101.
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Carslaw C. D. & Beevers D.S., Estimation of road vehicle
Figure 7. Correlation of the NOx mass dependence and primary NO2 exhaust emission fractions using moni-
number of passing vehicles (February 17, 2015). toring daata in London. Atmospheric Environment,
2005: pp. 167–177.
Colberg A. C. et al., Comparison of a road traffic
Table I. Analysis of variance (February 17, 2015). emission model (HBEFA) with emissions derived
from measurements in the Gubrist road tunnel,
3 minutes intervals Fcalc Fcrit Switzerland Atmospheric Environment, 2005. 39(26):
pp. 4703–4714.
NO Passenger cars 1.634 1.7 Dohnal L., DESATERO PRO POROVNÁVÁNÍ
VÝSLEDKŮ DVOU METOD., in Štatistické metódy
Trucks + Buses 1.689
pro klinickú epidemiológiu a laboratornú prax. 2008,
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NO2 Passenger cars 1.232 1.7 Slovakia.
Trucks + Buses 1.617 Franco V. et al., Road vehicle emission factors develop-
ΣPC+(T+B) 1.448 ment: A review Atmospheric Environment, 2013.
NOx Passenger cars 1.554 1.7 70(84–97).
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ΣPC+(T+B) 1.127 NO2 emissions in Europe. Atmospheric Environment,
2009: pp. 2154–2167.
Hausberger S. et al., Emission Factors from the Model
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results show a significant overestimation of the 1997: pp. 29–33.
NOx emission calculated using HBEFA 3.1 model. Last A. J. et al., Ozone, NO and NO2: Oxidant Air Pol-
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75
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Sorption of heavy metals from aqueous solutions using different types


of sorbents

M. Chlupáčová & H. Parschová


University of Chemistry and Technology, Prague, Czech Republic

P. Kůs
Research Centre Řež, Husinec—Řěž, Czech Republic

ABSTRACT: Metals transported into the environment through industrial, agricultural processes or
waste disposal have a large effect on public health and the economy. In this study, we observed the sorp-
tion of Ni, Cu and Fe ions from solutions of citric acid by three different types of chelating sorbents:
Amberlite IRC 748; Lewatit Mono plus TP 207 and Dowex M4195. Another tested sorbents were weakly
acidic cation exchangers with carboxylic functional group: Lewatit CNP 80 and Amberlite IRC 86. Unde-
sirable ions were separated from the aqueous solutions in both batch and column experiments. The aque-
ous samples were analysed by atomic absorption spectroscopy. Experiments were carried out in aqueous
solutions with different concentrations of citric acid and various pH values for each type of the tested
sorbent in order to find practical operating conditions. Sorption efficiency and sorption kinetics were
measured. The operating conditions of sorption process were discussed in this paper.

1 INTRODUCTION Chelating sorbents are a special type of sorbents.


These sorbents are selective to metal ions in appro-
Heavy metals, released from chemical industries, priate pH value. A chelating sorbent essentially
are frequent contaminants of water. The main consists of two components: the chelate forming
sources of heavy metals are: the wastewaters from functional group and the polymeric matrix. If the
plating facilities; battery manufacturing; fertilizer; selectivity of the sorbents is determined mainly by
paper and pesticides; metallurgical; mining; fossil the chelating group, other analytical properties of
fuel; tannery and power plants. The pollution of the sorbents, namely the capacity, kinetic features,
heavy metals as they tend to accumulate in living mechanical and chemical strength and regeneration
organisms has been causing worldwide concern. depend on the polymeric matrix. The most com-
Heavy metals of particular concern, in treatment of mon chelating sorbents have iminodiacetate (IDA)
industrial wastewaters include copper, nickel, zinc, functional group. Chelating sorbents are produced
cadmium, chromium, lead and arsenic (Valverde by chloromethylation of polystyrene with divinyl-
et al., 2004; Dabrowski et al., 2004; Li-Chun Lin benzene than with reactions with ammonia and
et al., 2007). chloroacetic acid. These sorbents adsorb metal
Various techniques are used for removal of met- ions with combination of ionic and coordination
als: precipitation-filtration, ion exchange, reverse interactions (Figure 3) instead of electrostatic
osmosis, oxidation-reduction, solvent extraction interactions (Jelínek et al., 2009).
and membrane separation. Compared with other Another type of chelating sorbent is known as
usual methods ion exchange provides advantages. bispicolylamine, sorbent with bis(2pyridylmethyl)
The main advantage is that the sorbents can be amine functional group (Figure 6). Nowadays, sep-
easily recovered and reused by regeneration opera- aration and purification of metal ions from water
tion (Hubicki et al., 2012). According to previous with this type of sorbent is considered (Wolowicz
studies various types of sorbents (weakly acidic et al., 2012). The example of such commercially
cation exchanger, chelating sorbents, weakly basic available sorbent is Dowex M4195. The main
anion exchanger) can be used for removal of heavy advantage of this sorbent is the ability to selec-
metal ions from water and industrial wastewaters tively capture transition metal ions from solution
using ion exchange technique (Li-Chun Lin et al., with pH less than 2 (Diniz, C. V. et al., 2005).
2007; Dabrowski et al., 2004; Li-Chun Lin et al., In this study, we use batch experiments with five
2005). different commercial types of sorbents according

77
to find suitable operating conditions for the sepa- dirt and dust particles. After this treatment were
ration of metals from aqueous solutions of citric sorbents converted to Na+ form and H+ form.
acid. We identify the resin with the most appropri-
ate structure and, thus, properties for the separa-
2.2 Batch studies with nickel and copper solutions
tion process from acidic solutions.
In order to obtain the ion exchange equilib-
rium data, batch experiments were carried out
2 EXPERIMENTAL in monometallic aqueous solutions of various
concentration of citric acid (1, 2.5, 5 and 10
2.1 Reagents and sorbents g.L−1). A specified amount of resin in hydro-
gen and sodium form (0.25 ml) was added to
In the previous studies, the authors have estab-
polyethylene bottles containing 250 ml of aque-
lished the technical feasibility of applying chelat-
ous solutions with 5 mg.L−1 of metal (copper,
ing sorbents and weakly acidic cation exchangers
nickel) concentration. The bottles were sealed
to recover metals from the aqueous solution (Li-
and placed in constant temperature (23°C) for
Chun Lin et al., 2007; Dabrowski et al., 2004; Li-
49h to reach equilibrium. Sorption efficiency
Chun Lin et al., 2005; Wolowicz et al., 2012). In
was observed in following time intervals: 1h, 2h,
this study, for the separation of metals from aque-
4h, 24h, 48h and 49h. Aqueous samples were
ous solutions of citric acid, were chosen five differ-
analysed by atomic absorption spectrometry
ent types of commercial sorbents: Amberlite IRC
(Atomic Absorption Spectrometer SpectraAA
748, Lewatit Mono plus TP207 and Dowex M4195
220, VARIAN).
(Table 1.) and weakly acidic cation exchangers:
Amberlite IRC 86, Lewatit CNP80 (Table 2).
All solutions were prepared from analytical grade 2.3 pH effect on sorption process
chemicals: FeSO4(NH4)2SO4.6H2O, MgSO4.5H2O
Batch experiments with weakly acidic cation
and NiSO4.7H2O. For all solutions demineralized
exchangers were carried out in aqueous solutions
water with conductivity value <0.1 μ[Link]−1 was
of citric acid and the pH was adjusted to 3, 5, 6,
used. Before sorption all types of sorbents were
and 8 using dilute NaOH. The adsorption experi-
put in demineralized water. After sorbents swelled,
ment procedure was similar to the equilibrium
they were washed and decanted in order to remove
adsorption experiment as described previously.

Table 1. Basic specification of selected chelating 2.4 Batch and column studies with Dowex M4195
sorbents2,5,10.
Batch experiments were carried out in aqueous
Quality Amberlite Lewatit Mono Dowex solutions of citric acid (10 g.L−1) of pH value 2.
parameter IRC 748 plus TP207 M4195 A specified amount of sorbent in activated form
(0.25 ml) was added to polyethylene bottles con-
Matrix polystyrene polystyrene polystyrene
Functional iminodiacetic iminodiacetic bis-
taining 250 ml of aqueous solutions with 5 mg.L−1
group acid acid picolylamine of metal (copper, nickel, iron) concentration.
Ionic Na+ Na+ Weak base/ Column experiment was used as a simulation of
form as partial real working conditions. The experiment was car-
shipped H2SO4 salt ried out at room temperature (23°C). The amount
Total 1.75 eq.L−1 2.2 eq.L−1 1 eq.L−1 of 15 mL of Dowex M4195 in activated form was
exchange imported in a glass column with 1 cm diameter, and
capacity with the aid of a peristaltic pump the polymetallic
solution of citric acid (10 g.L−1), copper, nickel and
iron (5 mg.L−1) was flowed with constant speed
Table 2. Basic specification of selected weakly acidica- and specific flow rate (10 BV.h−1).
tion exchangers1,9.

Quality Amberlite Lewatit 3 DISCUSSION AND RESULT ANALYSIS


parameter IRC 86 CNP80
The experimental results and the relevant observa-
Matrix polyacrylic polyacrylic
Functional carboxylic carboxylic
tions are compared by ion concentration uptake
group acid acid to solid phase and sorption efficiency in per-
Ionic form as shipped H+ H+ centage. The ion concentration uptake to solid
Total exchange capacity 4.10 eq.L−1 4.3 eq.L−1 phase was computed using the following balance
equation (1):

78
cations. Thus, when the citric acid is in high
⎡ ⎛ ( ρ0 − ρi ) × Vs ⎞ ⎤
concentration, the sorption process could be
⎢ ⎝ Vr ⎠ ⎥
⎢q = × 1000 ⎥ × z [ ⋅ 1
] (1) complicated.
⎢ MA ⎥ Experiments were performed with sorbents in
⎢⎣ ⎥⎦ hydrogen and sodium form. Hydrogen form was
more efficient in most cases. It is possible that
Where: ρ0 is concentration of ions in the initial the hydrogen form helps to cleave complexes and
solution [mg.L−1], ρi is concentration of ions at the allows sorption of copper. Lewatit TP 207 Mono-
output in the sampling time [mg.L−1], q is amount plus in sodium form had the highest value of the
of captured ions by cation exchanger [eq.L−1], Vs sorption efficiency, in less concentrated solutions.
is volume of solution [L], Vr is volume of cation Also Amberlite IRC 748 had high values of the
exchanger [L], MA is molecular weight [[Link]−1], z sorption efficiency in both hydrogen and sodium
is ion charge. forms. It is obvious, for the sorption process in
Percentage adsorption was calculated using the environment of citric acid, tested sorbents
equation (2) as follows: are inadequate. The initial pH of solutions in
experiments with weakly acidic cation exchang-
(c0 ci ) ers was modified with 10 M NaOH within the
A= × 100 [%] (2) range of 3–8. The value of sorption efficiency was
c0 increasing with increasing value of pH, however
the sorption efficiency did not exceed 50%. Our
Where: A is sorption efficiency [%], c0 is inlet results indicate that tested sorbents should be
concentration [mg.L−1], ci is concentration of ions used in applications with low concentration of
at the output in the sampling time [mg.L−1]. citric acid.
Figure 1 and 2 reveals the amount of captured
3.1 Equilibrium adsorption experiment Cu copper ions to functional groups of chelating sorb-
ents with the highest value of sorption efficiency in
In Table 3 sorption efficiencies in percentage aqueous solutions.
of tested sorbents are shown. All experiments
with the concentration of citric acid 10 g.L−1
were unsuccessful and many experiments with
concentration of citric acid 5 g.L−1 likewise.
Based on the results of the performed batch
experiments it can be assumed that the presence
of citric acid complicates the sorption process.
The citrate ion forms complexes with metallic

Table 3. Percentage adsorption of selected sorbents in


experiments with copper ions and different concentration
of citric acid.

1 g/L 2.5 g/L 5 g/L 10 g/L


Figure 1. The amount of captured copper ions to func-
tional groups of Lewatit MonoPlus TP207.
Amberlite IRC 31% 19% 32% −
748 H+
Amberlite IRC 23% 31% − −
748 Na+
Amberlite IRC 30% 29% − −
86 H+
Amberlite IRC 26% 28% − −
86 Na+
Lewatit MonoPlus 21% 28% 29% −
TP207 H+
Lewatit MonoPlus 34% 32% − −
TP207 Na+
Lewatit CNP80 26% 26% 17% −
H+
Lewatit CNP80 10% 10% − −
Na+ Figure 2. The amount of captured copper ions to func-
tional groups of Amberlite IRC 748.

79
3.3 Equilibrium adsorption experiment Dowex
M4195
Batch experiments were carried out in aqueous
solutions of citric acid (10 g.L−1) of pH value 2.
Our results (Figure 5) showed that sorption proc-
ess with Dowex M4195 was successful in aqueous
solutions even at low pH.
The bis-picolylamine ligand contain three
nitrogen donor atoms of electron pairs (Figure 6)
and at low pH all nitrogen atoms are protonated
(Grinstead et al., 1984). This fact could explain the
successful sorption of metal ions in experiments
Figure 3. Structure of chelating sorbent. with monometallic solutions of copper and iron.
Apart from tested chelating sorbents with imino-
diacetate functional group and weakly acidic cation
Table 4. Percentage adsorption of selected sorbents in exchangers, in case of Dowex M4195 the presence
experiments with nickel ions and different concentration of citric acid simplify the sorption process.
of citric acid. In Figure 7 sorption efficiencies in percentage
1 g/L 2.5 g/L 5 g/L 10 g/L are shown. It can be clearly seen that even at high
citric acid concentration and very low pH sorp-
Amberlite IRC 26% − − − tion, Dowex M-4195 can adsorb many heavy metal
748 H+ ions from single-metal solutions, but has a low
Amberlite IRC 46% − − − affinity for nickel. Sorption efficiency in case of
748 Na+
Amberlite IRC 37% 29% 28% 24%
86 H+
Amberlite IRC 95% 70% 54% 50%
86 Na+
Lewatit MonoPlus 27% 19% 14% 12%
TP207 H+
Lewatit MonoPlus 33% 33% 12% 12%
TP207 Na+
Lewatit CNP80 46% − − −
H+ Figure 4. Structure of weakly basic cation exchanger.
Lewatit CNP80 54% 42%% 42% 41%
Na+

3.2 Equilibrium adsorption experiment Ni


In Table 4 sorption efficiencies in percentage
of tested sorbents are shown. In experiments
with nickel ions weakly acidic cation exchangers
(Figure 4) had the highest value of sorption effi-
ciency. Nevertheless it can be clearly seen that
the presence of citric acid complicates the sorp-
tion process as it did in experiments with copper
ions. Experiments were performed with sorbents
in hydrogen and sodium form. Amberlite IRC Figure 5. The amount of captured ions to functional
groups of Dowex M4195.
86 in sodium form had the highest value of the
sorption efficiency, in less concentrated solutions.
The initial pH of solutions in experiments with
weakly acidic cation exchangers was modified with
10 M NaOH within the range of 3–8. The value
of sorption efficiency was increasing with increas-
ing value of pH. Experiments proved that chelat-
ing cation exchangers are not suitable option for
nickel separation. Figure 6. Structure of bispicolylamine sorbent.

80
As Dowex M4195 seems to be promising, future
studies are needed to observe selectivity and kinet-
ics of sorption process in order to find practical
operating conditions.

ACKNOWLEDGEMENT

The authors gratefully acknowledge “Financial


support from specific university research (MSMT
No 20-SVV/2016)” and the financial support from
the Research centre Řež (project SUSEN).

Figure 7. Percentage adsorption of Dowex M4195 in


REFERENCES
experiments with nickel, copper and iron ions.
Amberlite IRC 86. 2006. Production information. Rohm
monometallic solution with copper and iron was
and Haas Company.
over 50%, thus could be considered as successful. Amberlite IRC 748. 2006. Production information. Rohm
Column processes results confirm results from and Haas Company, (2006).
batch experiments. Future studies are needed to Dabrowski, A., Hubicki, Z., Podkoscielny, P. & Robens, E.
observe selectivity and kinetics of sorption process 2004. Selective removal of the heavy metal ions from
in order to find practical operating conditions. waters and industrial wastewaters by ion-exchange
method. Chemosphere, 56: 91–106.
Diniz, C.V., Ciminelli, V.S.T. & Doyle, F.M. 2005. The use
4 CONCLUSIONS of the chelating resin Dowex M-4195 in the adsorp-
tion of selected heavy metal ions from manganese
solutions, Hydrometallurgy, 78: 147–155.
Batch experiments were carried out in aqueous Dowex M4195. 2002. Production information. Dow
solutions of citric acid of various concentrations Company.
and of various pH values for each type of the tested Grinstead, R.R. 1984. New Developments in the Chem-
sorbents in order to find practical operating condi- istry of XFS 4195 and XFS 43084 Chelating Ion
tions for the selected sorbents. Chelating sorbents Exchange Resins, Ion Exch. Technol., Horwood
are commonly used sorbents for the removal of Chichester: 509–518.
metal ions from different aqueous solutions. Those Hubicki, Z. & Kołodyńska, D. 2012, Selective Removal
containing heavy metal ions and complexing agents of Heavy Metal Ions from Waters and Waste Waters
require special attention. As it can be clearly seen in Using Ion Exchange Methods, Intech., Chapter 8,
193–194.
Table 3, all experiments with the highest concentra- Jelínek, L., Parschová, H., Paidar, M. & Mištová E. 2009.
tion of citric acid were unsuccessful. Many experi- Desalinační a separační metody v úpravě vody, Praha:
ments with concentration of citric acid 5 g.L−1 also VŠCHT, ISBN: 978-80-7080-705-7.
showed zero sorption efficiency. Sorbents with imi- Lewatit CNP 80. 2011. Production information, LanXess.
nodiacetate functional group are better option for Lewatit Mono plus TP 207. 2011. Production informa-
sorption processes with the presence of citric acid tion, LanXess.
than weakly acidic cation exchangers with carboxy- Lewatit TP-207, Journal of Chemical Technology and Bio-
lic group in case of copper removal. technology, 79: 1371–1375.
In experiments with nickel ions weakly acidic Li-Chun Lin & Ruey-Shin Juang. 2005. Ion-exchange
equilibria of Cu(II) and Zn(II) from aqueous solu-
cation exchangers had better sorption efficiency tions with Chelex 100 and Amberlite IRC 748 resins,
than chelating sorbents (Table 4). Nevertheless the Chemical Engineering Journal, 112: 211–218.
conclusion based on the results of the performed Li-Chun Lin & Ruey-Shin Juang. 2007. Ion-exchange
batch experiments is that the presence of citric acid kinetics of Cu(II) and Zn(II) from aqueous solutions
complicates the sorption process in both nickel with two chelating resins, Chemical Engineering Jour-
and copper removal. Tested chelating sorbents and nal, 132: 205–213.
weakly acidic cation exchangers are not considered Valverde, J., Lucas, A., Carmona, M., Gonzalez, M. &
as satisfactory for technological processes of cop- Rodrıguez, J.F. 2004. Equilibrium data of the exchange
per and nickel removal. of Cu2+, Cd2+ and Zn2+ ions for H+ on the cationic
exchanger.
On the contrary, Dowex M4195 with bispi- Wołowicz, A. & Hubicki, Z. 2012. The use of the chelat-
colylamine functional group was proved as useful ing resin of a new generation Lewatit MonoPlus
option in sorption processes even at high citric acid TP-220 with the bis-picolylamine functional groups in
concentration and very low pH (Figure 5,6) in case the removal of selected metal ions from acidic solu-
of copper and iron removal. tions, Chemical Engineering Journal, 197: 493–508.

81
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Separation of noble gas from helium

M. Janák & K. Ciahotný


Department of Gaseous and Solid fuels and Air Protection, University of Chemistry and Technology,
Prague, Czech Republic

ABSTRACT: The separation of noble gases from helium can be used for an advanced gas cooled nuclear
reactors. The noble gases as krypton and xenon can be released into a primary circuit during a nuclear
reaction and contaminate cooling medium - helium. This separation system is considered as safety puri-
fication system. For the separation was used an experimental adsorption column. Two types of activated
carbon were tested during experiments. The separation efficiency was confirmed at pressure of 40 bar and
a temperature 22°C. Efficiency of the separation was improved by decreasing temperature to −40°C. After
experiments were evaluated and compared results for both types of activated carbon. Experiments shows
a high capacity for xenon for both types of activated carbon. The used analytical method was GC/PDHID
(gas chromatograph with the pulsed discharge helium ionization detector).

1 INTRODUCTION contaminants such as H2, CO, CO2, CH4, N2, O2,


H2O. The contamination of helium coolant can
The growing world population is followed by ever occur among others due to degassing, water or
increasing demand of electrical energy. Currently oil leaks and desorption from structural materials.
in order to satisfy consumers demand the energy Impurities can lead to series chemical reaction and
sector is heavily dependent on fossil fuels. It should case corrosion of component of the reactor [7-10].
be taken into account that fossil fuels are a lim- Those impurities are non-radioactive and can be
ited resource and additionally their combustion separated in purification systems for primary cool-
is one of the main sources of atmospheric pollu- ant [11].
tion. In fact for instance the EU continues to limit The radioactive gases and volatiles from nuclear
the burning of fossil fuels through various legis- reaction (noble gasses Xe, Kr, Ar or I, Cs) can rise
lative instruments [1]. Therefore it is important to or defunding to primary coolant when fuel cover
develop energy sources stable, economical and with is damaged. For emergency situation, when larger
low environmental impact. Nuclear energy due to amounts of fuel cell, there can be used emergency
its long term sustainability has attracted a lot of purification system. System for adsorption of
attention as a way of electricity generation [2]. noble gases can be used for control of radiation in
The two of the six concepts for future nuclear primary circuit.
reactors the IV. Generation are gas cooled reac-
tors VHTR (Very High Temperature Reactor)
and GRF (Gas-cooled fast reactor). The Genera- 2 EXPERIMENTAL
tion IV systems are intended to provide significant
advances compared with the current Generation Laboratory experiments at UCT Prague were
III/III+ regarding efficiency, economic, safety, focused on sorption separation of xenon and kryp-
radioactive waste reduction, environmental per- ton as the impurities of noble gases from helium.
formance, and proliferation resistance. However, As tested adsorbents were used two types of closely
the commercial application of Generation IV reac- porous activated carbon. Tests were conducted in
tors is not expected sooner than 2030 [3]. laboratory adsorption apparatus assembled in lab-
For those future gas reactors according to the oratories ICT Prague. Model gas is composed from
high operating temperature (1000°C—VHTR, main component which is helium with admixture
850°C—GFR) is necessary use helium for pro- of Xe, Kr in various concentrations.
tection materials caused undesirable chemical
reactions [4-6].
2.1 Adsorbents
Gaseous helium is an inert gas, stable at high
temperature and non-reactive. However helium Two types of activated carbon marked as C-46
coolant is expected to contain trace amounts of and K-48 were used as an adsorption material in

83
an adsorption column. C-46 and K-48 are closely 2.4 Analytical instruments
porous activated carbon.
Gas from the adsorption apparatus was ana-
Adsorbents were activated before experiments
lysed by gas chromatograph Aglient technologies
at least 10 hours at temperature 150°C to displace
model 7890B with the pulsed discharge helium
impurities trapped in storage (water, ambient air,
ionization detector D-3-1-7890. Used column was
organic vapours …).
ShinCarbon ST 100/120, length 2 m, ID 1 mm, OD
1/16 “Silico.
2.2 Working gas The set thermostat mode: initial temperature
The mixture of working gas: Helium + Krypton 60°C (hold for 2 minutes), then a temperature gra-
(500 cm3 m−3) + Xenon (1000 cm3 m−3) in pressure dient 30°C per minute up to 220°C, after reaching
bottle was used as working gas for testing adsorp- 220°C holding time 2.67 min at this temperature.
tion capacity of both types activated carbon. After The total analysis time was 10 min.
first experiment was determined adsorption iso-
therms from the mixture of gases which contained 2.5 Condition of experiment
lover amount of noble gases.
The pressure bottle with prepared mixture of
helium and Xe + Kr was used as working gas.
2.3 Laboratory apparatus
Pressure in the adsorption column was set to 4
For experiments were prepared an adsorption MPa. Gas from the apparatus flowed at pressure
laboratory apparatus operating at ambient tem- 0.1 MPa, flow 0.52 dm3⋅min−1 (p = 101.325 kPa,
perature with an overpressure gas up to 4.5 MPa. t = 0°C). Temperature during experiments was
The experimental device is placed in the aluminium 22°C.
structure. The individual components of the appa- Before the measurement the sorption appa-
ratus are connected by a stainless steel capillary ratus was purging by helium of purity 99.9999%
with a diameter of 6 mm from Swagelok. for 15 minutes at pressure 1 bar and at a flow rate
The pressure in the apparatus is regulated by of 0.5 dm3 min−1 to displace ambient air from
a pressure regulator from Brooks, which allows system.
adjusting the pressure in the range 1.5 to 4.5 MPa. Then the apparatus was pressurized to 4 MPa
At the exit the gas pressure is reduced throttle by working gas for 10 minutes to stabilize system.
automatic needle valve to a pressure of 0.1 MPa. After stabilization the experiment had been started
Gas mixture flow is controlled by the flow con- under the required conditions. Part of the outgo-
troller from the Brooks company operating within ing gas was discharged into the gas chromatograph
0.0–0.5 dm3⋅min−1. Controlling the flow regulator for analysis.
and pressure regulator is provided a digital control
panel from Brooks with display.
Laboratory apparatus configuration scheme is 3 RESULTS AND DISCUSSION
de-picted in Figure 1.
An adsorption column is from stainless steel Several experiments were performed to verify the
with volume 50 mL, length 145 mm and diameter sorption ability for both types of closely porous
21 mm. activated carbon. Total capacity of adsorbents

Face Tough Face Tough

Face Tough Face Tough


Face Tough Face Tough

Face Tough
Face Tough
Face Tough
Figure 1. Adsorption laboratory apparatus.

84
were counted to breakthrough point of entrance 3.1 Adsorption isotherms
volume of krypton or xenon. In the figure 2 is
The adsorption isotherms can predict adsorption
shown breakthrough curves of krypton and xenon
capacity for different input amounts of xenon or
adsorbed on activated carbon K-48. (Entrance
krypton.
amount of Kr 0.050% vol., Xenon 0.101% vol.)
The adsorption capacity is calculated as total
Flowed mass of working gas is recalculating to
capacity for adsorption isotherms. Partial pressure
sample weight 100 g of activated carbon.
individual gas components depends on concentra-
In the figure 2 is clearly visible that xenon have
tion of entrance gas mixture.
much more affinity to activated carbon. During
In the figure 4 is the adsorption isotherm for
the experiment after reaching total capacity of
krypton on activated carbon K-48 and in the
adsorbents for krypton was krypton released in
figure 5 adsorption isotherm for xenon at tempera-
higher amount than in working gas.
ture 22°C.
In the figure 3 is example breakthrough curves
And in the figure 6 is adsorption isotherm for
of krypton and xenon adsorbed on activated car-
krypton on activated carbon C-46 and in the fig-
bon C-46 with lower entrance amount of noble
ure 7 adsorption isotherm for xenon at tempera-
gases (Kr 0.032% vol., Xenon 0.068% vol.).
ture 22°C.
The adsorption curves are very similar for both
Adsorption isotherms for both activated car-
activated carbon for all concentrations of impuri-
bons are almost similar. On the figure 6 is isotherm
ties, differences in incapacities are seen in adsorp-
tion isotherms.

Figure 4. Adsorption isotherm for Kr on activated car-


bon K-48 at temperature 22°C.

Figure 2. Progress of sorption K-48 at the initial con-


centration: 0.050 Kr, Xe 0.101% vol.

Figure 5. Adsorption isotherm for Xe on activated car-


bon K-48 at temperature 22°C.

Figure 3. Progress of sorption C-46 at the initial con- Figure 6. Adsorption isotherm for Kr on activated car-
centration: 0.032Kr, Xe 0.068% vol. bon C-46 at temperature 22°C.

85
For the optimization of sorption device is now
testing at the UCT Prague conditions with lower
temperature during adsorption experiments for
increasing adsorption capacity for krypton.

REFERENCES

Abram, T. and S. Ion, Generation-IV nuclear power: A


review of the state of the science. Energy Policy, 2008.
Figure 7. Adsorption isotherm for Xe on activated car- 36(12): pp. 4323–4330.
bon C-46 at temperature 22°C. Baker, K. and G. Stoker, Nuclear Power and Energy
Policy: The Limits to Governance. 2015, Palgrave
Macmillan.
Burnette, R.D., et al., Chemical impurities in the helium
unfortunately little irregular, it can be caused by coolant at the Peach Bottom HTGR, in Gulf Gen-
error during preparation of the mixture or injec- eral Atomic. 1971, Philadelphia Electric Company:
tion of adsorbent into the adsorption column. California.
The adsorption capacity for the highest amount Collins, A.C., B.J. Gliddon, and P.J. Phennah, Helium
quality control and circuit purification. Journal Name:
xenon in gas mixture (0.10% vol.) is 9.91 g of
pp. 105–28 of Component Design in High Tempera-
xenon per 100 g activate carbon K-48 and 10.68 g ture Reactors Using Helium as a Coolant. London
of xenon per 100 g activated carbon C-46. Institution of Mechanical Engineers (1972).; Other
The adsorption capacity for the highest amount Information: From Conference on component design
krypton in gas mixture (0.05% vol.) is 0.23 g kryp- for high temperature reactors using helium as a cool-
ton per 100 g activate carbon K-48 and 0.40 g of ant; London, England (3 May 1972). See CONF-
krypton per 100 g activated carbon C-46. 720549. Orig. Receipt Date: 30-JUN-73; Bib. Info.
Source: UK (United Kingdom (sent to DOE from)),
1972: p. Medium: X.
Dulera, I.V. and D.N. Sah, High temperature reactors.
4 CONCLUSIONS
Journal of Nuclear Materials, 2008. 383: pp. 183–188.
Flegros, F., K. Liger, and M. Sardin, He purification sys-
Adsorption technology with closely porous acti- tem for GENIV nuclear reactor: study of H2 and CO
vated carbon is possible to use for separation of oxidation on CuO. 2009.
xenon and krypton from helium. Gastaldi, O., et al. Helium purification. in 3rd Interna-
The adsorption capacity for xenon is 9.91 g per tional Topical Meeting on High Temperature Reactor
100 g of activated carbon K-48 and 10.68 g per Technology. 2006. Johannesburg.
100 g of activated carbon C-46. It is very good Jan, B., Č. Michal, and M. Josef, Vysokoteplotní héliová
sorption capacity for both types of activated car- smyčka—Nové experimentální zařízení v ÚJV Řež a.s.
Paliva, 2010. 2: pp. 64–70.
bon and it can be used for removing noble gas
Liger, K. Helium chemistry control and monitoring for
xenon from helium. Gas Cooled Reactors. [Presentation] 2006 [cited 2016
The adsorption capacity for krypton is 0.23 g 4.5.]; Available from: [Link]
per 100 g of activated carbon K-48 and 0.40 g per Miletić, M., et al., Development of gas cooled reactors
100 g of activated carbon C-46. It’s low capacity. and experimental setup of high temperature helium
But it is possible to use closely porous activated car- loop for in-pile operation. Nuclear Engineering and
bon for separation krypton from helium, amount Design, 2014. 276: pp. 87–97.
of krypton is expected more than twice lower than Yao, M.S., et al., The helium purification system of
xenon. It can be used for two-stages separation the HTR-10. Nuclear Engineering and Design, 2002.
218(1–3): pp. 163–167.
system, in the first one will be separated xenon and
in the second (freeze) one krypton.

86
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Study on physicochemical factors influencing sorption capacity


in carbonate loop

M. Staf, K. Ciahotný, V. Vrbová & L. Jílková


Department of Gaseous and Solid Fuels and Air Protection, University of Chemistry and Technology,
Prague, Czech Republic

ABSTRACT: The study is concerned with problems in applicability of natural limestones for regenerative
chemisorption of carbon dioxide. The factors influencing reaction reversibility and sorption capacity were
researched. Relation between changes in capacity and elemental composition was tested on 11 limestones
with widespread range of properties. Testing of periodical hydration of calcinates was realised in order to
verify this approach as the efficient method for restoration of the initial capacity. For this purpose a fixed
bed apparatus with vertical reactor was constructed. The system allowed cyclical carbonation-calcination
steps with or without introduction of steam and/or SO2 into the sample layer. Relation among reaction
conditions, sorption properties, specific surface etc. was discussed. The sample, assessed as the most suit-
able for industrial scale utilisation, showed very positive effect of steam upon its capacity. Long term
stable transferring capacity of this sample exceeded 20 g of CO2 per 100 g of the initial limestone.

1 INTRODUCTION chemical bonding of CO2 in the form of carbonate.


The conditions essential for the cyclic course is
1.1 Research aims thermolability of the resulting carbonate. Only in
this case regeneration of the sorbent is allowed by
On the basis of international agreements Czech
reversing the chemical reaction due to increasing
Republic assumes obligations to reduce emissions
the temperature above the threshold of instability.
of greenhouse gases into the atmosphere. One of
According to preliminary tests three factors above
the partial steps, enabling to achieve these commit-
mentioned have a considerable effect on the revers-
ments, is implementation of procedures of carbon
ibility of chemisorption reactions. Tests in the
dioxide capture from flue gas, produced by existing
laboratory apparatus with fixed bed reactor repre-
power plants and other industrial technologies.
sented the fundament of the research.
Among all possible options of CO2 capture,
being developed in the world as well as in the Czech
Republic, research of post-combustion separation of
1.2 Actual published research and state of the art
this greenhouse gas is preferentially selected for retro-
fitting the existing combustion plants. As a particular In terms of initial sorption capacity CaO-based
technology carbonate loop, exploiting natural lime- sorbents represent very good starting platform in
stone as inexpensive sorbents, is intensively investi- comparison with other materials as published by
gated. The study hereby presented focuses on three Ciahotný et al. Desiring to avoid structural changes,
key factors, which determine the sorption proper- significantly degrading these sorbents during their
ties of natural limestones in terms of their use in the cyclical use, the research teams began carrying out
regenerative capture carbon dioxide. The impact of experiments in the following areas:
the three factors can be in the positive as well as nega-
− Preparation of mixed sorbents and CaO sorb-
tive sense. The evaluated factors were as follows:
ents derived from limestones,
1. Chemical composition of the raw material, − fixation of CaO layer on the surface of a solid
2. irreversible reaction of calcinate with residual support or in the binder lattice,
SO2 concentration in flue gas, − physicochemical regeneration of the cyclically
3. influence of hydration using water steam on loaded sorbent.
changes in sorption capacity during cyclical
An example of the first of aforementioned
carbonation/decarbonation repetitions.
methods can be preparation of mesoporous CaO
Carbonate loop can be defined as high tempera- using wet precipitation method as described e.g.
ture chemisorption process, based on a transient by Gupta and Fan. As an alternative method

87
preparation of CaO and MgO based sorbent by very important factor besides the final temperature,
mixing the organic salts of both elements with at which the individual phases of the working
D-gluconic acid was described. Liu et al. declared cycle were performed. Since the heating rate, and
very high resistance against sintering for this especially the process temperatures, can be set up
sorbent. only within relatively narrow limits, additional
Apart from simple, e.g. precipitation, methods procedures for sorbent reactivation are investi-
of sorbents preparation there were some sophis- gated simultaneously. Manovic published also very
ticated procedures proposed, leading to materi- promising results, obtained after application of
als resistant to sintering. One category of these steam into the calcined limestone. Thus it was one
methods is a solgel process, which was used by of the reasons why the hereby presented study is
Chen to prepare CaO-based sorbent with incor- oriented in this way.
porated oxides MgO, MnO2 and TiO2. For these
sorbents the author presents excellent sintering
resistance even after 50 cycles. 2 EXPERIMENTAL PROCEDURE
As shown by Martavaltzi a mixed sorbent CaO-
Ca12Al14O33 should exhibit very stable characteristics. Cyclic carbonations and decarbonations of
The author built on previous research published by samples were carried out in a vertical steel reac-
Li, which led to similar results. Reddy and Smirni- tor with internal diameter 20 mm. Simplified
otis described composite sorbents, containing CaO schematic sketch of the laboratory apparatus is
together with alkali metals and having the effect of depicted in fig. 1. Each experiment was done using
capacity drop suppressed during cycles. the same sample weight of 100 g and particle size
It was found that conversion of CaO into the of 1–2 mm. The weighed amount of the sample
nanostructural form also leads to increase in sorp- was loosely thrown into the adsorber. A cylindri-
tion capacity after exposition to multiple cycles. cal furnace, placed on a scissor hoist, served for
Results of preparation and testing of these materi- programmable heating of the reactor and its fast
als published Lu and Hong. cooling after each experiment. The apparatus was
Regarding the sorbents stabilized by incorpora- designed to allow working with different atmos-
tion of CaO into a suitable matrix the study, pub- pheres during calcination and carbonation step.
lished by Manovic and Anthony, represents good The inlet gas flow was controlled using a mass flow
example. The authors described preparation of meter/controller Bronkhorst EL-FLOW Select,
affordable and sintering resistant sorbents from equipped with an electromagnetic regulator.
limestone and suitable calcium aluminates-based
cements representing a binder. After 30 cycles the
prepared sorbents showed significantly smaller
decrease in capacity than pure limestone. Com-
parable results were also achieved by Li, however,
using more expensive process for CaO stabiliza-
tion, consisting of the use of spinel MgAl2O4 as
a binder instead of cement. Another example of
structural stabilization of CaO is based on applica-
tion of SiO2 as a carrier, as shown in studies of Lu,
Reddy and Smirniotis. Summarized overview of
other methods of preparation CaO-based sorbents
resistant to sintering as well as structural changes
is available in studies of Wang, Hedin and so on.
All of the above listed processes proposed for
preparation of the promising sorbents, however,
have one common drawback—more or less extra 1—pressure bottle with inert gas, 2—pressure bottle with
costs associated with purchase of the reactants and CO2 mixture, 3—needle valve, 4—flow meter, 5—flow
with synthesis of the desired product. This disad- controller, 6—water steam generator, 7—condensate drain
vantage cannot be eliminated unless an effective (during vapour reactivation), 8—scissor lift, 9—cylindrical
and relatively cheap process of restoring sorption oven, 10—preheating reactor zone, 11—sample zone,
properties of natural limestone is found. Above 12—controller of capillar preheating, 13—thermometer/
datalogger, 14—reactor bypass, 15—air cooler,
all several influences accelerating, or suppressing, 16-controlling flow meter, 17—IR spectrometer, 18—drum
undesirable structural changes and sintering were gas meter, 19—analyser bypass, 20—gas outlet.
investigated.
Manovic and Anthony identified heating rate, Figure 1. Schematic drawing of the experimental
used for material calcination (decarbonation), as apparatus.

88
The gas leaving the reactor was cooled to room Table 1. Basic physicochemical properties of tested
temperature in a pair of spiral air coolers and then limestones.
CO2 content was continuously measured by IR
analyser. The temperature of the sample was also Apparent
density Elemental composition
measured continuously with the identical record-
ing rate of 5 s. The K-type thermocouple was wt. %
positioned in the axis of the reactor, while the meas- Sample
uring point was vertically located in the middle of name [Link]−3 Ca Mg Si Al Fe K
the bulk layer of the sample. Decarbonation phase
proceeded by heating from ambient temperature LM1 2.80 39.59 0.22 0.09 0.00 0.00 0.00
to a final 850°C with heating rate of 10°[Link]−1 LM2 2.72 39.33 0.27 0.15 0.11 0.12 0.00
in nitrogen atmosphere. The inert gas flow was LM3 2.82 39.25 0.19 0.34 0.20 0.08 0.00
always maintained at 2 [Link]−1. Carbonation, how- LM4 2.85 38.67 0.46 0.40 0.24 0.14 0.00
ever, in all cases run under isothermal conditions LM5 2.64 38.63 0.34 0.50 0.23 0.00 0.00
at 650°C. LM6 2.73 36.63 1.27 1.00 0.65 0.25 0.14
Tests with carbon dioxide capturing were real- LM7 2.79 33.73 1.05 4.82 0.55 0.20 0.19
ised using two different gas mixtures simulating LM8 2.77 33.09 3.60 1.45 0.41 0.25 0.00
dry, dust-free flue gas from coal-fired power plant. LM9 2.74 31.35 0.95 4.81 2.62 1.25 0.83
LM10 2.51 29.80 0.49 6.96 3.23 0.87 0.78
In the first case the binary gas mixture contain-
LM11 2.77 27.76 1.03 9.47 2.09 0.96 0.57
ing 14 mol. % CO2 in nitrogen was used, while the
second mixture consisted of 13 mol. % CO2 and
0.3 mol. % of SO2 in nitrogen. After the calcination
phase two alternative steps were possible. When the The samples, which properties are summarized in
first arrangement of the experiments was applied Tab. 1., were marked LM1 to LM11. The values
only pure nitrogen flowed through the adsorber of the equilibrium sorption capacity of each sam-
during both calcination as well as the reactor cool- ple were compared with the theoretical capacity,
ing down to the carbonation temperature. Second calculated on the basis of analytically determined
arrangement of experiments was intended in order contents of CaCO3 and MgCO3.
to test steam hydration, verifying positive effect Relatively big drops of initial sorption capacity
of this process to sorption capacity. To achieve were detected for all samples, however, the variance
introduction of water steam into the sample’s layer in recorded capacity drops was not uniform across
nitrogen stream was redirected through the steam the sample base, but it was rather very wide. There
generator, where this inert gas was saturated by were searched possible relations among the ele-
water vapour and subsequently superheated by mental composition, BET surface and changes in
passing the system of heated capillaries. the measured equilibrium sorption capacity.
In the following paragraphs there are all values of
sorption capacities expressed as the weight of CO2
3 RESULTS AND DISCUSSION
captured in 100 g of dry sample of the correspond-
ing crude limestone before its first calcination.
3.1 Influence of cyclic carbonation/decarbonation
Theoretical capacity of tested limestones varied
In total 11 samples of natural limestones were in the range from 32.4 to 43.9 g.100 g−1, wherein the
included in the study. Their range covered samples average value reached 40.3 g.100 g−1 throughout the
from high-percentage limestones with CaCO3 sample base. In the first experimental cycle capaci-
content exceeding 98.8 wt. % to limestones con- ties ranging from 6.1 to 37.1 g.100 g−1 were recorded.
taining less than 70 wt. % of CaCO3 and having, Thus the corresponding relative values, related to
on the other hand, increased content of MgCO3 the theoretical capacity, were from 18.0 to 84.6%.
(up to 12.5 wt. %) and other impurities. Among During the six testing cycles a decrease in capacity
the aforementioned impurities SiO2 was domi- at the final range from 3.5 to 35.6 g.100 g−1 (i.e. 3.5
nant in the four samples with a maximum content to 35.6% of theoretical values) was observed.
over 20 wt. %. Al2O3 was the second main impu- The sample LM1 showed the highest capaci-
rity, which maximum content detected within the ties in all cycles and vice versa the sample LM10
sample base exceeded 6 wt. %. offered the worst results in all cycles as well. The
The decrease in capacity due to periodically capacities, reached by the limestone LM5, were
repeated phases of high temperature calcina- the most approaching the arithmetic average of
tion and subsequent isothermal carbonation the values calculated throughout the whole sample
was tested for each sample in six cycles. Selected base. Since LM5 is, in fact, a typical representative
number of cycles was found sufficient because it of “ordinary” limestones Fig. 2 shows the changes
showed a trend in achieved equilibrium capacities. of sorbed and desorbed CO2 just for this sample.

89
subjected to cyclic testing of decarbonation/
carbonation, showed a significant decrease in the
value of specific surface. While calcinates prior
to first carbonation showed BET surfaces in the
range from 1.5 to 7.9 m2.g−1, after the last carbona-
tion this interval was only 0.2 to 3.5 m2.g−1.
The sample LM1, reaching the highest capac-
ity during each cycle, had also the highest value of
the BET surface detected after the last cycle. The
Face Tough sample LM10 with the lowest capacities meas-
Face Tough ured, however, had the specific surfaces closely
Face ToughFace Tough approaching the average values for the entire sam-
Face Tough ple base both after the first calcination and after
the calcination carried out after the last cycle. Also
Figure 2. Decrease in capacities of the sample LM5 in the sample LM6 its largest recorded decline in
during cycles without steam regeneration or SO2 the relative capacity did not correspond with inap-
contamination.
propriate decrease in the BET surface. The value
of surface 2.1 m2.g−1, measured after the first cal-
Generally the capacities, measured for the cination, correlated with the capacity achieved in
samples containing higher concentrations of the first cycle, if compared with other samples. In
CaCO3, reached better values, which was consistent contrast, the decrease in the specific surface, evalu-
with the assumption. On the other hand, different ated after the last cycle, was significantly smaller
behaviour of the sample LM11 should be men- than it would proportionally correspond with
tioned. This sample contained the lowest calcium dramatic capacity drop. Based on the comparison
carbonate concentration among all materials, and of the respective values it can be concluded that
the highest content of admixtures with dominating the BET surface represents only one, but not the
Si with a weight content of 9.47 wt. %. Theoretical most important factor, determining the capacity of
capacity of the LM11 was therefore low. Accord- limestones and its amendments.
ing to expectancies the values of laboratory meas-
ured capacities should reflect this fact. In reality,
3.2 Effect of steam reactivation
the sample reached the values significantly better.
The biggest relative decline in capacity 81.1%., Two samples of limestone were involved in the
compared to the value obtained in the first cycle, experiments with steam introduction into the pre-
was detected for the sample LM6. The elemental heated layer of calcinate. The first of these speci-
composition of this sample, however, was very mens was the sample LM1, which showed the
close to the average values across the sample base. highest sorption capacities within all of the six
In contrast, the sample LM9 showed the small- test cycles as described above. Selected raw mate-
est decline in relative capacities compared to the rial belongs to the category of high percentage
initial state (53.5%). This limestone had, however, limestones, which are, in addition to the civil engi-
the third lowest analytically determined content neering, used in various industries (chemical, food
of CaCO3 and also the third lowest theoretical etc.). Important use of these materials is as agents
capacity. The same sample contained the highest for flue gas desulphurisation.
proportions of Fe and K, and the second highest Mineable reserves of such quality limestones are
content of Al. As the above described tests dem- indeed limited. Therefore LM5, showing the aver-
onstrated, only the content of CaCO3 refers to the age sorption characteristics when compared to the
capacity that can be achieved by cyclically repeated whole sample base, was chosen as the second sam-
carbonations and calcinations. The elemental com- ple for this follow-up phase of tests. Each of the
position alone does not provide a guide that would samples was subjected to ten cycles of calcination
be used for estimation of the range, within which and carbonation, wherein introduction of steam
the capacity may vary during cycles. into the calcinate layer was realised after each cal-
BET surface of calcined limestones was exam- cination step.
ined as the second parameter, on the basis of Changes in the weight of carbon dioxide sorbed
which it should be possible to estimate the sorption and desorbed by the sample LM5 is shown using a
capacity. The tests compared the surface of the cal- bar graph in Fig. 3. Comparison of figures 2 and 3
cinates before the first carbonation and the same brings very illustrative demonstration of the effec-
parameter for the calcinates prepared by thermal tiveness of steam regeneration. Mutual compari-
treatment of the samples after the last measured son of capacities of the both samples, subjected
carbonation in the sixth cycle. All specimens, to cyclical calcinations and carbonations with

90
powder was observed. It was therefore obvious
Children Face Tough Issues that this material undergoes structural changes in
the greater extent than the LM1. Bigger manifesta-
tion of thermal sintering with consequent destruc-
Children Face Tough Issues tion of the grains due to hydration was considered
as the probable cause.

3.3 Effect of low concentrations of SO2 in the


model gas
Children Face Tough Issues As well as the impact of introduction of steam,
also the influence of residual SO2 concentrations
was tested on the pair of limestones LM1 and
Children Face Tough Issues LM5. During the tests following parameters were
monitored in order to assess how their values were
Figure 3. Restoration of capacity of the sample LM5 influenced by the presence of SO2 in the model gas:
due to application of steam regeneration. total equilibrium capacity, time to reach equilib-
rium during carbonation, specific surface, pore
sizes distribution and total pore volume. SO2 con-
tent in the gas mixture during carbonation had very
similar impact to the capacity of both samples.
In the sample LM1 the equilibrium capacity
decreased from the value of 31.4 g.100 g−1 in the
first cycle to only 5.3 g.100 g−1 in the last sixth
cycle. In the sample LM5 the decrease was similar
and was in the range from 26.4 g.100 g−1 in the first
to 4.9 g.100 g−1 in the last cycle. From the above
mentioned values, and especially from the graph
connected in Fig. 5, it is obvious that the effect
Face Tough of limestone contamination by sulphur dioxide is
Face Tough almost the same both for the sample that was eval-
Children Face Tough uated as the best in all of the previously realised
tests and for the average sample as well.
Children Face Tough During the cyclical measurements of capac-
ity without steam reactivation or contamination
Figure 4. Comparison of changes in capacities for by SO2 differences between the samples LM1 and
cyclical tests with and without steam reactivation.

periodically repeated introduction of steam and


without this regeneration step, is visualized using
the segment graph in Fig. 4.
Some important findings can be deduced from
observing the graphs. In the case of both tested
limestones the introduction of steam led to signi-
ficant reduction of the loss of sorption capacity.
Likewise both samples suspended decreasing of
the capacity approximately after three calcination/
carbonation cycles. After the stabilization the aver-
age capacity in the range between fourth to tenth
cycles was 22.30 and 22.04 g.100 g−1 respectively.
From this point of view very similar results for
Face Tough Face Tough
both limestones were achieved. For the sample Children Face Tough
LM5 bigger fluctuations in the measured values of
sorption capacity are noticeable during cycles. It Children Face Tough
is necessary to examine this phenomenon in more
details. Even during visual inspection of the sample Figure 5. Course of declines in equilibrium capacities
LM5 after completion of all cycles substantially during carbonations using gas mixtures with and without
greater disintegration of the material into a fine presence of SO2.

91
LM5 were substantially constant from the first to series of experiments with low concentration of
the last cycle. But if the gas contained a defined SO2 in the gas, were compared with the same vari-
concentration of SO2 during carbonation, gradual ables, measured on calcinates from the both of pre-
approximation of capacities occurred, so the values vious series of experiments. Fig. 7 and 8 provide a
became practically identical since the fourth cycle. graphical comparison of those parameters.
Also the change in shape of breakthrough Exposure to sulphur dioxide resulted in sub-
curves was recorded when measurements were stantial decrease in both BET surface and total
carried out with gas mixture containing SO2. The pore volume. As evident, reaction with SO2 leads
graph in Fig. 6 shows the course of these curves to reduction of the pore volumes within the whole
for all three series of measurements. It is therefore range of the measured diameters. The method
possible to visually compare the change in CO2
sorption rate during tests using steam regeneration
and contamination by SO2. Comparison of shapes
of the breakthrough curves, recorded during car-
bonation without steam reactivation and without
the presence of SO2, and recorded during carbona-
tion in the presence of SO2, points out to a certain
paradox.
In the initial phase of tests in the presence of
SO2 both examined limestones sorbed even some-
what better than in the case of sorption of a
mixture without this substance. However, within
a relatively short time there was always a sharp
Children Face Tough
decline in the sorption rate, which can be observed
at the curve as almost vertical rise of output CO2
Children Face Tough
concentration. During the last stage of sorption, in
the contrast, breakthrough curves converged to the Children Face Tough
inlet CO2 concentration significantly slower than
in tests without SO2 or tests using steam reactiva- Children Face Tough
tion. In this phase, apparently, slow diffusion of
carbon dioxide into the structure of the calcinate Figure 7. Comparison of pore size distribution of the
occurred. Thus it is necessary to pose the question calcinate, prepared from the crude sample LM5, with
why presence of SO2 in the gas led to significant calcinates obtained after cyclical experiments with car-
deterioration in capacity of the sample LM1, so its bonations and decarbonations under three different
conditions.
capacity gradually aligned with the material LM5.
Values of BET surface and pore size distribu-
tion, determined on the calcinate prepared after
Children Face Tough

Children Face Tough


Children
Children Face Tough
Face Tough Children Face Tough
Children Face Tough
Children Face Tough
Children Face Tough Children Face Tough
Children Face Tough
Figure 8. Comparison of BET surface of the calcinate,
Figure 6. Comparison of breakthrough curves during prepared from the crude sample LM5, with calcinates
carbonation in fifth cycles under three different experi- obtained after cyclical experiments with carbonations
mental conditions. and decarbonations under three different conditions.

92
used could not ascertain how SO2 influenced pores ACKNOWLEDGEMENT
with larger diameters. Anyway, hypothesis regard-
ing deactivation by sulphur dioxide is as follows. This research was supported by grant from Norway,
CaSO4 molecule has greater volume than CaO project number: NF-CZ08-OV-1-005-2015.
molecule. Its origin is manifested by mechanical
disruption of previously formed sintered sites on
the particle of the calcinate. REFERENCES
Acceleration of CO2 sorption in the initial phase
Chen, H., Zhang, P., Duan, Y., Zhao, C. 2016. Reactivity
thus has the same reason as in the case of breaking enhancement of calcium based sorbents by doped
sinters by formation of Ca(OH)2 during applica- with metal oxides through the sol–gel process. Applied
tion of steam hydration. In the next stage, however, Energy 162: 390–400.
CaSO4 closes the porous structure of the material Ciahotný, K., Staf, M., Hlinčík, T., Vrbová, V., Jílková, J.,
and also creates a intact layer on the particles sur- Randáková, S. 2015. Removing carbon dioxide from
face. This deteriorates diffusion of CO2. Decrease flue gas using high temperature carbonate looping.
in total equilibrium capacity is then given by irre- Paliva 7 (3): 84–90.
versible reaction CaO + SO2. Gupta, H., Fan, L.S. 2002. Carbonation−Calcination
The answer to the question why there were a sig- Cycle Using High Reactivity Calcium Oxide for
Carbon Dioxide Separation from Flue Gas. Ind. Eng.
nificant deterioration in the capacity of the sample Chem. Res. 41 (16): 4035–4042.
LM1 is probably following. Limestone LM1 con- Hedin, N., Chen, L.J., Laaksonen A. 2010. Sorbents for
sists of 98.9 wt. % of CaCO3, while limestone LM5 CO2 capture from flue gas—aspects from materials
has 3.5 wt. % of impurities in its structure. During and theoretical chemistry. Nanoscale 2: 1819–1841.
the reaction with SO2 therefore more uniform layer Hong, L., Khan, A., Pratsinis, S., Smirniotis, P. 2009.
of CaSO4 is formed the surface of particles of Flame-made durable doped-CaO nanosorbents for
the sample LM1. Subsequently diffusion of CO2 CO2 capture. Energy Fuel 23: 1093–1100.
is more limited than in the case of the limestone Li, L., King, D.L., Nie, Z., Li, X.S., Howard, C. 2010.
LM5. MgAl2O4 Spinel-Stabilized Calcium Oxide Absorb-
ents with Improved Durability for High-Temperature
CO2 Capture. Energy Fuels 24: 3698–3703.
Li, Z., Cai, N., Huang, Y., Han, H. 2005. Synthesis,
4 CONCLUSIONS Ex-perimental Studies, and Analysis of a New
Calcium-Based Carbon Dioxide Absorbent. Energy
During realisation of tests without the use of steam Fuels 19 (4): 1447–1452.
reactivation very wide dispersion in progressions Liu, W., Feng, B., Wu, Y., Wang, G., Barry, J., da Costa,
of capacity changes was observed. If in practical J.C. 2010. Synthesis of sintering-resistant sorbents for
application of carbonate loop a source of steam is CO2 capture. Environ. Sci. Technol. 44(8): 3093–3097.
not available to ensuring periodic reactivation it is Lu, H., Reddy, E.P., Smirniotis, P.G. 2006. Calcium oxide
based sorbents for capture of carbon dioxide at high
necessary to apply preferentially limestones with a temperatures. Ind. Eng. Chem. Res. 45: 3944–3949.
maximum available CaCO3 content. Lu, H., Smirniotis, P.G., Ernst, F.O. 2009. Nano-
In case when steam supply and its introduc- structured Ca-based sorbents with high CO2 uptake
tion into the calcinator is technically available efficiency. Chem. Eng. Sci. 64: 1936–1943.
good and stable sorption capacity at 22 g.100 g−1 Manovic, V., Anthony, E.J. 2007. Steam reactivation of
can be achieved, even with limestones with lower spent CaO-based sorbent for multiple CO2 capture
CaCO3 content. Other experiments demonstrated cycles. Environ. Sci. Technol. 41: 1420–1425.
strongly negative impact of the presence of even Manovic, V., Anthony, E.J. 2009. CaO-Based Pellets
low concentrations of SO2 in the flue gas. During Supported by Calcium Aluminate Cements for High-
Temperature CO2 Capture. Environ. Sci. Technol. 43:
the first six cycles the capacity decreases to only 7117–7122.
5 g.100 g−1. Manovic, V., Anthony, E.J., Grasa, G., Abanades, J.C.
The follow-up research will be focused on tests 2008. CO2 looping cycle performance of a high-purity
of influencing the steam reactivation process in the limestone after thermal activation/doping. Energy
case the samples are exposed to low concentration Fuel 22: 3258–3264.
of SO2. Special attention will be paid on forma- Martavaltzi, C.S., Pampaka, E.P., Korkakaki, E.S.,
tion of magnesium sulphate heptahydrate. Because Lemonidou, A.A. 2010. Hydrogen production via steam
MgSO4 is strongly hygroscopic and is converted reforming of methane with simultaneous CO2 capture
into MgSO4.7H2O very easily good efficiency of over CaO–Ca12Al14O33. Energy Fuel 24: 2589–2595.
Reddy, E.P., Smirniotis, P.G. 2004. High-Temperature
the steam reactivation can be expected for the Sorbents for CO2 Made of Alkali Metals Doped on
limestones containing higher concentrations of CaO Supports. J. Phys. Chem. B 108: 7794–7800.
MgCO3. The above mentioned experiments will be Wang, Q., Luo, J., Zhong, Z., Borgna, A. 2011. CO2 cap-
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93
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Treatment of pig-waste slurry by a microbial fuel cell using different


types of plate electrode

M.F. Lai
Department of Fiber and Composite Martials, Feng Chia University, Taichung, Taiwan

J.H. Lin
Department of Fiber and Composite Martials, Feng Chia University, Taichung, Taiwan
School of Textiles, Tianjin Polytechnic University, Tianjin, China
School of Chinese Medicine, China Medical University, Taichung, Taiwan
Department of Fashion Design, Asia University, Taichung, Taiwan

ABSTRACT: Microbial Fuel Cells (MFC) is an electrochemical and biological systems related to
chemical energy into electrical energy. Resource recycling and the proper treatment of animal waste to
reduce its environmental impact are currently important issues for the livestock industry. MFC, new bio-
logical technology, is expected to play roles in both wastewater treatment and energy recovery. In this
study, a two-chambered cubic microbial fuel cell was used to evaluate the effect of two type of plate
electrodes, which made of iron and copper and carbon fiber, on the electricity generation from pig-waste
slurry. The swine wastewater containing Total Chemical Oxygen Demand (TCOD) 3300 ± 300 mg/L was
used as the feedstock in the anode chamber, and the potassium ferricyanide was used as an electron accep-
tor in the cathode chamber. The MFC reactor was incubated with the initial pH 7.0 in an air shaker at a
temperature (ca. 35°C) and 100 rpm with the fed-batch mode. A fixed external resistance (R) of 100 Ω
was connected between the electrodes and the closed circuit potentials of the MFCs were recorded every
2 min. The results show that using iron electrode has the peak electricity generation of 176 mV at the first
two days and maintained the stable voltage of 110 mV during the 5th to 15th days. The COD removal
efficiency could reach 80%. Using copper electrode only can generate the peak electricity of 19.5 mV and
carbon fiber stable voltage of 160 mV with the COD removal efficiency of 70%.

Keywords: animal waste, microbial fuel cell, metal electrode, COD removal

1 INTRODUCTION play an important role in the performance (e.g.,


power output) and cost of Microbial Fuel Cells
Environmental pollution and the depletion of (MFCs), which use bacteria as the catalysts to
global fossil fuels are driving the search for a oxidize organic (inorganic) matter and convert
novel, sustainable energy production alternatives. chemical energy into electricity (Logan, Cheng
A Microbial Fuel Cell (MFC) is a simple device et al. 2007). The output power depends on the
that generates electricity by the degradation of rate of substrate degradation, the rate of electron
organic matter (Rabaey and Verstraete 2005), such transfer from the bacteria to the anode, the circuit
as glucose, lactate (Park and Zeikus 2003), acetate, resistance, the proton mass transfer in the liquid,
and butyrate (Liu, Cheng et al. 2005). the performance of the electrode and the external
MFC treatment can reduce the COD in waste operating conditions and so on (Zhou, Chi et al.
water by degrading organic matter (Liu and Logan 2011). Different plate electrode materials vary in
2004). Microbial fuel cells could reduce the organic their physical and chemical properties (e.g., surface
compounds in the wastewater and produce the bio- area, electric conductivity, and chemical stability),
electricity simultaneously (Zhou, Chi et al. 2011). thus, they also vary in their impact on microbial
The performance of the microbial fuel cell is attachment, electron transfer, electrode resistance
affected by many factors, such as substrate oxida- and the rate of electrode surface reaction. There-
tion, the ability of microbes to transfer electrons to fore, it is of great significance to select and develop
the electrode, external resistance, proton transfer suitable electrode materials to optimize and pro-
through membrane and reduction at the cathode mote the performance of MFCs (Zhou, Chi
(Rabaey and Verstraete 2005). Electrode materials et al. 2011). A good anode material should have

95
the following properties (Min, Kim et al. 2005):
(a) good electrical conductivity and low resist-
ance; (b) strong biocompatibility; (c) chemical
stability and anti-corrosion; (d) large surface
area; and (e) appropriate mechanical strength and
toughness.
Three-dimensional (3D) electrodes can support
an increased attachment of bacteria and increase
the volumetric power density, which should, in the-
ory, result in the better performance of the MFC
reactor. Therefore, this study aims to evaluate the
effect of a novel 3D electrode which made of iron
and copper in the electricity generation from pig-
waste slurry in a two-chambered cubic microbial
fuel cell.
Figure 1. Photo of electrode (a) Cu anode, (b) Cu
cathode, (c) Fe anode, (d) Fe cathode, (e) carbon-fiber
anode, (f) carbon-fiber cathode.
2 MATERIALS AND METHODS
Table 1. Working surface of the electrodes.
2.1 Seed inoculums
The MFC was inoculated with the enriched pig Item Working surface (m2)
manure which was cultivated (operated at 37°C) in
Type Cu (g) Fe (g) Carbon-fiber (g)
a two-chambered cubic microbial fuel cell.
Electrode 0.073 0.054 0.002

2.2 MFC configuration and experimental


conditions (R) of 100 Ω was connected between the electrodes
and the closed circuit potentials of the MFCs were
The cubic two-chamber MFCs consisted of two
recorded every 5 min with a DAS-5000 (Jiehan
polycarbonates or poly (methyl methacrylate)
Technology Corporation) data logger. Analytical
halves separated by an Ultrex anion exchange
method APHA Standard Methods (Association
membrane (CMI-7000, Membranes International,
and Association 1981) was used to determine pH
Ringwood, NJ). The working volumes of both
and Chemical Oxygen Demand (COD) concentra-
anode and cathode were 75 mL. Metal electrodes,
tion. The power density was calculated according to
plate electrode (5.0 × 6.0 × 0.3 cm, McMaster-Carr,
the equation, P = I × V/A, where V is voltage (V),
Aurora, OH) were used in both chambers and they
I (I = V/R) the current (amp), and A the surface
were pretreated as described by Bond and Lovley
area of the anode electrode (m2). Polarization char-
(Bond and Lovley 2003) before and between each
acteristics of the MFCs were determined by vary-
MFC run (Xing, Cheng et al. 2010). The metal plate
ing the resistance (between 1 M Ω and 5 Ω) by using
and 3D electrodes were made of Fe fiber (BR50)
a variable resistor box from the open circuit voltage
and Cu fiber (CI50) (Taiwan special metal mesh
stepwise in 5-min intervals. The internal resistances
Co., Ltd.). The diameter of each fiber is 0.23 mm.
of the MFCs were calculated by the polarization
The plate electrode is constructed with plain weave
slope method (Lay, Kokko et al. 2015). In a plot of
method to form a plain net with a dimension of
current versus measured voltage, the slope of the
3 cm × 5 cm (Fig 1a, 1c). The carbon fiber electrode
linear polarization curve is the internal resistance
was waved with Plain weave method (Kim, Jung
of the MFC.
et al. 2007) (Fig 1e). The working surfaces of the
three type electrodes are shown in Table 1.
The pig-waste slurry containing Total Chemical
3 RESULTS AND DISCUSSION
Oxygen Demand (TCOD) 3300 ± 300 mg/L was
used as the feedstock in the anode. Potassium ferri-
3.1 Power generation
cyanide (50 mM, K3Fe(CN)6) with phosphate buffer
(100 mM Na2HPO4, pH 7.0) was used as catholyte. Figure 2 reveals the voltage performance using Cu
The MFCs were inoculated (10%, v/v) with the electrode, Fe electrode, and Carbon fiber electrode.
enriched inoculums and operated in a shaker at 37°C It shows that using metal electrode could generate
using a fed-batch mode with feed cycle every 2 days. the bioelectricity rapidly. The maximum voltage
During each feeding, catholyte was replaced by fresh of 175 mV and the average voltage of 75 mV were
K3Fe(CN)6, solution. A fixed external resistance obtained using Fe electrode. Fe electrode has the

96
peak electricity generation of 176 mV at the first
two days and maintained a stable voltage of 110 mV
during the 5th to 15th days. The maximum voltage
of 170 mV and the average voltage of 75 mV were
obtained using Carbon fiber electrode. Carbon
fiber electrode has the peak electricity generation
of 176 mV at the first six days and maintained the
stable electricity voltage of 166 mV during the 6th
to 15th days. However, the lower average voltages
of 15 mV are carried out using Cu electrode.
Figure 3 shows that the higher current density
was obtained using Fe electrode. The maximal cur-
rent density was 23 mA/m2 using Fe electrode. The
current density of 22 mA/m2 using carbon fiber
electrode. This value is stable the current density of
using carbon fiber electrode. Lower current densi-
ties ranged from 0–2 mA/m2 using Cu electrode.
The reason might be that the leachate from Cu elec-
trode poisons the microorganisms in the anode.

3.2 Polarization curves and power density curves


analysis
Figure 4 and Table 2 show the analysis results by
polarization curves and power density curves at
three types of electrodes. The maximum power
density of 12.3 mW/m2 and a current density of
240 mA/m2 using carbon fiber electrode. Figure 3. Current density using (a) Cu electrode and
(b) Fe electrode and (c) carbon-fiber electrode.

Figure 4. Polarization curves and power density curves


Figure 2. Voltage performance using (a) Cu electrode at (a) Cu electrode and (b) Fe electrode and (c) carbon-
and (b) Fe electrode and (c) carbon-fiber electrode. fiber electrode.

97
Table 2. Maximum power and current density at vari- electricity generation performance compared with
ous types of electrodes. Cu electrode and carbon fiber electrode. Fe plate
electrode has the peak stable electricity voltage of
Power density Current density 110 mV. The COD removal efficiency could reach
Electrode type (mW/m2) (mA/m2)
81%. Using copper electrode only can generate the
Cu 0.33 1.91 peak electricity of 19.5 mV and carbon fiber stable
Fe 3.95 23.22 electricity of 160 mV with the COD removal effi-
Carbon fiber 12.3 240 ciency of 70%.

ACKNOWLEDGEMENTS

This study was acknowledged by the professors


from Green Energy Development Center and
department of Fiber and Composite Materials at
Feng Chia University, Taiwan.

REFERENCES

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Bond, D. R. and D. R. Lovley. 2003. Electricity production by
Geobacter sulfur reducers attached to electrodes. Applied
and environmental microbiology 69(3): 1548–1555.
Kim, J. R., et al. 2007. Electricity generation and micro-
bial community analysis of alcohol powered microbial
fuel cells. Bioresource technology 98(13): 2568–2577.
Lay, C.-H., et al. 2015. Power generation in fed-batch and
continuous up-flow microbial fuel cell from synthetic
wastewater. Energy 91: 235–241.
Liu, H., et al. 2005. Production of electricity from acetate
or butyrate using a single-chamber microbial fuel cell.
Environmental science & technology 39(2): 658–662.
Liu, H. and B. E. Logan. 2004. Electricity generation
using an air-cathode single chamber microbial fuel
cell in the presence and absence of a proton exchange
membrane. Environmental science & technology 38(14):
4040–4046.
Logan, B., et al. 2007. Graphite fiber brush anodes for
Figure 5. COD removal efficiency using (a) Cu elec- increased power production in air-cathode microbial
trode and (b) Fe electrode and (c) carbon-fiber electrode. fuel cells. Environmental science & technology 41(9):
3341–3346.
Min, B., et al. 2005. Electricity generation from swine
wastewater using microbial fuel cells. Water research
3.3 COD removal efficiency 39(20): 4961–4968.
The removal efficiency of COD from wastewater Park, D. H. and J. G. Zeikus. 2003. Improved fuel cell
using Fe electrode and Cu electrode could reach and electrode design for producing electricity from
microbial degradation. Biotechnology and bioengineer-
higher than 90% and 81% respectively. Lower COD
ing 81(3): 348–355.
removal efficiency ranged from 53–75% using car- Rabaey, K. and W. Verstraete. 2005. Microbial fuel cells:
bon fiber electrode. The experimental results show novel biotechnology for energy generation. TRENDS
that the COD removal efficiency depends on the in Biotechnology 23(6): 291–298.
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Zhou, M., et al. 2011. An overview of electrode mate-
Three types of plate electrodes could be applied in a rials in microbial fuel cells. Journal of power sources
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98
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Anaerobic digestion of sludge in municipal wastewater treatment


plant—example of European Solution

P. Jenicek, J. Bartacek, J. Kutil & J. Zabranska


Department of Water Technology and Environmental Engineering, University of Chemistry and Technology,
Prague, Czech Republic

ABSTRACT: The anaerobic digestion of sludge (primary and excess activated) is the process which
has the potential to produce significant amount of energy for the sewage treatment wastewater treatment
plant operation. The all heat requirement and big part of electricity requirement can be saturated using
the combined heat and power production from biogas. The full scale experience with intensification of
sludge treatment technology obtained in Prague Central Wastewater Treatment Plant (PCWWTP) will
be presented. The main intensifying measures applied were: improvement of primary sludge separation,
thickening of activated sludge, improvement of mixing, use of lysate centrifuge, change op operational
temperature. Thanks to mentioned optimization measures the PCWWTP is able to produce more than
50 000 m3 of biogas per day. The heat and electricity produced from biogas cover heat demands com-
pletely and about 70–80% of electricity demands.

Keywords: anaerobic digestion; energy self-sufficiency; lysate centrifuge; sludge disintegration; thermo-
philic digestion

1 INTRODUCTION process. Provided that biogas is being recovered


in Combined Heat and Power production (CHP)
Main objectives of anaerobic treatment of sewage units, the higher biogas yield enables an increase in
sludge are reduction and stabilization of sludge electricity production. Maximal profit is achieved,
solids. In the last years more effort was put into if the plant can sell thus-gained “green” energy to
increasing biogas production and minimizing of power supply network for a special tariff.
the output sludge solids that have to be disposed
of, in order to limit ecological and economical dis-
advantages of their handling. (Appels et al., 2008).
2 INTENSIFICATION OF SLUDGE
The advantage of anaerobic digestion system of
TREATMENT TECHNOLOGY
sludge is production of energy in biogas. The pro-
duced energy can cover not only the energy need
The efficiency of sludge treatment technology
for the sludge treatment, but a substantial part of
can be influenced by many parameters, individual
the energy consumption of the whole treatment
treatment steps are closely connected, type and
plant. The potential of using the biogas as energy
arrangement of mechanical and aerobic biologi-
source has long been widely recognized and cur-
cal step strongly influence amount and composi-
rent techniques are being developed to upgrade
tion of primary and secondary sludge, the quality
quality and to enhance energy use.
and ratio of sludges are changing with impact on
The EU policies concerning Renewable Energy
sludge treatment.
Systems (RES) have set forward a fixed goal of
The ways able to influence and intensify sludge
supplying 20% of the European energy demands
treatment resulting in biogas production enhance-
from RES by year 2020. A major part of the
ment are mainly connected with following points
renewable energy will originate from European
in technological line:
farming and forestry. At least 25% of all bioenergy
in the future can originate from biogas, produced • pretreatment of input material to enhance
from wet organic materials such as: sewage sludge, anaerobic biodegradability,
animal manure, whole crop silages, wet food and • higher amount of input organic matter to anaer-
feed wastes, etc. (Holm-Nielsen et al., 2009). obic digestion,
Anaerobic sewage sludge stabilization is the only • optimization of technological conditions of the
energy producer in the whole wastewater treatment anaerobic degradation process.

99
2.1 Disintegration combined with thickening thermophilic conditions leads to a better utilization
of existing facilities and consequently avoids the
Because of very low specific energy consumption
digester overloading. The higher degradation effi-
the optimal solution is the disintegration of acti-
ciency is associated with a higher biogas produc-
vated sludge combined with a thickening. The par-
tion and a lower content of volatile solids in the
tial destruction of excess activated sludge bacteria
digested sludge which represents a lesser amount
cells can be reached during the thickening by means
of output stabilized sludge with better dewatering
of the centrifuge equipped with a special disinte-
properties. The efficiency in destroying the patho-
grating device. The disintegrating gear is mounted
gens is also considerably higher. Thermophilic tem-
at the end of the flow of thickened sludge and does
peratures kill most pathogenic bacteria and most
not influence the centrate quality (Dohanyos et al.,
viruses. The effect on the pathogens was found to
2004). The method is capable of producing 5–15%
be a combined effect of temperature and anaerobic
degree of disintegration, but is able to handle high
environment.
volume flow rates. Energy consumption is depend-
The stable and efficient operation of the ther-
ent on the centrifuge flow rate capacity and for
mophilic anaerobic digester strongly depends on
the high capacity centrifuges is almost negligible
the activity of anaerobic consortia in the digester
(Zabranska et al., 2000).
(Zabranska et al., 2000). The occurrence of ther-
The practical impact of the installation of dis-
mophiles depends upon the history of the waste
integrating device into thickening centrifuges is
material. Sewage sludge or other types of waste
the most obvious from the enhancement of biogas
contains mainly mesophilic microbes including
yield on several WWTPs, ranging between 15 and
anaerobes, therefore the number of thermophiles
26%. The extent of increase depends on the oper-
and especially some specific groups such as ace-
ating conditions of the WWTP, the most impor-
tate-utilizing methanogens, propionate-degraders
tant factors are the excess activated sludge age,
or cellulose-degraders is often very low or these
content and type of the organic material in raw
groups can even can be missing (Ahring, 1994).
sludge and the hydraulic retention time in digest-
When starting a thermophilic digester it is very
ers (Zabranska et al., 2000). The higher effect of
important to use a strategy allowing for optimal
disintegration is achieved with a younger activated
growth of the necessary thermophilic minority
sludge, shorter retention time in digesters and with
population. (Ahring, 2001)
a higher activity of anaerobic microorganisms in
The adequate thickening of waste activated
digesting sludge (Dohanyos et al., 1997).
sludge is a basic parameter influencing the econ-
omy of heat energy consumption and the utiliza-
2.2 Improvement of digesters efficiency and tion of digester volume.
biogas production The further improvement of biogas production,
when the digesters operation is optimized, can be
The measures that can contribute to the more stable reached by installation of disintegration technol-
operation of digesters, to accelerate organic matter ogy as pre-treatment and by increasing efficiency
degradation, and thus make it more efficient, are of primary settlers resulting to a higher amount of
based on the improvement of: organic matter fed to digesters. That can be realized
• the homogeneity of fermentation mixture in by dosing of some kind of coagulants (e.g. Fe salts)
digesters; to wastewater before the primary settling thus a
• the frequency of feeding; higher amount of very fine particles of organic mat-
• the total solids concentration in the raw sludge; ter is caught to primary sludge. The most of this type
• the process temperature to thermophilic level. of organic matter is converted to biogas and organic
loading rate of activated sludge system is decreased.
The homogeneity of fermentation mixture in
digesters is a very important factor depending on
the mixing efficiency and the frequency of feeding. 3 DESCRIPTION OF THE CENTRAL
Sufficient mixing enables a good heat distribution, WASTEWATER TREATMENT PLANT
a good contact of substrate and microorganisms. IN PRAGUE (CWWTP)
The feeding should to be closed to a continual
system that avoids shock overloading and keeps All above mentioned methods of sludge treatment
dynamic balance in microbial consortia. intensification have been gradually applied to the
The thermophilic anaerobic process brings an technology in the Central Wastewater Treatment
acceleration of biochemical reactions and a higher Plant in Prague to increase the quantity of self-
efficiency in the degradation of organic matter produced energy (Jenicek et al., 2012).
in comparison with the mesophilic process. The CWWTP in Prague is the large plant (1 600 000
change of temperature from the mesophilic to PE) treating the main part of the city wastewaters.

100
CWWTP has been in operation from 1967 and and biogas yield from primary, waste activated
several reconstructions of the plant were carried and mixed raw sludge. These methods were used
out according to essential technology changes during a long time monitoring of the operation of
and economic situation. The last reconstruction full scale digesters in the co-operative project of the
has been accomplished in 1997 with increased University of Chemical Technology and the Central
wastewater treatment capacity and a change of Wastewater Treatment Plant in Prague.
the activated sludge process technology to a nutri-
ent removal system. These measures logically
3.2 Intensification steps in CWWTP in prague
influenced also sludge amount and composition,
as illustrates Figure 1 and thus a need for sludge Intensification steps and innovations of technical
treatment intensification arose. equipment have been applied gradually, starting
The sludge treatment facilities of the plant with the installation of five thickening centrifuges
consist of 12 digesters, each with an operational for the thickening of excess activated sludge and
volume of 4800 m3. Digesters are configured in four dewatering centrifuges instead of belt presses.
series as the first and second stages and operated To one thickening centrifuge the disintegrat-
in a semi-continuous flow with about 24 feedings ing device was experimentally installed and after
daily. Six 1st stage digesters are mixed and heated, successful proof of efficiency in 1997 all other
2nd stage digesters (provided with a gasholder) centrifuges were equipped with disintegration
are without heating and mixing. Waste activated technology. The reconstruction of the biogas utili-
sludge is pre-thickened in a gravity thickener and zation system changed old gas turbines to 3 motor
thickened and disintegrated in lysate-thickening generators each of 1 MWel and improved the heat-
centrifuges. This sludge is mixed with primary ing system of digesters. Later the new two motor
sludge in the mix tank and the mixture is fed into generators with the power capacity of 1.2 MWel
the first stage of digesters. Digested sludge is dewa- were installed, a system for automated control of
tered by dewatering centrifuges and after compost- the sludge treatment process has been finished and
ing is applied to land. the mixing system of digesters has been upgraded.
The digestion process were intensified mainly by
a transfer operational temperature from mesophilic
3.1 Methods used for monitoring of digesters
to thermophilic range and biogas production was
operation
increased through an enhancement of primary
The determination of COD, Total Solids (TS), Total sludge organic matter concentration by dosing of
Suspended Solids (TSS), Total Dissolved Solids coagulants to wastewater prior primary settlers.
(TDS), Volatile Solids (VS), Volatile Dissolved Sol- The each step will be discussed in more details.
ids (VDS) and Volatile Suspended Solids (VSS) was
carried out as proposed by the Standard Methods.
3.3 Disintegration of waste activated sludge
The gas and volatile fatty acids composition were
analyzed by gas chromatographs. The frequency of The first experimental full-scale lysate-centrifuge
sampling was controlled according to a situation with input sludge flow 100–110 m3/h has already
in volatile fatty acids production and uptake. The been installed in 1995. Daily excess activated sludge
batch laboratory tests were carried out to deter- input flow during the normal operation was 4600 m3
mine the digested sludge methanogenic activity (7 g/l TS), and the thickened sludge production was
about 650 m3/d (70 g/l TS). The improvement of
methane yield and biodegradability was influenced
by the quality of input excess activated sludge and
the parameters and efficiency of the thickening
centrifuge. The improvement of methane yield from
thickened activated sludge measured in batch labo-
ratory tests was on average 11.5–31.3% dependent
on the sludge quality. (Dohanyos et al., 1997).
The method of proving the real effect of sludge
disintegration in full-scale has to be based on a
long-term monitoring of specific biogas produc-
tion, i.e. the amount of biogas released from 1 kg
of input organic matter in the digester. The evalu-
(PS—primary sludge, TES—thickened excess sludge, ation process needs very close cooperation with
RS—raw sludge). the operator of the plant. But it is very difficult to
find a long period in any WWTP operation with-
Figure 1. Development of sludge production in CWWTP. out technical and/or process problems. During the

101
observation time some exceptional situations and measured and analyzed, the foaming tests and
conditions occurred, e.g. digester foaming, failure microbiological analyses were also made. The
of dewatering centrifuge and recycle of digested experiment gave the unique opportunity to moni-
sludge to wastewater inflow, repair and replace- tor and study both mesophilic and thermophilic
ment of rotating part of disintegrating device, stop system in a full-scale parallel under the same con-
of operation of one digester that doubled volumet- ditions of input sludge and technical equipment
ric loading, failure of gas measurement etc. of digesters. The results of the comparison are
The other problem of evaluation is reliability following:
of values of sludge concentration, as they strongly Specific biogas production per input volatile
depend on the point, way, time and frequency of solids in mesophilic and thermophilic digesters is
sampling, methods and technique of analyses, time presented in Table 1. The average loading rates of
and conditions of storing etc. Differences from the first stage mesophilic and thermophilic digest-
real values combined with not recorded short-term ers during the last year of experimental operation
technology changes contribute to unavoidable data were 3.1 and 4.1 kg /m3.d of volatile solids respec-
fluctuation and an evaluation has to be based on tively. The daily volume of input raw sludge was
statistics. round 350 m3 to mesophilic tank and 420 m3 to
For the objective evaluation of economic and thermophilic tank.
energetic balance of the CWWTP following data The response of digesters to increasing load-
were available: volumes and concentration of total ing rate is presented in Figure 2. The loading rates
and volatile solids in primary sludge, excess acti- varied dependent to the actual operational volume,
vated sludge and thickened excess activated sludge; which was connected with an incidence of the
running hours and electric energy consumption intensive foaming in mesophilic digesters. In the
of individual thickening centrifuges; volume and case of foaming, the sludge level in the tank must
temperature of produced biogas that need to be be lowered to set a free space for the foam. Due to
re-calculated for normal conditions (Nm3) and as the resistance of thermophilic sludge to foaming,
a dry gas without the water vapor; temperature in thermophilic digester disposed of a full volume
digesters; volumes and concentration of total and of the tank. During the wintertime the resist-
volatile solids in digested sludge, dewatered sludge; ance of thermophilic digesters against foaming
quality of effluent from dewatering; polymer con- was verified, all mesophilic tanks were frequently
sumption for dewatering; net price of polymer,
net price of dewatered sludge disposal; electrical
Table 1. Specific biogas production per input volatile
efficiency of cogeneration; net price of electric- solids in mesophilic and thermophilic digesters (Nm3—
ity from power supply network; net buyout price recalculated for standard temperature and pressure).
of “green” energy; utilization of produced heat
energy (months/year); the extent of biogas utiliza- Specific biogas Mesophilic Thermophilic
tion in cogeneration unit. production
After the evident proof of stimulating effect of
lysate on methane production and degradation (m3/kg) 0.547 0.710
rate in full-scale, all thickening centrifuges were (Nm3/kg) 0.480 0.600
equipped with a disintegrating device (Zabranska
et al., 2006) and have been operated continuously
till now.

3.4 Thermophilic digestion in CWWTP


Since 1998 the full-scale experiment of thermo-
philic digestion of sewage sludge has been carried
out, one of the 1st stage of thermophilic tank was
heated to 55°C and the 2nd stage due to a good
insulation maintained the temperature almost
at the same level (only one or two degrees less).
(Zabranska et al., 2000) After an adaptation to
thermophilic temperature are digesters success-
fully operated with unexpected operational stabil-
ity (Jenicek et al., 2013) and remarkable increment
of biogas production.
During the experiment the input raw sludge, Figure 2. Daily biogas production per thermophilic
output sludge from each stage and biogas were and mesophilic tank dependent to loading rate.

102
foaming at the volumetric loading rate of 4.5 kg wide propellers SCABA to the first stage digesters.
TS/m3.d, no of thermophilic tanks foamed even at Nowadays the jet type mixers are prepared to
6 kg TS/m3.d. installation to the second stage digesters to use the
The composition of the biogas from thermo- residual temperature of the sludge from the previ-
philic digesters was the same as from the other ous stage and prolong the retention time for better
digesters and was very stable, the methane content utilization of organic matter.
ranging from 66.1% to 66.5%, but biogas from ther-
mophilic tanks contained less hydrogen sulphide
3.6 Evaluation of combined effect of
and other malodorous substances. (Zabranska
intensification steps
et al., 2002a) The content of hydrogen sulfide was
21 mg/m3 and no other malodorous compounds During the last years of CWWTP operation many
have been found in thermophilic biogas, in mes- changes have been realized in the technological
ophilic biogas dimethylsulfide, dimethyldisulfide line.
and methylpropylsulfide were determined and the Additionally some non-standard situations
amount of hydrogen sulfide was about 33 mg/m3. and unexpected events, such as activation tanks
The batch laboratory tests were carried out to and settlers’ reconstruction or catastrophic flood
determine the digested sludge methanogenic activ- in 2002, contribute to difficulty of the stable
ity and proved that the specific methanogenic operational data evaluation. The most important
activity of thermophilic sludge was always higher changes in sludge treatment were the installation
than the activity of mesophilic sludge. of thickening centri-fuges, the introduction of dis-
The better effect of destroying pathogens in integration technology, the improvement of mixing
the thermophilic digester was proved as counts efficiency and the transformation of all digesters
of thermotolerant coliforms and enterococci from mesophilic to thermophilic temperature. The
per g of total solids of sludges reached the limit changes have been realized individually in different
of 103 CFU/g TS for more than 60% of samples, time and extent but the impact on the final effect
and an occurrence of Salmonella sp was negative. is always a combination of all processes. The devel-
(Zabranska et al., 2002b) The mesophilic anaero- opment of biogas production is shown in Fig. 3.
bic process destroyed about 2–3 logs of indica- The implementation of thermophilic anaero-
tor bacteria; thermophilic anaerobic process was bic digestion (55°C) combined with excess sludge
reducing 4–5 logs. disintegration by means of lysate-thickening cen-
Based on the excellent experience with the trifuge brought the increment of specific biogas
experimental thermophilic process the operator of production from 0.470 to 0.650 Nm3/kg of VS
the CWWTP decided to transfer all other digesters input. Consequently 115 MWh/d of electric energy
to thermophilic conditions. By upgrading existing and 178 MWh/d of heat energy are produced in the
mesophilic digesters to the thermophilic tempera- combined heat and power production units.
ture range, the digesting capacity was doubled and With a heat recuperation of sludge output heat
considerable increment of biogas production and production covers the total energy demand of the
energy balance were obtained. When three from all plant even in wintertime (Kutil, 2005). For utiliza-
six first stages had already been successfully trans- tion of a full energetic potential of daily produced
formed to thermophilic digesters, a catastrophic biogas the capacity of existing 5 motor-generators
flood in 2002 interrupted the further transforma-
tion process. Nowadays all digesters are success-
fully operated at 55°C.

3.5 Hydraulic conditions in digesters


The efficient mixing is the key parameter for a
sufficient hydraulic retention time and a maxi-
mal utilization of digesters volume. Hydraulic
dead zones in the digester and a short-circuiting
reduce the effective hydraulic retention time and
thus have detrimental effect on the digestion effi-
ciency (Zabranska et al., 2001b). Mixing in the
first stages of digesters had been ensured only by
a sludge recirculation. Later the hydraulic mix- Figure 3. Daily course of biogas production (---♦---)
ing was strengthened with recirculation of biogas. and volatile solids input (— —) at CWWTP including
The further improvement in mixing efficiency was mean value lines (----- biogas production and—volatile
achieved by the installation of slowly rotating solids input).

103
Dohanyos, M., Zabranska, J. & Jenicek, P. (1997).
Enhancement of sludge anaerobic digestion by using
of a special thickening centrifuge. [Link].,
36(11), 145–153.
Dohanyos, M., Zabranska, J., Kutil, J. & Jenicek, P.
(2004). Improvement of anaerobic digestion of sludge.
[Link]., 49(10), 89–96.
Holm-Nielsen, J.B., Al Seadi, T. & Oleskowicz-Popiel, P.
(2009). The future of anaerobic digestion and
biogas utilization. Bioresource Technology, 100(22),
5478–5484.
Jenicek, P., Bartacek, J., Kutil, J., Zabranska, J. &
Dohanyos M. (2012). Potentials and limits of anaero-
bic digestion of sewage sludge: Energy self-sufficient
Children Face Tough
Children Face Tough municipal wastewater treatment plant? Wat. Sci.
Tech., 66(6) 1277–1281.
Figure 4. Percentage of energy self-sufficiency of
Jenicek, P., Kutil, J., Benes, O., Todt, V., Zabranska, J. &
CWWTP Prague.
Dohanyos, M. (2013). Energy self-sufficient sewage
wastewater treatment plants: is optimized anaero-
bic sludge digestion the key? Wat. Sci. Tech., 68(8)
are for the present insufficient and an installation
1739–1744.
of the sixth engine is planned. The clear trend to Krugel, S., Nemeth, L. & Peddie, C. (1998). Extended
energetic self-sufficiency is presented in Figure 4. thermophilic anaerobic digestion for producing class
A biosolids at a greater Vancouver regional district
Annacis Island Wastewater Treatment Plant. Proceed-
4 CONCLUSIONS ings of IAWQ 19th Biennial International Conference,
21–26 June 1998, Vancouver, Canada, Book 4, Anaer-
The Central Wastewater Treatment Plant in Prague obic Treatment and Membrane Technologies, 88–95.
has been during an operation intensified in several Kutil, J. (2005). Intensification of anaerobic digestion in
CWWTP Prague—the way to energetic self-sufficiency.
steps and the impact of individual phases espe-
Technical report, in Czech.
cially connected to sludge treatment is presented. Zabranska, J., Dohanyos, M., Jenicek, P. & Kutil, J.
The main changes in the operation of sludge treat- (2000). Thermophilic process and enhancement of
ment were related to an increase of input organic excess activated sludge degradability—two ways
matter, better mixing of digesters, pretreatment of of intensification of sludge treatment in the Prague
waste activated sludge by mechanical disintegra- Central Wastewater Treatment Plant. Wat. Sci. Tech.,
tion combined with thickening and transfer of 41(9), 265–272.
mesophilic digestion temperature to thermophilic. Zabranska, J., Dohanyos, M., Jenicek, P., Zaplatílková, P. &
Intensification steps in sludge treatment technol- Kutil, J. (2002)a. The contribution of thermophilic anaer-
obic digestion to the stable operation of wastewater treat-
ogy have gradually brought significant improve-
ment plant. Wat. Sci. Tech., 46, (4–5), 447–453.
ment in the sludge stabilization efficiency and a Zabranska, J., Dohanyos, M., Jenicek, P., Růžičková, H. &
substantially higher biogas production connected Vránová, A. (2002). Efficiency of autothermal thermo-
with a better energetic and economic situation of philic aerobic digestion and thermophilic anaerobic
the plant. Electric energy produced from biogas digestion of municipal wastewater sludge in removing
can almost cover the total demand of the plant and Salmonella sp. and indicator bacteria. Wat. Sci. Tech.,
bring it close to energy self-sufficiency. 45(10), 335–340.
Zabranska, J., Dohanyos, M., Jenicek, P. & Kutil, J.
(2006). Disintegration of excess activated sludge—
evaluation and experience of full-scale applications.
ACKNOWLEDGEMENT
Wat. Sci. Tech., 53(12), 229–236.
This study was supported by the CWWTP and the
project MSM 6046137308.

REFERENCES

Appels, L., Baeyens, J., Degrève, J. & Dewil, R. (2008).


Principles and potential of the anaerobic digestion of
waste-activated sludge. Progress in Energy and Com-
bustion Science, 34(6), 755–781.

104
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Simulation of purification circuits of next generation gas-cooled


nuclear reactors

T. Hudský & K. Ciahotný


University of Chemistry and Technology, Prague, Czech Republic

J. Berka
Research Centre Řež, Husinec—Řež, Czech Republic
University of Chemistry and Technology, Prague, Czech Republic

ASBTRACT: Helium in the primary circuit of gas-cooled nuclear reactors contains low concentrations
of gaseous impurities (CO, CO2, H2O, CH4, H2, N2, O2) and dust particles. These impurities can cause
early corrosion, and dust particles can damage the turbine blades. The coolant gas is being continually
cleaned in purification circuits in the gas-cooled nuclear reactors. In this paper we simulate the processes
that occur in the purification circuits (adsorption of gasses on molecular sieves, oxidation of carbon
monoxide on CuO) on an experimental apparatus that is located at the University of Chemistry and
Technology Prague and on High-Temperature Helium Loop in Research Centre Rez.

1 BACKGROUND a fraction of flowing helium is being constantly


cleaned there. (A Technology Roadmap, 2002)
Along with increasing population the consumption
of basic needs and energy is growing. Because the
fossil fuels are limited in supply and one day will 1.1 Impurities
be depleted, people are trying to find new energy Helium of gas-cooled nuclear reactors contains
resources and use them in processes with higher undesirable impurities. Gaseous impurities are
energy conversion efficiency. mainly N2, H2, H2O, CO, CO2, CH4 and O2, but oxy-
Generation of electricity by nuclear fission does gen immediately reacts with other agents. Dust par-
not create any direct carbon dioxide emissions and ticles and fission products (Kr, Xe, I, Cs) are present.
the amount of fuel consumed is relatively small. All these impurities cause early corrosion of the
Therefore it can be considered to be less harmful to equipment and oxidation of graphite. Dust particles
the environment compared to burning fossil fuels. can cause mechanical erosion of the equipment.
New types of nuclear reactors, the fourth gener- Concentrations of the impurities are relatively
ation reactors, are nowadays being developed and low (0.1–30 ppm), but they can interact with each
will be operational in the next decades. Reactors
of the fourth generation should meet eight defined
technology goals in sustainability, economics,
safety and reliability, proliferation resistance and
physical protection. Some of the reactors will have
closed fuel cycle that enables to recycle spent fuel
and some reactors will enable hydrogen production
and other process heat applications. Two out of six
suggested designs of the nuclear reactors are gas-
cooled with helium as the coolant gas due to its
radiochemical inertness and advantageous thermal
properties. The two concepts are Gas-Cooled
Fast Reactor (GFR) and Very-High-Temperature
Reactor (VHTR). Helium in the reactors can be
contaminated with impurities and they must be
constantly removed, thus there is a purification Figure 1. Diagram of the Very-High-Temperature
circuit in every gas-cooled nuclear reactor and Reactor (A Technology Roadmap, 2002).

105
other and with materials in the primary circuit and helium by leakage from the ambient air and during
their concentrations may change. maintenance and refueling. Fission products can
Sources of gaseous impurities are various. escape from the fuel cladding to the primary circuit.
Helium is mainly contaminated by impurities Hydrocarbons can contaminate the primary cir-
during production and transport of the helium to cuit from bearings of pumps (Burnette R. D. et al,
the primary circuit. When the temperature rises 1971, Yao M. S. et al, 2002).
in the primary circuit, the impurities desorb from
the construction materials of the primary circuit
1.2 Purification circuits
and from the fuel. The impurities contaminate the
Purification circuits of the previous gas-cooled
nuclear reactors were similar, although every cir-
cuit had its deviations. At the inlet of purifica-
tion circuits there are mechanical filters to clean
dust particles bigger than 5 μm from the gas. The
helium flows to oxidizer bed where hydrogen and
carbon monoxide are oxidized to water and carbon
dioxide at temperatures around 250°C. These two
impurities are captured on molecular sieve beds at
the room temperature. Remaining impurities (N2,
CH4, O2, Kr, Xe) are adsorbed in low temperature
adsorption beds at temperatures around −160°C.
(Yao M. S. et al, 2002)

2 METHODOLOGY

2.1 Adsorption experiments


Adsorption of carbon monoxide, carbon dioxide
Figure 2. Diagram of the Gas-cooled Fast Reactor and methane on zeolite molecular sieves was exam-
(A Technology Roadmap, 2002). ined in this paper. An experimental apparatus was

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Figure 3. Schema of the HTR-10 helium purification system (Yao M. S. et al, 2002).

106
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Figure 4. Diagram of the apparatus. 1—cylinder with nitrogen (99.999% purity), 2, 3—cylinder with helium (99.9999
purity), 4—cylinder with mixture of helium and adsorbed gas, 5—gas pressure reduction valve, 6, 7—shut-off valve,
8—pressure controller Bronkhorst F-232M, 9—needle valve, 10—pressure gauge, 11—shut-off valve, 12—adsorption
column, 13—shut-off valve, 14—flow and pressure controller Bronkhorst P-202C a F-033C, 15,16,17—shut-off valves,
18—FTIR spectrometer.

4 high pressure aluminum cylinders (one with


sample that is adsorbed in the column, one with
nitrogen (99.999% purity) and two with helium
(99.9999% purity) that are used to flush the apara-
tus). Pressure and gas flow in the apparatus was
controlled on a personal computer with FlowDDE
and FlowWiew software in range of pressures
0–10 MPa and flow 0–33 l⋅min−1.
Series of adsorption experiments were carried out
with gas mixtures containing helium and one gase-
ous impurity (1—mixture of helium and 101 ppm of
methane, 2—mixture of helium and 510 ppm of car-
bon dioxide, 3—mixture of helium and 990 ppm of
carbon monoxide). The mixture of helium and gas-
eous impurity was flowing through the adsorption
column filled with molecular sieve and the gas flow-
ing out of the apparatus was analyzed on the FTIR
spectrometer and concentration of the impurity was
observed. Usable and total sorption capacities were
calculated from breakthrough curves for the three
impurities under various pressures. Usable capac-
ity is amount of impurity adsorbed on the molecu-
lar sieve, until the concentration of the impurity in
the mixture flowing out of the apparatus is higher
than 5% of total concentration, per one gram of the
molecular sieve. Total capacity is the total amount
of impurity adsorbed on the molecular sieve, per
one gram of the molecular sieve. The molecular
sieves we used were the 3A, 4A, 5A and 13X.
Figure 5. The adsorption apparatus.
2.2 HTHL
designed and constructed (on fig. 1). The appa- High-Temperature Helium Loop (HTHL) was
ratus consists of gas pressure reducing valves for built in Nuclear Research Institute Rez as part
low and high pressures, pressure gauges, pressure of its experimental program concerning VHTR
and flow controllers Bronkhorst F-232M, P-202C research. In the loop the physical and chemical
a F-033C, an adsorption column and a Fourier properties of the coolant under the conditions in
transform infrared spectrometer Nicolet Antaris VHTR can be stimulated. HTHL is used to test
IGS. Equipment in the apparatus is connected structural materials suitable for components of
with stainless steel ubing. The apparatus comprise gas-cooled reactors and to research the chemical

107
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Figure 6. Diagram of High-Temperature Helium Loop (Berka et al, 2015).
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processes taking place in the gas coolant. HTHL


is composed of several components: the active
channel with the testing zone and the circulatory
compressor on the top, the helium purification sys-
tem, the dosing system and the coolant chemistry
monitoring system—see fig. 6.
The maximum helium temperature in space for
placing the test specimens in HTHL is approxi-
mately 900°C, the pressure in the loop is 7 MPa and
the maximal gas flow rate in the loop is 38 kg⋅hr−1.
(Berka J. et al, 2012, Berka J. et al, 2015)
Figure 7. Breakthrough curves of CO2 on 3A molecular
sieve under various pressures.
3 RESULTS AND DISCUSSION

Breakthrough curves were measured and total and


usable capacities were calculated using the follow- where cu is usable capacity of 1 gram of sorbent
ing equation (1) derived from the equation of state [mg⋅g−1], ρ0 is concentration of impurity in the inlet
of an ideal gas: gas [ml⋅m−3], ρi is concentration of impurity in the
outlet gas in the time of analysis [ml⋅m−3], M is
molar weight [g⋅mol−1], ma is weight of the sorb-
⎛ −t
i + 1 i * q * p * M ⎞⎟
t ent [g], t is time [min], q is flowrate [l⋅min−1], p is
⎜ atmospheric pressure [Pa], R is molar gas constant
⎜ ρ −ρ 60 ⎟
⎜ 0i i R * T ⎟ [8,314 J⋅K−1⋅mol−1] and T is temperature [K].
cu = ∑ * (1)
⎜ 6 m ⎟ Breakthrough curves were collected and com-
⎜ 10 a ⎟ pared for three impurities under various pressures.
⎜ ⎟ The 3A molecular sieve doesn’t capture CO, CH4
⎜⎝ ⎟⎠ and CO2 in desirable amount. Capacity is almost

108
null for CO and CH4, capacity for carbon dioxide
grew with higher pressure. The 4A molecular
sieve is not also suitable for carbon monoxide and
methane capture. The 5A molecular sieve shows
poor results for CH4 and CO capture, while CO2
is captured effectively. The 13X molecular sieve is
not suitable for carbon monoxide capture and the
sorption capacity is low. Methane adsorbed more
on the 13X molecular sieve, but the capacity is still
too low to be used industrially.

Figure 8. Breakthrough curves of CO on various


molecular sieves at 6MPa. 4 CONCLUSIONS

Sorption of carbon monoxide, carbon dioxide and


methane was examined, breakthrough curves were
measured and sorption capacities were calculated.
The sorption capacities are shown in figure 10.
Highest sorption capacity of CO2 shows the 5A
molecular sieve. At the pressure of 2 MPa the sorp-
tion capacity is 2.62 mg⋅g−1 and at 8 MPa the capac-
ity is 15.62 mg⋅g−1.
In an effort to simplify the classical purifica-
tion circuit it would be useful to find adsorbents
that capture methane at room temperature, thus it
would not be necessary anymore to have a nitrogen-
Figure 9. Breakthrough curves of CH4 on various cooled adsorption column to remove methane
molecular sieves at 6 MPa. in the purification circuit. Finding adsorbents

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Figure 10. Adsorption properties of selected molecular sieves.

109
that capture carbon monoxide is desirable so the Berka, J., Matěcha, J., Černý, M., Víden, I., Sus, F. &
oxidizers in the purification circuit wouldn’t be Hájek, F. 2012. New experimental device for VHTR
needed anymore. Sorbents investigated in this structural material testing and helium coolant chem-
paper, however, don’t have high adsorption capac- istry investigation—High Temperature Helium
Loop in NRI Řež. Nuclear Engineering and Design.
ity for methane or carbon monoxide. These agents 251:203–207.
could be captured by organometallic sorbents and Berka, J., Hlinčík, T., Víden, I., Hudský, T. & Vít, J. 2015.
impregnated activated carbon and it is desirable to The design and utilization of a high-temperature
examine them in the apparatus in the future. helium loop and other facilities for the study of
advanced gas-cooled reactors in the Czech Republic.
Progress in Nuclear Energy. 85:156–163.
REFERENCES Burnette, R.D., Bell, W.E., Turner, R.F. & Knapp, W.J.
1971. Chemical Impurities in the Helium Coolant
A Technology Roadmap for Generation IV Nuclear at the Peach Bottom HTGR.U.S. Atomic Energy
Energy Systems, 2002. U.S. DOE Nuclear Energy Commission.
Research Advisory Committee and the Generation Yao, M.S., Wang, R.P., Liu, Z.Y., He, X.D. & Li, J. 2002.
IV International Forum. Available on [Link] The Helium Purification System of the HTR-10.
[Link]/gif/upload/docs/application/pdf/2013-09/ Nuclear Engineering and Design. 218:163–167.
[Link] cit. 28. 7. 2016.

110
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Detection of diethylene glycol by polyaniline coated electrode


in a voltammetry system

T.K. Tran
Faculty of Applied Science, Ton Duc Thang University, Ho Chi Minh City, Vietnam
Green Energy Technology Research Group, Ton Duc Thang University, Ho Chi Minh City, Vietnam

H.J. Leu & C.Y. Lin


Green Energy Technology Research Group, Ton Duc Thang University, Ho Chi Minh City, Vietnam
Green Energy Development Center, Feng Chia University, Taichung, Taiwan

ABSTRACT: A simple method of detecting of diethylene glycol (DEG) with different concentrations
was provided by using the electrochemical processes in the three electrodes electrochemical system. The
electrodeposition of polyaniline on the working electrode was made, using Cyclic Voltammetry (CV)
method; was not only show a capable result on the electrochemical performance of the electrode but also
created a promised material for the detection of the organic compounds in the aqueous phase. Several
samples of DEG with different concentrations were prepared and tested with Differential Pulse Voltam-
metry (DPV) method and indicates notable results of the detection process, especially at low concentra-
tion. The performance of coated electrode is also characterized electrochemically by both CV and DPV
method.

Keywords: volatile organic compounds, diethylene glycol, differential pulse voltammetry, cyclic
voltammetry

1 INTRODUCTION

Diethylene glycol (DEG) is a toxic organic


compound that can be easily found in our daily life Face Tough
as well as in household and industrial wastewater. Face Tough
On June 2007, the US Food and Drug Adminis-
tration (FDA) reported that there are toothpaste
products contained more than 3% of DEF in weight
Face Tough
(Brent 2001), (Velez et al. 2007), (Hassani et al.
2013). Long-term exposure from toothpaste usage Face Tough
is highly harmful to human, especially for children
Figure 1. Ethylene Glycol and Diethylene Glycol.
and people who suffered from kidney and liver
problems. Overdosing of DEG also cause a head-
ache, pain and even fetal renal failure (Hanif et al. samples. As we can see, the signal from the figure
1991), (Marraffa et al. 2008), (O’brien et al. 1998). response was not linearly dependent on the con-
Figure 1 shows the basics definition about the centration of DEG in the toothpaste, probably
production of DEG from its original chemical because the total amount of DEG could not be
Ethylene Glycol. linearly released from the toothpaste mixtures due
DEG is a colorless, odorless, poisonous, and to the comprehensive interactions that occurred at
hygroscopic liquid with a taste of sweet which the molecular level.
is also popular in many industries: fibers, leath- Not only dangerous to human life, DEG con-
ers, papers, polymer based industry, synthesis tained wastewaters can cause some serious prob-
fibers, film and thin films, antifreeze, resins and lems to the environment such as negative effects
many more others. Figure 2 determined the rela- on aquatic life, destruction of aquatic ecosys-
tionship between the measured intensities and tems, soil pollution, reducing the oxygen level in
the concentrations of spiked DEG in toothpaste the water absorption through skin contact, brain

111
of the system should be modified by a suitable
material such as conducting polymers. Conduct-
ing polymers are a magnificent material that com-
bines the advantages of organic polymers with the
electrical and optical properties of the metal or
inorganic semiconductors (Gangopadhyay & De,
2000). Moreover, the conducting polymers are very
sensitive to their surrounding environment and
also possessed synergistic properties between the
polymer and inorganic materials, which are mak-
Helping Children Face Tough ing them a very capable candidate for the appli-
cation in several fields such as catalysis, sensors,
electronics, and medicine (Oh et al. 2013).
Figure 2. Calibration curve in logarithmic scales for
detection of DEG in toothpaste samples (Ding et al.
The coating of the conducting polymers to the
2009). working electrode should extend the surface area
of the electrode which will result in enhancing the
interaction between the materials and analytes.
With the increase interaction between the mate-
rial and the analytes, the sensitivity is increased
and a smaller dimension facilitates adsorption/
desorption kinetics for analytes in the materials,
which allows a faster response time and higher sig-
nal reproducibility (Cheng et al. 2011).
Several of DEG sample with different concen-
trations were prepare (from 0 to 50% of DEG)
and analyzed by electrochemical method. The key
factor of the work would be the coating of poly-
aniline (PANI) on the working electrode to create a
capable sensor for the detection of DEG. PANI is
a conducting polymer which possessed advantages
of cost-effective, high conductivity (Khomenko
et al. 2005), ease of synthesis, good stability in air.
Those latter properties made PANI a well-affected
material for acid/base chemical vapor sensors,
Figure 3. The effects of DEG to human health, espe- biosensors, and supercapacitors (Park et al. 2002,
cially dangerous to children and people who have liver Li et al. 2010, Heeger et al. 2000).
and kidney problems (Suresh & Anil. 2015).
Figure 4 show the main structure of the PANI
with n+m = 1 and x = half a degree of the polymeriza-
damages, damage to the Central Nervous System tion process. Polyaniline (PANI) possessed three dif-
(CNS) and joints, eye damage, toxicity, as it were ferent oxidation states with different properties and
indicated in Figure 3. color, as it was shown in Figure 5 (Sun et al. 2009).
According to those facts, the treatment of the Polymerized from the cost effective organic
sources that contained DEG is a very important material of aniline, the polyaniline can be easily
and necessary process to every related industry. found in the three oxidation states as it was indicated
This paper would like to provide a method to in figure 5. These are the three different states of
detect the DEG in aqueous phase using the three polyaniline: Leucoemeraldine: (C6H4NH)n clear and
electrodes electrochemical system (voltammetry colorless, Emeraldine: [(C6H4NH)2 (C6H4N)2]n green
system). Electrochemical has been long known due the emerald base and Pernigraniline: (C6H4N)n
as a capable and effective method for wastewater blue/violet.
treatment, especially with heavy metals contained In this work, we would like to present a method
wastewater source, organic compounds, and chem- of detecting the different concentrations of the
ical oxidation demands species. Not only that, the
electrochemical method also appears as a very good
method for detecting organic compounds such as
DEG in this work, where the performance of the
working electrode plays a significant role.
In order to use the voltammetry system to detect
DEG in the aqueous phase, the working electrode Figure 4. Organic structure of Polyaniline.

112
1M HCl containing 0.5M of aniline monomer
(Yu et al., 2007). The PANI nanowires were syn-
Face Tough thesized by a two steps method which includes the
nucleation of PANI as step 1 and the growth of
PANI as step 2.
The nucleation of PANI was performed by
Face Tough cycling the working electrode potential between
−0.2 V and 1V with all the potential values were
recorded versus the saturated Ag/AgCl reference
electrode. The distance between the working elec-
Face Tough trode and the counter electrode was fixed at 2 cm.
Figure 7 indicates the coating processes on the
working electrode which are carried out separated
Figure 5. Three different oxidation states of the but under the same condition.
Polyaniline. There are two different samples of working
electrode were created, one possessed the high con-
ductive carbon layer and the other one did not. The
DEG in the aqueous phase by using the voltam- thickness of the polymer layer was estimated from
metry method. The working electrode of the sys- the amount of charge (Q) that is necessary to switch
tem will be modified with a suitable coating layer from the leucoemeraldine (LE) (a reduced form of
which is polyaniline (PANI). The performance PANI) into the emeraldine (EM) (an oxidized form
of the coating process would be characterized by
means of Cyclic Voltammetry (CV). Differential
Pulse Voltammetry (DPV) method was adopted to Face Tough
examine the efficiency of the detection process. All
of the experiments were carried out with the sup-
port of low voltage input energy and under room
temperature. The processes which involved the use
of a strongly acidic solution such as HNO3, HCl
and H2SO4 proceeded with the care of proficiency
and safety.
Face Tough
2 METHODOLOGY

Polyaniline was distilled in acid solution before


used. We used the hydrochloric acid HCl 98%
FaceFace
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Tough
for the electropolymerization and other measure- FaceFace
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Tough
ments in this work. Electrochemical experiments
were carried out in a single compartment three-
electrode cells with a glassy carbon electrode as the Figure 6. Voltammetry system.
working electrode. The details on the electrochem-
ical system we used were shown in Figure 6. We
did not perform the etching process on the glassy
carbon electrode, but to improve the adhesion of
the coating layer as well as its quality and dura-
bility; we coated a layer of the high conductivity
carbon solution before the synthesis of polyaniline
take part in. Generally, the Cyclic Voltammetry
(CV) result on the two different coating methods
of polyaniline would be compared for its electro-
chemical performance before they can be used in
the DEG detection process.
Before each experiment, the working electrode
was clean and polished by aluminum powder then
rinsed in DI water, followed by the 30 minutes of
drying in 50°C. Polyaniline was electrochemically Figure 7. The coating processes on the working
synthesized from the aqueous acidic solution of electrode.

113
Table 1. The DEG samples with different concentrations. out in 1M H2SO4 with the potentials between 0 and
1V. As we observe in figures 5–7, the electrochemi-
Samples (%) 0 5 10 15 20 25 30 cal performance of the (b) sample (with a double
DI Water (mL) 30 28.5 27 25.5 24 22.5 21 coating layer of carbon material and PANI) pro-
DEG (mL) 0 1.5 3 4.5 6 7.5 9 vided a better coating efficiency result. The coating
process of the carbon material really increases the
quality of the working electrode with higher con-
ductivity, surface area, and even durability. The
of PANI which is more stable in comparison with meaning of the conductive carbon material was
other states). coated on the glass electrode in the first place is to
According to Obiad (Obiad et al. 2014), the enhance the quality of the PANI layer which will
thickness of the polymer layer can be calculated by be coated later. The conductive carbon materials
the following equation: really increase the area surface, conductivity, dura-
bility and the roughness of the expected area so
Q M.w that the PANI layer can be easy to be coated on
d= afterward. The result we obtained from the coating
Z.F.A.ρ
process was shown in figures 5–8 also prove that
the etching process can be replaced by a capable
Where: Q is the charge, d is the thickness of
surface treatment of other active materials. How-
the polymer layer, Mw is the molecular weight of
ever, the area for the coating process is small; carry
the monomer, z is the number of the electrons/
out these processes in a much larger area should
monomer unit, A is the area of the electrode,
be a challenge (Fonseca et al., 2011). The etching
ρ is the specific density of monomer and F is the
process was proven to be very necessary, not only
Faraday’s constant.
for the creation of the coated layer but also for its
The Cyclic Voltammetry (CV) response of the
durability and the adhesion between the substrate
electrodes was measured at different scan rates var-
and the coating layer (Jurewicz et al., 2001; Peng
ying from 10–100 mV/s. The voltammetry testing
et al., 2007; Frackowiak et al., 2006). The electro-
was carried out at potentials from 0 to 1V in 1M
oxidation of aniline that leads to the polymeri-
of H2SO4 aqueous electrolyte solution. After suc-
zation process followed a two electrons transfer
cessfully created a capable working electrode, the
process:
following work should be the detection of DEG
by using differential voltammetry (DPV) meas-
urement. With several samples of different DEG
concentrations were prepared, the DPV method
would play it role on the measurement of the redox
properties of the DEG in the prepared solution.
A series of DEG samples with different concen-
trations were prepared accorded to the following
Table 1.

3 RESULT AND DISCUSSION

3.1 The polyaniline coating process


The coating of PANI plays a significant role in this
work. In order to provide a capable working elec-
trode for the detection process, the electrochemi-
cal performance and the efficiency of the coating
process are determined by its Cyclic Voltammetry
(CV) result and Differential Pulse Voltammetry
(DPV) results. The coating efficiency should be
indicated by the appearance of the PANI on the
surface of the glassy carbon electrode which will
be characterized in Figure 8.
In these coating processes, a very important
fact is the lack of the etching process. The coated Figure 8. The examination of the PANI existence on
working electrodes electrochemical performances (a) the directly coated sample and (b) the double coated
are tested by a voltammetry measurement carried of conductive carbon solution/PANI.

114
x–ph–NH2 → (ph-NH)x + 2x H+ + 2xe− (Shim et al., 1990). The rate of formation of the
conductive species is closely related to the mobil-
There are many electrochemical methods are ity of anions inside the film which compensates for
suitable for the nucleation and growth of PANI the polymeric positive charge (Bard et al., 1980).
but cyclic voltammetry is proven to be able to pro- Therefore, one usually selects solution with good
duce uniform and compact PANI layers (Gasparac mass transport and limited ion pairing should help
and Martin, 2001). In this work, the PANI was the growth of PANI information. Since the voltam-
electrodeposited onto a surface of a glassy car- metry charge increases on repeated potential scans,
bon electrode with a small desired area from HCl the coating of PANI can be visually observed on
solution of 1M HCl contained 0.3M Polyaniline. the glassy carbon surface. It is inferred that the oxi-
Figure 9 shows the successive cycles of the growth dation potential of aniline overlaps with the poten-
of PANI on the two different substrates which are tial of the oxidation process on the glassy carbon
(a) the inert surface of glassy carbon and (b) the surface. Accordingly, the initial layer of the deposit
conductive carbon layer after 100 circles of CV. is a composite, which consists of the surface oxide
The oxidative peaks in the result are related to on glassy carbon and PANI.
the LE/EM redox couple at first, followed by the According to the result, we obtained, the
appearance of the formation of diradical cations adsorption of aniline is the primary step for the
(bipolaronic pernigraniline) (Hand end Nelson, deposition of the PANI, and it appears that
1974). As we can observe, the supports from HCl the adsorption of the monomers takes place on the
electrolytes solution help the mobility of radical electrode surface followed by the oxidation steps.
cations to travel to the electrode surface for the When the electrode is passivated with the depos-
formation of PANI. The increasing of the current ited PANI layer in the initial cycle, the surface oxi-
in voltammetry peaks is a capable indicator for the dation of the expected coating area is prevented. It
growth of PANI. is expected the kinetics of PANI deposition during
The higher concentration of the HCl can enhance the subsequent potentiodynamic cycles may not
the mass transport of the electrodeposition process depend on the substrate properties. Therefore, the
surface of the working electrode is a very impor-
tant factor in the electron transfer process to the
outer layer of the PANI.

3.2 The detection of diethylene glycol (DEG)


As we mentioned above, there are several samples
of DEG solution were made for these tests. The
detection of DEG process is performed by using
voltammetry method with a modified working
electrode. The result of these processes would be
shown through the Differential Pulse Voltammetry
(DPV) measurement of each sample. Figure 10
shows the DPV result of the 0% of DEG sample,
this sample plays a very important role here, as
a standard sample. The other results were made
according to the comparison with the standard
sample.
The signal of the linear sweep in figures 5–11
indicates that there are peaks appeared. Without
the existence of the DEG, those peaks should be
related to the other species in this electrolyte solu-
tion such as KNO3 with a very small amount.
There were totally seven samples prepared for the
test in which we classify them into 2 groups: the
low concentration samples (5%, 10%, and 15%)
and the average concentration samples (20%, 25%,
and 30%). The DPV results of those samples were
Figure 9. Cyclic voltammograms (100th circles) from shown in the following figures.
1M HCl/0.3M Polyaniline of (A) the directly coated sam- Figure 11 shows the DPV result of the low con-
ple and (B) the double layer coated sample (Conductive centration samples, followed by (a) 5% of DEG
carbon layer/PANI). sample, (b) 10% of DEG sample and (c) 15% of

115
Figure 10. The DPV result of the standard sample
(0% of DEG).

DEG sample. According to the observed peaks,


the detection of DEG can be obtained at different
current density value applied to each sample.
It appears that, at low concentration of DEG,
the detection process obtained a very good signal
due to the superiority of the modified working
electrode. The measurement process seems to be
very stable, after several runs for each measure-
ment on each sample; the DPV results remain
almost unchanged. Figure 12 shows the results of
the average concentration group which is include
3 sample of DEG with concentrations of DEG
from 20 to 30%. At first sight, the failing of cur-
rent in these tests is easy to notice. The failing of
current indicates that the signal of the detection is
decreasing, and the stable state is about to be bro-
ken. If peaks from the low concentration group
appeared to be in the order of forms and signal,
the peaks we obtained from here is getting smaller
and weaker. With the same applied potential, the
current of the detection process decide the mass
transport inside the DEG solution, and through
that indicate the appearance of this compound Figure 11. DPV results of (a) 5% of DEG Sample,
in the aqueous phase (with different concentra- (b) 10% of DEG sample and (c) 15% of DEG sample.
tions). From (d) to (e), the current is continuing
its decreasing which lead to the unstable of the of average concentration group. The result of that
obtained peaks. test was shown in Figure 13.
The resulted peaks are getting smaller and As we can observe, the result appears in
smaller which means the voltammetry measure- Figures 5–13 is similar to the one in Figures 5–10
ment is occurring problem to detect the DEG com- as the sensors fail to detect the appearance of the
pound. At 30% of DEG in solution, the sample DEG in the solution. Generally, the differences
appears to have no peak (similar to the 0% DEG between the two sample in the two related figure
sample). The detection result obtained at the sam- is clear, however, the fall of detection is due to the
ple of 30% DEG indicates that the samples which damage of the PANI layer on the surface of the
are possessed more than 30% of DEG should be working electrode. With a higher concentration
adopting a different method of condition to detect of DEG, the contact between the sensors and the
the appearance of DEG compound. To ensure this organic compounds increases rapidly, and thus to
conclusion, we carried out more test on the 50% have some effects and damage to the PANI layer.
of DEG sample and encountered the very same With the quality of the PANI layer decreased, the
problem in comparison with the previous results signal we obtained was getting weaker and fails.

116
This issue can be solved easily by applying a capable
material which can enhance the adhesion between
the PANI layer and the glassy carbon surface, or
a protection layer that can keep the PANI coating
working for a longer time should be an idea.

4 CONCLUSION

Several experiments and tests were carried out in


order to detect the DEG in the aqueous phase at
this work. It appears that the method we provided
is working well with the sample of low concentra-
tion DEG. Voltammetry method is proven to be
a capable method for the detection of DEG, not
only that, the method also performed as a preci-
sion characterized method for electrochemical
process performance. The key factor that decided
the notable result of the detection of DEG is the
performance of our working electrode. Without
using the etching process, the coating method we
performed still shows a remarkable result.
With the supports from the conductive carbon
layer, the PANI layer is successfully coated on the
working electrode and providing capable proper-
ties, which possessed a higher sensitivity, selectiv-
ity, surface area, environmental stability and even
the surface properties. However, the coating proc-
esses were carried out on a small expected area
which turns out to a challenge for applying the
same method on a larger substrate.
The signal we obtained was becoming weaker
as we increased the concentration of the DEG in
the test sample. The problem can be explained by
the damage of the PANI layer at the surface of the
glassy carbon electrode. With a higher concentra-
tion of DEG occurred, the contact between the
DEG and the PANI has become more and more
Figure 12. DPV results of (d) 20% of DEG sample, regular, thus resulted in the losing of PANI. With-
(e) 25% of DEG sample and (f) 30% of DEG sample. out a proper amount of PANI at the surface of the
sensor, the detection process became less efficient.
Accordingly, a method of increasing the adhesion
between the PANI and the surface of its substrate
is needed and necessary to apply. The results we
obtained from the detection process indicate that
there is still improvement needs to be done with
the process, where the detection of DEG at higher
concentration and applying the removing of DEG
should be considered as future works.

ACKNOWLEDGEMENT

All the experiments were carried out at room tem-


perature, original pH value and no special treatment
of chemical. The work is completed and finished at
the lab of the Green Energy Development Center,
Figure 13. DPV result of 50% DEG sample. Feng Chia University, Taichung City, Taiwan.

117
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trochemistry of one dimensional nanostructured
Bard, A.J., Faulkner, L.R. 1980. Electrochemical Methods, MnO2/PPy composite for electrochemical capacitor.
Fundamentals and Applications, Wiley, New York. App. Surf. Sci. 256, 4339–4343.
Brent, J. 2001. Drugs. 61, 979–988. Marraffa, J.M., Holland, M.G., Stork, C.M., Hoy, C.D.,
Cheng, Q., Tang, J., Ma, J., Zhang, H., Shinya, N., Hodgman, M.J.J. 2008. Emerg, Med., 35: 401–406.
Qin, L.C. 2011. Polyanilline Coated Electro Etched Obiad, A.Y., El-Mossalamy, E.H., Al-Thabaiti, S.A., El-
Carbon Fiber Cloth Electrodes for supercapacitors. Hallag, I.S., Hermas, A.A., Asiri, A.M. Electrodepo-
American Chemical Society. sition and characterization of polyaniline on stainless
Ding, J., Gu, H., Yang, S., Li, M., Li, J., Chen, H. 2009. steel surface via cyclic, convolutive voltammetry and
Selective detection of diethylene glycol in toothpaste SEM in aqueous acidic solutions.
products using natural desorption reactive extractive O’brien, K.L., Selanikio, J.D., Hecdivert, C., Placide,
electrospray ionization tandem mass spectroscopy. M.F., Louis, M., Barr, D.B., Barr, J.R., Hospedales,
Analytical Chemistry, 81. C.J., Lewis, M.J., Schwartz, B., Philen, R.M., Victor, S.,
Fonseca, C.A., Almeida, D.A.L., Baldan, M.R., Espindola, J., Needham, L.L., Denerville, K. 1998.
Ferreira, N.G. Influence of PANI morphology deposited J. Am. Med. Assoc., 279, 1175–1180.
on the carbon fiber: An analysis of the capacitive behav- Oh, W.K., Kwon, O.S., Jang, J. 2013. Conducting polymer
ior of this hybrid composite. nanomaterials for biomedical applications: Cellular
Frackowiak, E., Khomenko, V., Jurewicz, K., Lota, K., interfacing and biosensing. Polym. Rev., 53, 407–442.
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Gasparac, R., Martin, C.R. 2001. J. Electrochem. Soc., 20–25.
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Hand, R.L., Nelson, R.F. 1974. J. Am. Chem. Soc., 96, 850. Conducting polymer based nanohybrid transducers: a
Hanif, M., Mobarak, M.R., Ronan, A., Rahman, D., potential route to high sensitivity and selectivity sen-
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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Removal of ion Pb2+, Zn2+, Cu2+ in aqueous solutions by red mud


of Bao Loc Bauxite

T.T.O. Truong
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: Red mud is a waste of aluminum production industry from bauxite ore, which is difficult
to handling waste, destruction and highly alkaline should be classified as toxic to organisms. One to two
tons of red mud is discharged based on production of each ton of aluminum. There have been many stud-
ies to use red mud to make bricks, ceramics, cultivate and materials. In this study, the red mud is mixed
with additives to produce adsorbent heavy metal ions for the application in wastewater treatment. The
results showed that the model adsorption gave more efficiency performance than the dynamics model.
This material has the capacity of asbsorbent for the ion Pb2+ is around 97%, while with the ion Cu2+ and
ion Zn2+ is about 25% and 22% when using 1 gr of material red mud for about 10 h.

Keywords: adsorption, red mud, heavy metal, performance

1 INTRODUCTION produce granular material red mud. The experi-


mental planning is performed according to the fol-
Water pollution is a serious problem for the entire lowing diagram (Figure 1).
world as well as in Vietnam due to its strong impact Preparation of adsorbent: Before conducting
to the human beings and the delicate balance in the the survey adsorption capacity of red mud, the
natural ecosystem. The water source is located close sample material Bao Loc bauxite red mud is dena-
to the industrial zones containing high concentra- tured by thermal shock with the additive needed
tions of toxic substances and heavy metals. The in the parameters have been optimized to create
other problematic is that heavy metals being released granular adsorbent solid. The results showed that
into the environment if very difficult to handle, they the absorption capacity of the material metallic red
spread under water, soaked into the soil, absorbed mud increases quite high (about 3.3 times) com-
by plants from which enters the body through which pared to non-modified raw.
the creatures and go on the human body. Heavy Examination followed by adsorption properties
metals can not be destroyed by time which increas- of two models of adsorption static and dynamic.
ingly accumulate and cause serious adverse effects In fact wastewater treatment by adsorption method
and problematic for the environment. has two static and dynamic models, need to select
Red mud is the major solid waste produced in appropriate models to achieve high processing
the process of alumina extraction from bauxite.
This waste cannot be disposal easily and it is being
dump into the sea or in lakes containing liquid
slurry and dried naturally before burial. However Face Tough FaceFace
Tough
Tough
both methods of treatment are not good solution Face Tough
Face Tough
in short term and long term. Many researchers
around the world and in Vietnam showed that red
mud has adsorption capacity of heavy metals and
other pollutants [1–6]. In our study, we investigated
initially available adsorption capacity of sludge to
be used in wastewater treatment.

2 RESULTS AND DISCUSSION

Red mud is used in this experiment is red mud of


bauxite Bao Loc, combined with the additives to Figure 1. Experimental planning.

119
performance, greater absorption, saving time and absorption (1.33 times larger) than the dynamic
cost of the most is consistent with the actual condi- adsorption model.
tions. The experimental results for comparison of Adsorption capacity of heavy metal ions (Pb2+,
the two models static and dynamic are presented in Cu2+, Zn2+) on the adsorbent materials depended on
the following table (Table 1). the influencing factors. The studies on the adsorp-
Tab.1 shows that the static adsorption model tion capacity of heavy metal ions and the influ-
is more efficiency (1.25 times higher) and greater encing factors in the static model were examined.

Table 1. Comparing results for the two models static and dynamic adsorption.

Experimental
Model replicates E% Eaverage% a (mg g−1) atb (mg g−1)

Dynamic D-1 43.96 44.31 ± 0.49 0.6896 0.6973 ± 0.0094


D-2 44.87 0.7078
D-3 44.088 0.6946
Static S-1 55.72 53.8 ± 1.7 0.9631 0.930 ± 0.029
S- 2 53.03 0.9169
S- 3 52.57 0.9097

Face Tough Issues Face Tough Issues

Face Tough Issues Face Tough Issues

Figure 2. The effect of contact time on different Figure 3. The effect of contact time on different
concentration Pb2+. (2a. red mud dose: 1 g; 2b. red mud concentration Cu2+ (a. red mud dose: 1 g; b. red mud
dose: 2 g). dose: 2 g).

120
The test included: the impact of material volume was studied. The some parameter of adsorption
(1 g and 2 g of red mud adsorbent), the effect of such as the contact time, the dose of red mud and
adsorbed solution concentration (30–60 mg L−1 the concentration of Pb removal was studied and
(ΔC = 10 mg L−1)), the effect of contact time presented in Figure 3.
between the adsorbent and the adsorption solution Figure 3 shows the performance adsorbed of ion
(2–10 hours (Δt = 2 h). Cu2+ is not high, the highest performance reached
Removal efficiency on ion Pb2+: the effect of just over 25% (for 1 g of adsorbent, [Cu2+] = 49 mg
contact time and the dose of red mud (adsorbent) L−1, contact time: 10 h). In both experiments with
on different concentration of Pb removal are pre- 1 g and 2 g of red mud, it can be found when the
sented in Figure 2. contact time increased; the adsorption capacity of
According to the results in Fig. 2, the perform- adsorbent is also increased (Figure 4).
ance adsorbed ions Pb2+ is higher than 97% (dose On the contrary of the case Pb2+ initial con-
red mud: 1 g, initial concentration [Pb2+]: 31 mg L-1, centration of Cu2+ increases, the performance
contact time: 10h). The removal of Pb is rapid and adsorption decreases. In this case, when the first
the percentage of the adsorption is 100% when dose concentration (Co) of the solution Cu2 + increased
of adsorbent is 2 g at all concentrations of ion Pb. from 36–49 mgL−1 and from 54–64 mgL−1, the
Removal efficiency on ion Cu2+: in this study, performance increases. The reason is that in the
the removal of ion Cu2+ from aqueous solution case, the concentration of adsorbed ions Cu2+

Children Face Tough Children Face Tough


Face Tough Issues Face Tough Issues

Children Face Tough


Face Tough Issues Children Face Tough
Face Tough Issues
Figure 4. The effect of adsorption on removal effi-
ciency of ion Cu2+ (a. factors: dosage of Cu, contact
time, adsorbent dose: 1 g; b. factors: dosage of Cu, con- Figure 5. The adsorption isotherm ion Cu2+ (a. dose of
tact time, adsorbent dose: 2 g). adsorbent 1 g; b. dose of adsorbent: 2 g).

121
Children Face Tough Children Face Tough
Face Tough Issues Face Tough Issues

Children Face Tough


Children Face Tough
Face Tough Issues
Face Tough Issues
Figure 7. The effect of adsorption on removal efficiency
Figure 6. Efficiency performance of ion Zn2+ ( contact of ion Cu2+ (a. dose of Cu, contact time, adsorbent dose:
time 2h–10h, (a. red mud dose: 1 g; b. red mud dose:2 g). 1 g; b. dose of Cu, contact time, adsorbent dose: 2 g).

increase causing the adsorption particularly high. adsorption between the two levels of 49 mgL−1 and
According adsorption theory, the solution concen- 54 mgL−1 is shorter because the complex has more
tration increases, and the adsorption also increases. time to migrate to the surface of the adsorbent and
However the results in the Figure 5 shows that the adsorption happens.
when the concentration of ion Cu2+ increased from Removal efficiency on ion Zn2+: effect of
49 mgL−1 to 54 mg L−1, its adsorpbent is reduced. contact time and the dose of red mud (adsorb-
This may be due to the concentration ion of Cu2+ ent) were examined in this experiment. Accord-
increases up to a value large limit, it can be formed ing to the results on the performance ion Zn2+
complexes [Cu(OH)4]2− with OH− of adsorbent (ion is low, the highest efficiency is just over 22% at
exchange). Because of the complex size is much [Zn2+] = 45 mgL−1 (adsorbent: 1 g, the contact time:
larger than the size and negatively charged ions 10 h) and only percentage of adsorption 37% at
so it has poor adsorption capacity than the metal [Zn2+] = 63 mgL−1 (adsorbent: 2 g, contact time is
ion adsorption; thereby it reduces the absorption. also 10 h).(Figure 6).
On the other hand, the adsorption rate of complex Similar to the adsorption of ion Pb2+ and Cu2+,
[Cu (OH)4]2− is less than the rate of ion adsorp- when the contact time increases, the efficiency per-
tion. This is shown in the Fig. 5.a and [Link] at formance adsorption of ion Zn2+ also increases.
the contact time of between solution aqueous and Figure 7a shows that with the contact time is 2, 4, 6,
adsorbent red mud is 2h, the adsorption at concen- 8 hours, the concentration of Zn2+ increased from
tration 49 mgL−1 and 54 mgL−1 is much different. 57 mgL−1 to 63 mgL−1, the absorption is decreased.
When increasing the contact time, the difference in It reveres with the adsorption theory which is the

122
absorption increases as long as the concentration Ayoob, S., Gupta, A.K. & Bhakat, P.B. 2007. Performance
increases. The cause of it may be due in concen- evaluation of modified calcined bauxite in the sorptive
tration Zn2+ is 63 mgL−1 and formed a complex of removal of arsenic(III) from aqueous environment.
[Zn(OH)4]2−. Colloids and Surfaces A: Physicochemical and Engi-
neering Aspect, 293 (1–3):247–254.
Therefore its adsorption is less complex and Bertocchi, A.F. et al. 2006. Red mud and fly ash for
the adsorption ion also slower, these factors remediation of mine sites contaminated with As, Cd,
make the absoprtion decrease. When testing with Cu, Pb and Zn. Journal of Hazardous Materials, 134
the contact time is 10 h, the new isotherm follow (1–3):112–119.
BET adsorption theory, because there is a com- Gupta, V.K., Ali, I. & Saini, V.K. 2004. Removal of
plex form [Zn(OH)4]2− with the concentration Chlorophenols from Wastewater Using Red Mud:
Zn2+ = 63 mgL−1. However with a long contact An Aluminum Industry Waste. Environmental
time (10 h) the complexes still have enough time Science & Technology, 38(14):4012–4018.
to move and is adsorbed onto adsorbent material; Kikuchi, T. et al. 2009. Assessment of Heavy Metal
Pollution in River Water of Hanoi, Vietnam Using
thus it increases the adsorption. Multivariate Analyses. Bulletin of Environmental Con-
tamination and Toxicology, 83(4):575–582.
Klauber, C., Gräfe, M. & Power, G. 2011. Bauxite residue
CONCLUSION issues: II. options for residue utilization. Hydrometal-
lurgy, 108(1–2):11–32.
Through the research results obtained in this Nguyen, D.N.H. 2012. Preparation of coagulant agent
paper, the red mud denatured has remove of metal from aluminum residues of Tan Binh chemical factory.
in a wide pH range. This is an advantage in apply- Master thesis—National University—HoChiMinh City.
ing materials to handle heavy metals the different Truong, B.U. 2007. Study of characteristic of mate-
rial adsorbent of red mud. Master thesis—National
types in aquoues. Adsorption capacity of Pb2+ ions University—HoChiMinh City.
of the material is quite high while the absorption Wang, S., Ang, H.M. & Tadé, M.O. 2008. Novel applica-
capacity Cu2+ and Zn2+ ions are relatively low (less tions of red mud as coagulant, adsorbent and catalyst
than 7 times the Pb2+). Application this materials for environmentally benign processes. Chemosphere,
for remove the heavy metal in aqueous is good 72(11):1621–1635.
results, but for the kind of concentration ion metal Wang, S. et al. 2005. Removal of dyes from aqueous
is too high. However, the adsorption capacity of solution using fly ash and red mud. Water Research,
the red mud with Cu2+ ions and Zn2+ are limited 39(1):129–138.
and need to optimize the experimental conditions
to increase the adsorption capacity better.

REFERENCES

Apak, R., Güçlü, K. & Turgut, M.H. 1998. Modeling of


Copper(II), Cadmium(II), and Lead(II) Adsorption
on Red Mud. Journal of Colloid and Interface Science,
203 (1): 122–130.

123
Clean energy and sustainability
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Single-stage biohythane production via co-immobilized fermentative


microorganisms

C.Y. Lin
Department of Environmental Engineering and Science, Feng Chia University, Taichung, Taiwan
Master Program of Green Energy Science and Technology, Feng Chia University, Taichung, Taiwan
Green Energy Development Center, Feng Chia University, Taichung, Taiwan
Green Energy Group, Ton Duc Thang University, Ho Chi Minh City, Vietnam

D.T. Ta
Master Program of Green Energy Science and Technology, Feng Chia University, Taichung, Taiwan

C.Y. Chu
Master Program of Green Energy Science and Technology, Feng Chia University, Taichung, Taiwan
Green Energy Development Center, Feng Chia University, Taichung, Taiwan

T.M.N. Ta
Faculty of Food Technology, Nha Trang University, Nha Trang, Vietnam

ABSTRACT: Single-stage biohythane production via co-immobilized fermentative microorganisms was


investigated in order to achieve a hythane percentage of 15%H2/45%CH4. At current stage, a double-layer
immobilization method was being developed and an examination of single-layer methanogen beads in a
batch reactor was carried out in 6 runs with different sugar concentration (3.33–14.2 g/L) and acidogen/
methanogen ratio. Double-layer beads were successfully made with a total diameter of 5 mm and a core
diameter of 3.5 mm in averages. The finest H2 and CH4 content of 3.94% and 52.85% were obtained in
Run 6 at 26.5 h.

Keywords: single-stage biohythane, fermentative microorganisms, batch reactor

1 INTRODUCTION which guarantees the regulation of H2/CH4 ratio


by adjusting the conditions of cultivation (Suresh
It have been report that in order to keep the global Babu et al., 2015). However, due to large space
warming rise below 2°C throughout the twenty- occupation and complication, this process may
first century, the limiting cumulative carbon emis- have some difficulties in setup, operating and
sions over 2000 to 2050 should not exceed 1000 Gt maintenance. Therefore integration of both stages
of CO2 (Meinshausen et al., 2009). To meet this into one single system is designed to solve these
target, globally one third of oil reserves, half of problems.
gas reserves and over 80% of current coal reserves Cell immobilization has gained significant appli-
was suggested to remain unused from 2010 to 2050 cations in different industries such as food produ-
(McGlade and Ekins, 2015). In this worldwide tion (Mensour et al., 1996), waste-water treatment
critical circumstance, renewable energy is the key (Park et al., 1998), pest control (Kim et al., 2012),
to conserve the existing global fossil fuel reserves and productions of therapeutic agents (Byrd et al.,
and resolve the global warming issues. 2005), enzyme (Elibol et al., 2003) and biofuel
Hythane, a mixture of hydrogen and methane, (Ogbonna et al., 2001). Immobilized-cell systems
is a sustainable energy carrier in which the slow have reactor performance advantages over freely
burning and hard igniting methane is comple- suspended culture in easy separation of the bio-
mented perfectly by the inflammable hydrogen mass from the liquid, easy product recovery, enlarg-
(Bauer and Forest, 2001; Porpatham et al., 2007). ing the cell density, avoiding washout and specific
The biological hythane production can be accom- metabolic improvements or products created upon
plished by a two stage dark fermentation system, immobilization (De Vos et al., 2009; Zhu, 2007).

127
This immobilization technology is attractive in the conditions to achieve the goal of hydrogen 15%
co-immobilization of hythane-producing micro- and methane 45%. Methanogens were immobi-
bial communities within gel beads in such a way lized in k-carrageenan/gelatin 2%/2% in a ratio of
that methanogens and acidogens are in outer and 3g methanogens: 1 g polymers (Run 1) and 27g
core layers, respectively (Santos et al., 1996). More- methanogens: 4.5 g polymers (Run 2) (Gardin and
over, a polymer matrix gel can possibly protect the Pauss, 2001). Free methanogens were also used to
cells from harsh pH condition and the separation compare. In this batch experiment, 6 runs were
of these bacteria could help preventing them from carried out.
the nutrient competition and over growth (Rathore
Run 1: Adding 12 g sugar, 30 mL free acidogen and
et al., 2013). On the other hand, the product of the
3 g immobilized methanogen to make the Vreactor
core layer could be easily used by the outer one.
reaching 1.2 L after loading stuffs. The initial
These characteristics enhance the application of
pH was 7.92.
immobilization technology to biohythane in a sin-
Run 2: Adding 6 g sugar and 27 g immobilized
gle reactor (Santos et al., 1996).
methanogen to make the Vreactor reaching 1.8 L.
This study described both qualitative and quan-
The initial pH was 7.48.
titative aspects of co-immobilization of acidogens
Run 3: Vreactor was reduced to 1 L to prevent an over-
and methanogens by extrusion method to form
flow. After that, adding 20 g sugar and 33 ml
double-layer gel beads for biohythane production
free acidogen to make Vreactor reaching 1.4 L. The
with percentage of 15%H2/45%CH4. Methanogens
initial pH was 7.7.
were entrapped with potassium k-carrageenan in
Run 4: Vreactor was reduced to 1 L, adding 10 g sugar
outer layer of the beads and acidogens were cored
and 7 g free methanogen to make Vreactor reach-
with calcium alginate. At current stage, while devel-
ing 1.2 L. The initial pH was 7.5.
oping the possibility of creating double-layer beads,
Run 5: Adding 10 g sugar and 38 g free methano-
single-layer beads were batched tested to examine the
gen to make Vreactor reaching 1.4 L. The initial
capability of producing hythane in only one reactor.
pH was 7.11.
Methanogens were immobilized in k-carrageenan
Run 6: Vreactor was reduced to 1 L, adding 15 g sugar
beads while acidogens were freely suspended.
and 100 mL free acidogen to make Vreactor reach-
ing 1.4 L. The initial pH was 7.43.
2 MATERIALS AND METHODS
2.4 Double-layer immobilization procedure (Dos
2.1 Microorganisms Santos et al., 1996)
Seed methanogens and acidogens were collected Methanogens were added to a final mixture of 3%
from laboratory of Green Energy Development (w/w) alginate and 1 M KCl (solution 1). Solution
Center, Feng Chia University, Taiwan. In the 2 had k-carrageenan, CaCl2 and BaCl2 of 1.5%
examination of single-layer methanogen beads in (w/w), 0.08 M and 0.02 M, respectively. Solution
a batch reactor, the methanogens were aggregated 1 was extruded dropwise through a hollow needle
into granules of 0.5–2.0 mm in diameter, the aci- into solution 2 to obtain double-layer beads.
dogens were suspended. In the double-layer immo-
bilization test, the methanogens and acidogens
were centrifuged then re-suspended. 3 RESULTS

3.1 Examination of single-layer methanogen


2.2 Media beads in a batch reactor
The nutrient medium had components of (per Run 1: Total biogas was 4650 mL in which 4430ml
1000 ml): (NH4)2HPO4 (700 mg), NH4Cl (850 mg), was obtained at 21.5 h. The highest CH4 per-
MgSO4.7H2O (250 mg), KCl (750 mg), MgCl2.6H2O centage (0.053%) was achieved at 94.5 h, while
(810 mg), FeCl3.6H2O (420 mg), NaHCO3 (6720 mg) the H2 production reached its peak of 50.77%
and CoCl2.6H2O (18 mg) (Lin, 1986). Glucose was at 52.5 h (Fig. 1a). At 21.5 h, the reactor’s color
used as a substrate. Different concentrations (3.33– was totally white, the pH was 5.17 and no CH4
14.2 g/L) were used in 6 runs. was obtained, then 159ml of 0.2M KOH was
added to adjust the pH to 7.93. At 27.5 h, the
reactor’s color turned grey but still no CH4 was
2.3 Examination of single-layer methanogen
obtained, the pH dropped down to 7.32. CH4
beads in a batch reactor
started to produce after the reactor’s liquid
In order to examine the feasibility of hythane pro- turned to black at 52.5 h. The pH also increased
duction, a batch reactor was performed in certain slowly from 7.32 at 27.5 h to 7.7 at 94.5 h.

128
Figure 1. Biogas component of: (a) Run 1, (b) Run 2, (c) Run 3, (d) Run 4, (e) Run 5, (f) Run 6.

Run 2: Total biogas was 3730 mL in which 3566ml (31.57%) from great increment of free methano-
was obtained at 22 h. The highest CH4 percent- gen (Fig. 1e). The pH dropped to 6.4 at 22.5 h
age increased to 3.16 at 73 h since the addition and slowly went up to 6.81 at 123 h.
of methanogen while H2 percentage dropped Run 6: Total biogas was 2452 mL. Adding more
dramatically with its peak of 24.13% at 22 h acidogen resulted in both CH4 and H2 incre-
(Fig. 1b), which might be resulted from the ment (52.85% and 3.94% at 26.5 h, respectively)
growth of methanogen. The pH dropped to (Fig. 1f). In this Run, gas test was carried out
6.46 at 22 h and slowly went up to 7.41 at 73 h. without taking the gas out of gas bag. The pH
Run 3: Total biogas was 6098 mL. At 3.5 h, only dropped to 6.54 at 26.5 h and slowly went up to
362 of biogas was obtained. Low percentage of 7.32 at 77 h.
CH4 (1.33%) and a bit higher percentage of H2
(25.1%) were obtained. High sugar concentra-
tion indicated high gas accumulation (Fig. 1c). 3.2 Double-layer immobilization
The pH dropped to 7.46 at 3.5 h and to 6.67 at A double-layer bead was successfully made which
22 h. had a white k-carrageenan outer layer and grey
Run 4: Total biogas was 2670 mL, at 9.5 h, most of alginate core. Total beads’ diameter was 5 mm and
the biogas had been produced (2564 mL). The core diameter was 3.5 mm in averages (Figure 2).
CH4 percentage was 7.9% at 9.5 h and increased
to 8.21% at 32.5 h. The H2% peak was 18.56% at
9.5 h. (Fig. 1d). The pH dropped to 6.51 at 9.5 h 4 DISCUSSION
and slowly went up to 6.7 at 32.5 h.
Run 5: Total biogas was 2452 mL in which 2392 K-Carrageenan beads had good capability to with-
was obtained at 22.5 h. Almost no H2 was stand the operation conditions in the batch reac-
obtained (0.15%). CH4 increased significantly tor. However, it needs to be strictly handled with

129
R OH + H2 PO −4 → R − O PO3H2 + OH − (1)

The formation of hydro-phosphate groups


(R-O-PO3H2) on the k-carrageenan molecules
would not permit the K+ insertion and the gela-
tion. Therefore the phosphate buffer could no
longer be used in the specific activity tests (Gardin
and Pauss, 2001).
As strict temperature condition is necessary
for handling k-carrageenan, a droplet operation
at lower than 40°C might cause all of the already-
made beads to stick together (Fig. 2d). The other
problem was the high viscosity of Solution 2,
Figure 2. A double-layer bead (a), half-cut double-layer which made it difficult for the droplet to penetrate
bead (b), cut double-layer bead (c), double-layer beads
(Fig. 2e). This might be solved by increasing the
stick together because of low temperature droplet (d),
double-layer bead floated on the surface of Solution 2 (e). droplet height or increasing the stirring speed,
which should have enough levels to create a vortex
for Solution 2 to drag the droplet inside.

a proper temperature. The size of the beads could


be adjusted by replacing the granule bacteria with 5 CONCLUSION
suspended one. Most of the gas was produced
within 6–9.5 hours. After that, very low gas vol- For preparing the double-layer beads, a proper tem-
ume was observed with most content being CO2 perature of over 40°C should be applied; otherwise
and CH4. Since the pH was not controlled, after k-carrageenan must be not used. For efficient bio-
adding nutrient and sugar the pH was around 7.5 hythane production, in double-layer beads acidog-
but dropped to 6.4 at the time that most of the gas ens should be placed in the core layer to increase
was produced, then pH slowly went up to around the contact chances of the produced H2 with the
7.0 before another nutrient and sugar were loaded. methanogens for increasing CH4 production.
This could be explained as the acid production
of acidogen at acidogenesis stage and the acid
consumption of methanogen at methanogenesis ACKNOWLEDGEMENTS
stage in dark fermentation (McCarty et al., 1982).
The ratio of acidogen/methanogen played a quite This work was financially supported by Ministry
important role in adjusting the gas component. In of Science and Technology, Taiwan (MOST 104-
the case of encapsuling the acidogens in the out 2221-E-035-006-MY3).
layer, the immobilized methanogens had a very low
chance to consume H2 to produce CH4. It might be
possibly due to the limitation of H2 traveling into REFERENCES
the beads. This can be solved by swapping the cap-
sule places of acidogens and methanogens. Bauer, C.G., Forest, T.W., 2001. Effect of hydrogen
In order to decrease the floating problems of the addition on the performance of methane-fueled
beads, some gelatin was added to the k-carrageenan vehicles. Part I: Effect on S.I. engine performance.
gel. Besides its gelling properties, gelatin is a tradi- Int. J. Hydrogen Energy 26, 55–70.
Byrd, W., de Lorimier, A., Zheng, Z.R., Cassels, F.J.,
tional component of culture media for microbial 2005. Microencapsulated subunit vaccine approach to
growth (as carbon and nitrogen sources). This enterotoxigenic Escherichia coli and other mucosal
polymer was likely to be consumed by the immo- pathogens. Advanced Drug Delivery Reviews 57 (9),
bilized microbial communities. The disappearance 1362–1380.
of gelatin from the gel matrix might change the gel De Vos, P., Bucˇko, M., Gemeiner, P., Navratil, M.,
porosity and favour the release of biogas (Gardin Švitel, J., Faas, M., Strand, B.L., Skjak-Braek, G.,
and Pauss, 2001). Morch, Y.A., Vikartovska, A., Lacik, I., Kollarikova,
With KH2PO4 (30 mmol/l), the k-carrageenan G., Orive, G., Poncelet, D., Pedraz, J.L., Ansorge-
beads disappeared after 16 h, although same con- Schumacher, M.B., 2009. Multiscale requirements
for bioencapsulation in medicine and biotechnology.
centration of K+ was available. A specific reaction Biomaterials 30 (13), 2559–2570.
would be possible between the phosphates (H2PO4–) Elibol, M., Moreira, A.R., 2003. Production of extra-
and the non-charged secondary alcohols of the cellular alkaline protease by immobilization of the
k-carrageenan molecules. The reaction would be marine bacterium Teredinobacter turnirae. Process
as follows (Equation 1): Biochemistry 38 (10), 1445–1450.

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Gardin, H and A. Pauss, 2001. k-carrageenan/gelatin Park, Y.S., Yun, J.W., Kim, D.S., Song, S.K., 1998.
gel beads for the co-immobilization of aerobic Wastewater treatment in a packed-bed reactor with
and anaerobic microbial communities degrading immobilized cells onto a new ceramic carrier. Biotech-
2,4,6-trichlorophenol under air-limited conditions. nology Techniques 12 (6), 459–462.
Appl Microbiol Biotechnol 56: 517–523. Porpatham, E., Ramesh, A., Nagalingam, B., 2007. Effect
Kim, I.Y., Pusey, P.L., Zhao, Y., Korban, S.S., Choi, H., of hydrogen addition on the performance of a biogas
Kim, K.K., 2012. Controlled release of Pantoea agglo- fuelled spark ignition engine. Int. J. Hydrogen Energy
merans E325 for biocontrol of fire blight disease of 32, 2057–2065.
apple. Journal of Controlled Release 161 (1), 109–115. Santos, V.A.P.M., Bruijnse, M., Tramper, J. Wijffels,
Lin, Chiu-Yue 1986. Effects of substrate loading rate and R.H., 1996. The magic-bead concept: an intergrated
temperature on methanogenesis process in anaerobic approach to nitrogen removal with co-immobilized
digestion. Doctoral thesis, Tohoku University, Japan. micro-organisms. Applied Microbiology and Biotech-
McCarty, P.L., In “Anaerobic Digestion 1981” Eds. nology 45: 447–453.
Hughes, D.E., 3-22 (1982) Elsevier Biomedical Press, Suresh Babu Pasupuleti, S. Venkata Mohan, 2015. Single-
Amsterdam, New York, Oxford. stage fermentation process for high-value biohythane
McGlade, C., Ekins, P., 2015. The geographical distribu- production with the treatment of distillery spent-
tion of fossil fuels unused when limiting global warm- wash, Bioresource Technology 189, 177–185.
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Meinshausen, M., Meinshausen, N., Hare, W., Raper, Valeria Liew, Lai Wah Chan, Paul Wan Sia Heng,
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M.R., 2009. Greenhouse gas emission targets for lim- Journal of Food Engineering 116, pp. 369–381.
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Mensour, N.A., Margaritis, A., Briens, C.L., Pilkington, H., tion of chemicals and fuels. In: Yang, S.T. (Ed.), Bio-
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Bioresource Technology 76 (1), 1–8.

131
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Anaerobic bio-hythane production in a single reactor

C.Y. Lin
Department of Environmental Engineering and Science, Feng Chia University, Taiwan
Green Energy Development Center, Feng Chia University, Taichung, Taiwan
Master’s Program of Green Energy Science and Technology, Feng Chia University, Taichung, Taiwan
Green Energy Technology Group, Faculty of Labour safety and Environment Engineering, Ton Duc Thang
University, Ho Chi Minh City, Vietnam

P.C. Hung
Department of Environmental Engineering and Science, Feng Chia University, Taichung, Taiwan

C.H. Lay
Master’s Program of Green Energy Science and Technology, Feng Chia University, Taiwan
Green Energy Technology Group, Faculty of Labour safety and Environment Engineering, Ton Duc Thang
University, Ho Chi Minh City, Vietnam

ABSTRACT: Hythane is a mixture of hydrogen and methane and has high combustion efficiency.
Batch and semi-continuous feeding modes of dark fermentation were tested to investigate the feasibility
of producing biohythane in a single bioreactor with a target gas components of hydrogen 15%, methane
45% and carbon dioxide 40%. The operation conditions were glucose substrate concentration 5g/L, pH 7
and temperature 35°C. The experimental results indicated that in a two-day cycle feeding mode, 4th feed-
ing run (at 6th hour) resulted in a biohythane component of hydrogen 15%, methane 50% and carbon
dioxide 36%.

1 INTRODUCTION together is a sustainable process for bio-hythane


as biofuel (Cavinato et al., 2010; Lee et al., 2010).
Hythane is traditionally a gas mixture of hydrogen- However, such anaerobic hythane gas production
enriched natural gas and is recently used as a gas uses two separate hydrogen and methane bioreac-
mixture of hydrogen and methane. Gattrell et al. tors and is space and operation uneconomical. If a
(2007) had defined that hythane is a mixture of single anaerobic reaction tank can directly produce
methane gas with hydrogen 10–60% (v/v). Com- bio-hythane gas will be more significance. This
paring with natural gas or methane, hythane has study is to investigate the effects of various mix-
characteristics of increasing combustion efficiency ing ratios of hydrogen- and methane—producing
and reducing pollutant emissions when it is com- bacteria on biohythane production.
busted in an internal combustion engine. When
hydrogen is mixed with methane (in a ratio of 3: 7
or less), the combustion efficiency can be increased
2 MATERIALS AND METHODS
by 20–30%; fuel consumption is reduced and the
emissions of CO, CO2, NOx and other pollutants
2.1 Seed, nutrient and substrate
are well reduced (Alavandi and Agrawal, 2008 ).
A literature has shown that hythane consisting of Highly active hydrogen- and methane—producing
CH4 44.8%, CO2 38.7% and H2 16.5% had high- bacteria cultivated in continuous flow bioreac-
est combustion efficiency (Porpatham et al., 2007). tors were used. The hydrogen seed was cultivated
Hythane is a potential gaseous alternative energy using a beverage wastewater. The methane seed
source in the future. was cultivated using a textile desizing wastewater.
Most of the current hythane production is con- These seeds were mixed based on a biomass con-
verting from natural gas by catalyst and is not a centration (volatile suspended solids, VSS). The
sustainable process. Using anaerobic fermentation VSS ratios tested were (hydrogen bacteria: meth-
to produce methane and hydrogen gas and mixed ane bacteria) 1:1, 1:1.5, 1:2 and 0:1 with a fixed

133
biomass concentration of 4 g VSS/L. Glucose sub- 3 RESULT AND DISCUSSION
strate was in a concentration of 10 g/L.
Experiments of a semi-continuous feeding mode 3.1 Batch production of biohythane
were conducted using glucose substrate (concen-
Figure 2 shows that higher methane seed resulted
tration 5 g/L).
in higher cumulative hydrogen and methane pro-
The nutrient formula used was for methanogens
duction. The possible reason was that the methane
(Lin, 1986): (NH4)2HPO4 0.7, MgSO4•7H2O 0.25,
seed was well acclimated by textile desizing waste-
NH4Cl 0.85, MgCl2•6H2O 0.81, FeCl3•6H2O 0.42,
water. In this case, the methane seed contained
NaHCO3 6.72, CoCl2•6H2O 0.018, KCl 0.75.
highly active acidifiers and methanogens. Mixing
ratios (acidogens: methanogens, based on VSS
2.2 Reactors concentrations) of 1:2 and 0:1 gave same levels of
maximum biogas productions with 990 mL and
Batch experiments were conducted using serum
972 mL, respectively and methane productions
vials (each had a volume of 235 mL) (Figure 1).
of 339 mL and 330 mL, respectively. Noted that a
Experiments of a semi-continuous feeding mode
mixing ratio of 0:1 gave a maximum hydrogen pro-
were conducted using 1 L bioreactor.
duction (69 mL). Other mixing ratios might result
in too high concentrations of acidogens which
2.3 Experiment analysis were not favoring hydrogen production from less
organic loading rate. This figure shows that hydro-
This study used a gas chromatograph (CHINA
gen production stopped at the second day but
Chromatograph 8700T) to analyze gas composi-
methane production slowly increased with time.
tion. A Thermal Conductivity Detector (TCD)
Figure 3 shows that the hourly variations of the
was used. Carrier gas was argon. Column was
biogas components were independent on the mix-
stainless steel pipe (1/8 mm ID*4 m). Injector
ing ratios. Peak hydrogen percentages (around 20%)
temperature was 40ºC. The detector temperature
occurred at near 12 h after the cultivation began.
was 40ºC. Column temperature was 28ºC. A liquid
The depletions of hydrogen and carbon dioxide
chromatograph (SHIMADZU GC-14 GAS Chro-
went with increasing methane gas, which indicating
matograph) to analyze Soluble Microbial Product
conversion of hydrogen and carbon dioxide into
(SMP). The detector was Flame Ionization Detec-
methane. One day later, hydrogen was consumed
tor (FID). Column was glass pipe (3.2 mm ID*1.6
and reached very low values (0.02–0.3%). These
m). Filer was FON 10%. Carrier gas was argon.
Injector and detector temperature were 175 and
145 ºC, respectively. Flow rate was 60 mL/min.
Water quality analysis was according to APHA
for Chemical Oxygen Demand (COD) and volatile
suspended solid (VSS). Total sugar concentration
was measured via a phenol-sulfuric acid method
(Dubios et al., 1956).

Figure 2. The cumulative gas, hydrogen and methane


Figure 1. A serum vial for batch tests. productions using glucose substrate.

134
Figure 5. Variations of liquid metabolite in the semi-
continuous fermentation.
Figure 3. The varying trends of the biogas component
(a mixing ratio of hydrogen- to methane—producing
bacteria): (A) 1:1, (B) 1:1.5, (C) 1:2 and (D) 0:1. desired biogas components were obtained. Hydrogen
concentration reached a peak value of 49.2% at the
first 12 h in the third feeding run. In the fourth feeding
run, in the biogas a component of hydrogen 10.3%,
methane 31.0% and CO2 19.7% was obtained at 8 h.
Noted that pH decreased with the progress of hydro-
genesis (acidification).
Hydrogen production accompanied with pro-
ducing Volatile Fatty Acids (VFA). Figure 5 depicts
daily variations of VFA concentrations indicat-
ing low values for the first feeding run and then
increased gradually for other feeding runs. For the
fourth feeding run, maximum cumulative VFAs
concentrations were in the order acetate, butyrate
and propionate. Acetate was the main fermenta-
tion byproduct.

4 CONCLUSION

Batch dark fermentation suggested that the biogas


components were independent on the mixing ratio
of hydrogen- and methane-producing bacteria and
hydrogen, could not effectively accumulated if cul-
tivation was too long.
A semi-continuous feeding mode with a two-
days feeding cycle could result in a biogas compo-
Figure 4. Semi-continuous fermentation for biohythane
production. nent of hydrogen 15%, methane 50% and CO2 36%
after 6 h cultivation. This biogas fraction closed to
the a desired value of hydrogen 15%, methane 45%
facts suggested that a semi-continuous mode of and CO2 40%. The main metabolites were acetic
feeding might be helpful in accumulating hydrogen and butyric acids.
component. At the ends of the experiments, meth-
ane and carbon dioxide were observed as 10–13%
and 79–83%, respectively. REFERENCES

Alavandi, S. & Agrawal, A. 2008. Experimental study of


3.2 Semi-continuous feeding mode for biohythane combustion of hydrogen-syngas/methane fuel mix-
production tures in a porous burner. Int J Hydrogen Energy, 33(4),
pp. 1407–1415.
Figure 4 shows hourly variations of the biogas pro- APHA. 1995. Standard Methods for the Examination
duction in the semi-continuous feeding experiments of Water and Wastewater, 19th ed. American Public
with a two-days feeding cycle. Various but high in the Health Association, New York, USA.

135
Cavinato, C., Fatone, F., Bolzonella, D. & Pavan, P. 2010. Porpatham, A., Ramesh, & B. Nagalingam. 2007. Effect
Thermophilic anaerobic co-digestion of cattle manure of hydrogen addition on the performance of a biogas
with agro-wastes and energy crops: comparison of fueled spark ignition engine. International Journal of
pilot and full scale experience. Bioresource Technology, Hydrogen Energy, vol. 32, pp. 2057–2065.
101(2), pp. 545–550.
Gottschalk, G. 1986. Bacterial metabolism. New York,
NY: Springer-Verlag. pp. 1–359.

136
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Biomass fly ash application for AMD treatment

E. Remešicová & A. Király


Institute of Environmental Engineering, Faculty of Mining and Geology, VŠB—Technical University Ostrava,
Ostrava, Czech Republic

P. Andráš
Institute of Environmental Engineering, Faculty of Mining and Geology, VŠB—Technical University Ostrava,
Ostrava, Czech Republic
Faculty of Natural Sciences, Matej Bel University, Banská Bystrica, Slovakia

ABSTRACT: Formation of Acid Mine Drainage (AMD) at Banská Štiavnica deposit is connected
with mining of base metals and of hydroquartzite containing fine-grained pyrite. Oxidation of sulphides
causes acidification of the environment and increases mobility of heavy metals. In this study, two types
of fly ash (from domestic and plant biomass combustion) were used to investigate possible decontamina-
tion of AMD. Used AMD is characterised by high concentrations of Fe (753 mg⋅l−1), Mn (16.2 mg⋅l−1),
Zn (2.46 mg⋅l−1) and low pH (2.4). The ash samples were dosed (1 g, 5 g, 10 g, 20 g) to AMD to increase
pH values and remove metals. Changes of pH were observed in selected time intervals within 4 hours. The
pH values of the aqueous medium were increased proportionally with the amount of applied agent. The
application of plant fly ash enabled to adapt the pH up to 8.1 and adding of the domestic fly ash modi-
fied the pH of AMD up to 5.9. Although used ashes contained high concentrations of Fe (39594 and
4304 mg⋅kg−1), Mn (15084 and 2007 mg⋅kg−1) and Zn (5347 and 3564 mg⋅kg−1) removal of these metals
from AMD was effective. Problem occurred in case of domestic fly ash which caused the enrichment of
AMD with Pb, Mn and Cr (by concentrations 0.01–0.1 mg⋅l−1).

Keywords: acid mine drainage, biomass fly ash, metals removal, neutralisation

1 INTRODUCTION is between pH values of 6–9 (except for Fe (III),


which precipitates at pH of about 3.5; Skousen,
The procedures applied in the acid mine water 2000; Douglas & Degens, 2006).
treatment can be divided according to the aim There are various agents used for neutralization
of remediation to the activities focused on acid- of AMD, such as limestone, calcium hydroxide,
ity reduction and activities for elimination of sodium hydroxide, sodium carbonate, magnes-
heavy metals (Lottermoser, 2007). The best choice ite and dolomite. Relatively new reagent used for
among the alternatives depends on technical as decontamination of waters is fly ash from coal
well as economic factors. The technical factors combustion, which has become the subject of
are the pH value, flow rate, type and concentra- many researches in the removal of contaminants
tion of metals in the water, the necessary degree and acidity from mine waters. Nowadays, great
of chemical treatment and the required final emphasis is put on the use of renewable resources
water quality (Skousen et al., 2000; Douglas & as energy resources, among which the biomass is
Degens, 2006). Among the economic factors are considered the most prospective. The use of bio-
the financial costs of reagents, labour, machin- mass as an energy source also generates a great
ery and equipment, the number of years that amount of by-product—fly ash. The most of ele-
will be needed for neutralisation and risk factors ments contained in biomass retain after combus-
(Skousen et al., 2000). In order to increase pH tion in fly ashes and therefore the potential further
value, the supply of hydroxide (OH-) and alkalin- use of this product has specific importance. Prop-
ity should be increased. After pH rises, dissolved erties of the biomass ash depend on several factors.
metals form insoluble metal hydroxides, which These include the type and characteristics of the
are able to be removed from the water. The pH biomass and used technology (Isnam & Knapp,
at which the metals precipitate at the biggest rate 2011; Heviánková et al., 2014).

137
2 MATERIALS AND METHODS 100 ml with distilled water. After 10 minutes long
reaction and precipitation was solution filtered
2.1 Study area through filter Munktell grade 390.
Used neutralizing agents were analysed for sul-
Studied acid mine water is a drainage emanat-
phur content using a Wavelength Dispersive Spec-
ing from the waste dump of hydroquartzite
trometer (WDS). 4 g of dried ash samples were
Šobov quarry in the district of Banská Štiavnica.
mixed with 0.9 g of wax. Material was afterwards
Banská Štiavnica is situated in the southern part
transformed to the palette of dimensions 32 mm
of Central Slovakia and belongs to the Protected
and analysed by wavelength dispersive spectrom-
Landscape Area Štiavnické Vrchy Mts. The deposit
eter Mack GV.
is formed by secondary quartz with pyrite which is
The pH of the ashes was measured in suspen-
present in two generations—fine dispersed pyrite
sions of 5 g of ash in 25 ml of distilled water after
syngenetic with quartz and epigenetic pyrite which
one hour long agitation as well as in suspensions
forms tiny clumps and small veins in quartz (Bella
of 5 g of ash and 25 ml of KCl.
et al., 2010). Waste dump has been formed since
1956 to the present. It consists of overburden soils
and rocks with dispersed sulphide with domi-
3 RESULTS
nant pyrite (Masarovičová et al., 2007; Križáni &
Andráš, 2008). Šobov quarry meets technical
Acid mine drainage from Šobov quarry contains
and legislative requirements for categorisation in
high concentrations of Fe (753 mg⋅l−1) and Mn
the group of permanent environmental burdens
(16.21 mg⋅l−1). Drainage has low pH (2.4), high
(Masarovičová et al., 2007; [Link], 2015). Plant
electroconductivity values (6457 μS/cm) and total
Biomass fly Ash (PBA) was sampled from the bag
dissolved solids (3226 ppm; Tab. 2).
filter in the heating plant combusting biomass.
After the AAS analysis the experiment for
Domestic Biomass Ash (DBA) was collected from
decontamination of AMD was realised with use of
the chimney of the fireplace after combustion of
two biomass fly ashes. The pH value of the solu-
beech and oak wood.
tions was continuously measured during reaction
2.2 Experimental
Table 1. AAS analysis of Acid Mine Drainage (AMD).
The aim of this study was to verify the possibility
of using fly ash from biomass combustion in the Fe Mn Pb Zn Cu Cr Ni Co
neutralization and decontamination of mine water.
Application of fly ash was realised under laboratory mg⋅l−1
conditions. Chosen fly ashes were stirring with acid
mine drainage during 4 hours, each of them in four 753 16.21 <D.L. 2.46 1.41 0.06 0.42 1.42
different doses (1 g⋅l−1; 5 g⋅l−1; 10 g⋅l−1 and 20 g⋅l−1).
While mixing, pH value of each sample was meas- Table 2. pH, Electro Conductivity (EC), Dissolved
ured in time intervals (1 min, 20 min, 40 min, 60 min, Oxygen (DO) and Total Dissolved Solids (TDS) values
120 min and 240 min). Heavy metals analysis was in AMD.
performed after 40 and 240 minutes of stirring in
samples filtered through KA4 filter. EC DO TDS
Water samples were after four-hours long react- pH (μS/cm) (ppm) (ppm)
ing with dosed ashes analysed for the metal and 2.4 6457 6.2 3226
sulphate composition. Metal concentrations (Fe,
Pb, Zn, Mn, Co, Cr, Ni, Cu) were analysed in
AMD and in used fly ashes by Atomic Absorp-
tion Spectroscopy (AAS) using Varian AA 280FS
in laboratory IEI VŠB Ostrava. Sulphates concen-
trations were in water samples measured before
and after experiment with use of absorption spec-
trometer HACH LANGE-DR. 2800 at the wave-
length of 430 nm. Preparation of the samples for
sulphate measurements was as follows: 1 mL of
NaCl and 3 ml of BaCrO4 were added to 100 ml
of the distilled sample. The compound was boiling
until a coarse BaSO4 was formed. After the cool-
ing of the solution, 1 mL of ammonium hydroxide Figure 1. Dependence of pH changes on the amount
was added, the volume was refill to the volume of of dosed reagent.

138
between the agents and AMD. Both of the applied was increasing with the rising time of the reaction
ashes had tendency to increase the pH of the water, however the biggest increase in pH was observed
while the rise of the pH was directly proportional between 20th and 40th minute of the reaction
to the amount of added ash (Fig. 1). The pH value (Tab. 3). The maximum pH value of AMD dur-
ing the plant biomass ash application was 8.1 and
Table 3. Change of pH of AMD during reaction with with use of domestic biomass fly ash was the high-
applied biomass ash. est reached pH value 5.9. When the biomass ashes
were applied to the distilled water and KCl both of
time (min.) the dilutions showed alkaline reaction (Tab. 4).
Elemental analysis of the biomass ashes showed
dose 1 20 40 60 120 240 that the most concentrated element is Fe (PBA—
agent g⋅l−1 pH
39597 mg⋅kg−1; DBA—4304 mg⋅kg−1). Heating
plant biomass fly ash contained in comparison
PBA 1 2.7 2.7 2.8 2.9 2.9 2.9 with domestic biomass ash higher concentrations
5 3.4 3.8 3.9 3.9 3.9 3.9 of analysed metals.
10 4.3 4.4 4.5 4.5 4.6 4.7 Heating plant fly ash from the bag filter proved
20 6.0 7.2 7.5 7.7 7.9 8.1 to be a good agent for removal of almost all of the
analysed metals. Although fly ash itself contained
DBA 1 2.6 2.6 2.7 2.7 2.8 2.9
up to 39593 mg⋅kg−1 of Fe (Tab. 5), its application
5 2.8 2.9 2.9 3.0 3.0 3.0
has led to the complete removal of this metal. Good
10 2.7 3.3 4.2 4.3 4.4 4.4
20 3.0 3.5 4.3 4.5 5.0 5.9
results were obtained during application of 20, 10
and 5 g of the ash. However with the addition of
Explanatory notes: PBA—plant biomass ash; DBA— 1 g, Fe concentration in water has increased. The
domestic biomass ash. most problematic metal to remove was Mn, whose
content in water was by addition of the fly ash
Table 4. pH of agents during leaching increased. Only positive result in Mn removal was
in distilled water and KCl. obtained after 240 minutes stirring of water with
20 g of the fly ash (Tab. 6).
agent pHH2O pHKCl Biomass ash from domestic combustion showed
to be successful only in Fe removal (Tab. 7). The
PBA 12.1 12.0
concentrations of other analysed metals were
DBA 8.3 8.4
slightly reduced and some of the metals (Ni, Cr,

Table 5. AAS and WDS analysis of used biomass ash.

Fe Mn Pb Zn Cu Cr Ni Co S

agent mg⋅kg−1

PBA 39594 15084 337 5347 497 137 98.33 38.14 48.26
DBA 4304 2007 224 3564 101 20.29 25.84 <D.L 39.95

Table 6. Heavy metal concentrations in AMD after Plant Biomass Ash (PBA) addition in set time intervals.

dose time Fe Mn Pb Zn Cu Cr Ni Co

G⋅l−1 min. mg⋅l−1

0 − 753 16.2 <D.L 2.5 1.4 0.1 0.4 1.4


1 40 781 22.2 0.06 4.6 1.7 0.1 11.6 1.9
240 777 23.5 0.05 4.7 1.5 0.2 26.2 1.2
5 40 1.2 36.7 0.02 13.3 1.9 0.05 1.4 1.5
240 0.5 40.1 0.02 14.3 1.5 0.03 9.3 1.7
10 40 <D.L 42.3 0.01 19.4 1.1 <D.L 0.6 1.0
240 <D.L 49.5 <D.L 21.2 0.8 <D.L 0.6 1.3
20 40 <D.L 27.8 <D.L 0.2 <D.L <D.L 0.1 0.2
240 <D.L 10.4 <D.L 0.1 <D.L <D.L 0.0 <D.L

139
Table 7. Heavy metal concentrations in AMD after Domestic Biomass Ash (DBA) addition in set time intervals.

dose time Fe Mn Pb Zn Cu Cr Ni Co
−1 min. −1
g⋅l mg⋅l

0 – 753 16.2 <D.L. 2.5 1.4 0.1 0.4 1.4


1 40 647 10.8 0.01 2.4 1.5 0.2 6.2 1.9
240 599 11.1 0.01 2.6 1.3 0.2 11.5 1.1
5 40 569 11.2 <D.L. 2.2 1.4 0.3 12.6 1.9
240 339 11.9 <D.L. 2.9 1.3 0.2 31.7 1.2
10 40 403 11.4 0.02 2.9 1.4 0.2 0.5 1.8
240 54.1 11.7 0.03 6.8 1.4 0.1 0.5 1.4
20 40 186 11.7 0.04 2.1 1.4 0.1 0.6 1.3
240 0.46 16.3 0.02 2.2 1.4 0.1 0.4 0.9

Table 8. Sulphates concentration in tested AMD (after by low pH and high concentrations of Fe, Mn and
240 min. of reaction). sulphates which highly exceed general require-
ments for surface water quality (Government
SO4
Regulation 296/2005 Coll.) Fe concentrations in
mg⋅l−1
analysed AMD (311 mg⋅l−1) also exceed the limit
0 1 5 10 20 concentrations of Fe (4.0 mg⋅l−1) for water result-
ing from the extraction of ores by Government
dose g⋅l−1 Regulation 269/2010 Coll., which stipulates cri-
teria for achieving good water balance (Annex 8,
PBA 3919 4290 4348 3315 3902 Part B, Tab. 3.2.). The cause of the contamination
DBA 3919 4094 3372 3301 3906 and of the acidity of water is the weathering of
pyrite present in mined hydroquartzite. Oxidation
of the pyrite may be enhanced with activity of aci-
dophilic sulphide-oxidizing bacteria (Acidithioba-
Pb) were after application of the domestic fly ash cillus ferrooxidans), whose presence was in the past
released to the water and their concentrations in in the acid mine drainage emanating from Šobov
water were increased. quarry proved (Bella & Šlauková, 2006). Limit-
Manganese removal from AMD showed to be ing factor during oxidation is conversion of Fe2+ to
the most complicated among all of the analysed Fe3+. In the presence of bacteria at low pH is oxi-
metals. On the contrary the best removed metal dation significantly higher than during the abiotic
was Fe which was successfully precipitated with conditions with pH>5 (Šottník, 2005).
use of both of applied ashes. Heating plant fly The neutralization of AMD and the active
ash showed to be more suitable for metals removal removal of heavy metals from water showed
from examined AMD than ash from domestic bio- positive results when using heating plant fly ash.
mass combustion as well as for increasing the pH. Agents which are able to neutralize the acidic mine
Regarding the content of sulphates in AMD, drainage can achieve the best results in the removal
results did not show any relationship between the of heavy metals (Komnitsas et al., 2007, Rios et al.,
dose of added agents and changes in the concen- 2008). Fly ash is a relatively new and still tested
trations of SO4 (Tab. 8). The largest decrease of agent in decontamination of mine water. Many
sulphates in AMD was achieved for both ashes studies have already showed positive results of fly
after application of 10 g of ash. ash in AMD treatment. Mostly used fly ash is ash
from coal combustion (Pérez—López, 2007; Gitari
et al., 2008; Kumar Vadapalli et al., 2008) however
4 DISCUSSION good results were achieved also by the use of fly
ash from the combustion of biomass (Heviánková,
Studied acid mine water is characterized by ele- 2014).
vated concentrations of heavy metals. This phe- The most actively removed metal was Fe. Dur-
nomenon is conditioned by mining activities which ing stirring was Fe2+ oxidised to Fe3+ and Fe was
have facilitated weathering of rocks and the subse- precipitated at relatively low pH (about 3.5). Used
quent release of hazardous elements into the envi- ashes were the least suitable for the elimination of
ronment (Ďurža, 2007). The water is characterized Mn. Manganese ion is extremely mobile and its

140
removal from the water is a very difficult process. Ďurža, O. 2007. Využitie pôdnej magnetometrie pri
For effective Mn removal should be water pH štúdiu kontaminácie pôd ťažkými kovmi. Acta
greater than 8.3 (Heviánková, 2014). The closest environmentalica universitatis comenianae. Bratislava,
value (pH 8.1) was achieved using a heating-plant 15 (1), 5–15 p.
Gitari, W. M., Petrik, L.F., Etchebers O., Key, D. L.,
fly ash, when the Mn content decreased from the Iwuoha, E. & Okujeni, C. 2008. Passive neutralisation
value 16.21 mg⋅l−1 to 10.44 mg⋅l−1. Higher levels of acid mine drainage by fly ash and its derivatives:
of Mn in the water compared to the values at the A column leaching study. Fuel. 87, 1637–1650 p.
beginning of the process during use of DBA can Government regulation SR 269/2010 Coll., which stipu-
be explained by re-dissolution of the formed pre- lates criteria for achieving good water balance.
cipitates (Komnitsas et al., 2004). Government regulation SR 296/2005 Coll. Establishing
While the elimination of Mn and Fe was pH Targets for Surface Waters and Limit Values of Pollu-
dependent, changes in SO42− concentrations vary, tion Indicators of Wastewater and Spacial Waters.
what can be caused by dependence on Ca2+ release Heviánková, S. 2014. Biomass ash in AMD treatment.
TU Košice. 79 p. ISBN: 978-80-553-1766-3.
from the agent to the aqueous medium (Girati Insam, H. & Knapp, B. A. 2011. Recycling of Biomass
et al., 2008). Sulphate removal of the analysed Ashes. Springer: Berlin, Heidelberg, ISBN 978-3-642-
waters was not successful. 19354-5, 164 p.
Komnitsas, K., Bartzas, G. & Paspaliars, I. 2004. Effi-
ciency of limestone and red mud brriers: laboratory
5 CONCLUSIONS column studies. Minerals Engineering. 17, 183–194 p.
Križáni, I. & Andráš, P. 2008. Modelovanie perkolácie
Success of the decontamination of analysed AMD sedimentov háld a odkalísk banskoštiavnického rud-
with use of biomass ash is dependent on the pH ného revíru. Mineralia Slovaca. 40, 59–72 p. ISSN
0369-2086.
value. Heating plant fly ash from the combustion Kumar Vadapalli, V. R., Klink, M. J., Etchebers, O.,
of biomass had in comparison with domestic fly Petrik, L. F., Gitari, W., White, R. A., Key, D. &
ash better effect for metals removal due to higher Iwuoha, E. 2008. Neutralization of acid mine drain-
pH increase. The best results were obtained during age using fly ash, and strenght development of
applying 20 g⋅l-1 of the ash, after 240 minutes of the the resulting solid residues. South African Journal
reaction. Šobov quarry represents an environmen- of Science. 104, 317–322 p.
tal burden and produces extremely acidic, con- Lottermoser, B. G. 2007. Mine wastes: characteriza-
taminated mine water. Fly ash from the biomass tion, treatment and environmental impacts. 2nd ed.
combustion can be a suitable agent for acidity London: Springer. 304 p. ISBN 35-404-8629-1.
Masarovičová, M., Slávik, I. & Kovalková, J. 2007.
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lysed metals. Rate of the neutralization and of odkalísk SR (časť 5). STU Bratislava.
metal removal depends on the properties of the fly Pérez-López, R., Nieto, J. M. & Ruiz de Almodóvar, G.
ash. In the present research achieved ash contain- 2007. Utilisation of fly ash to improve the quality of
ing higher concentrations of metals better results the acid mine drainage generated by oxidation of a
than ash containing lower concentrations. Percent- sulphide—rich mining watse: column experiments.
age of metal removal depends on many factors and Chemosphere. 67, 1637–1646 p.
on the interaction between the decontamination Ríos, C. A., Williams, C. D. & Roberts, C. L. 2008.
agent and the decontaminated water. Removal of heavy metals from acid mine drainage
(AMD) coal fly asj, natural clinker and synthetic zeo-
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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Application of staged biomass gasification for combined heat


and power production

J. Brynda, S. Skoblia & Z. Beňo


University of Chemistry and Technology, Prague, Czech Republic

M. Pohořelý & J. Moško


University of Chemistry and Technology, Prague, Czech Republic
Institute of Chemical Process Fundamentals of the CAS, Prague, Czech Republic

ABSTRACT: Multi-stage gasification combined with internal combustion gas engine is an efficient way
of Combined Heat and Power production (CHP) from woody biomass. In this work the performance of a
multi-staged fix bed gasifier is reported. In this type of generator, all subsequent processes like pyrolysis,
partial oxidation of volatile matter and gasification of char take place in different parts of the generator.
The used multi-stage concept enables to increase cold gas efficiency over 80% and produce a clean gas
with low tar content. Another advantage is the possibility of controlled biochar production. The same
multi-stage gasifier design was used in eleven cogeneration units built in the Czech Republic with an elec-
trical output from 200 to 750 kW. This study presents the experience with operation of the largest CHP
facility in the Czech Republic. The CHP facility consists of five generators with a maximum electrical
power of 750 kW each.

1 INTRODUCTION conditions. The first process, called pyrolysis, is


slightly endothermic and takes place in zones with-
Combined heat and power generation in small out oxygen access at temperatures above 250°C.
cogeneration plants is a promising approach to Products of pyrolysis are carbon residue or char-
power production from biomass. Combination of coal and volatile matter, consisting of flammable
woody biomass gasification with power produc- and non-flammable gaseous compounds. The
tion by an Internal Combustion (IC) gas engine amount of volatile matter can be as high as 80%
coupled with power generator is an efficient way wt. and it is the main source of tar. The second
of power production in smaller units. To make the process, taking place during gasification, is partial
whole cogeneration process feasible and economi- oxidation (POX) of volatile matter. An amount
cally effective, it is necessary to efficiently trans- of oxygen lower than the stoichiometric ratio
form the chemical energy of input fuel to power reacts with the volatile matter during POX and the
and maintain low capital and operating costs. needed thermal energy for endothermic reactions
Modern IC gas engines can transform chemical is produced. The last process is reduction, also
energy of producer gas to power with efficiency called gasification of charcoal by CO2 and H2O.
higher than 36%. However, required gas purity This process is strongly endothermic and produces
has to be attained for steady long term operation. flammable gases like CO, H2 (Bario 2002).
Particular attention should be given to tar content
which should not exceed the limit. Multi-stage gas-
ifiers are capable of producing gas with sufficiently 2 TWO-STAGED GASIFIERS IN THE
low tar content and high cold gas efficiency. There- CZECH REPUBLIC
fore, it is possible to avoid expensive gas treatment
technologies and only filtration of dust particles The main advantage of staged gasification is
is needed. the possibility to separate these partial processes
Gasification is a thermochemical process trans- into different sections of the generator. The most
forming input fuel into flammable gas, generally important aspect of tar destruction is to ensure
called producer gas, which consists of CO, H2, that all of the volatile matter evolves in the pyroly-
CO2, H2O, N2 and CxHy. Gassification can be sis section and then undergoes transformation
divided into three separated processes. Each of in the partial oxidation zone and partially in the
these partial processes has its own optimal reaction reduction zone.

143
2.1 Two-staged gasifier design by Tarpo Ltd. wall of the generator and by radiation of the hot
inner separator. Due to the separator all volatile
In 2010, Czech company Tarpo Ltd. Patented a
matter flows to the partial oxidation (POX) zone
new biomass gasifier concept based on staged gasi-
inside the separator and tar free charcoal falls to
fication. In Figure 1 the basic scheme of this type
the reduction zone in the bottom of the genera-
of gasifier is depicted. In this type of fixed-bed
tor. Secondary air (A2) is added to the POX zone
multi-stage gasifier all three partial processes take
and due to oxidation reactions, temperature in
place in different sections of the same reactor body.
this zone rises up to 1200°C. Most of the volatile
Pyrolysis (Py) section, which is the biggest one, is
matter is decomposed in this zone and output gas
in the upper part of the reactor. Pyrolysis section
contains mainly gaseous compounds (H2, CO,
is separated from the partial oxidation (POX) zone
CO2, H2O, CH4). The hot gas then flows through
and the reduction (RED) zone by an inner ceramic
the reducing bed of charcoal (RED). Gasification
separator (in conus shape). The separator con-
of tar free charcoal by endothermic reactions with
struction and used materials are “know-how” of
H2O and CO2 takes place in this reduction zone
Tarpo Ltd. (Picek 2013)
and gas temperature drops below 700°C. Producer
Dried biomass chips are fed to the top of the
gas then flows through the grates into a gas jacket
generator where the pyrolysis zone is. Input fuel is
and heats up the pyrolysis zone through the inner
heated up to temperature between 450 and 550°C.
reactor wall. Conveyor dryer is an integral part of
Under this temperature input fuel transforms to
the whole technology, which reduces moisture con-
charcoal and volatile matter. Heat necessary for
tent of raw wooden chips from 40–50% wt. to less
complete pyrolysis of the fuel is gained partially
than 5% wt. by using low potential heat of exhaust
by burning part of the fuel by primary air (A1)
gases.
and partially by heat conduction through the inner

2.2 Overview of installed units


The first prototype of two-stage gasifier in the
Czech Republic was GP200 with an electric output
of 200 kW. It was built and successfully launched
in 2012 and it replaced the previously used down-
stream gasifier GP300 (Skoblia et al. 2014). The
overall electrical efficiency of existing power plant,
using combustion engines CKD Hořovice (S160),
increased from the initial 25% to 27%. Tar content
in the producer gas decreased from approximately
2000 mg.m−3 for GP300 to a value below 25 mg⋅m−3
for GP200. Experiences from the operation of this
prototype gasifier were implemented into numer-
ous projects aimed to commercialize multi-stage
gasifiers. Till now, several versions with a dif-
ferent power output (GP200 series, GP200XL,
GP500 and GP750) were built in power plants
in the Czech Republic and in one power plant in
Slovakia. A brief list of gasifiers based on the two-
stage design is summarized. in Tab. 2., including
location and year of start-up, gasifier type, type
of IC gas engine, nominal electric output and esti-
mated overall efficiency.

2.3 Operation of CHP plant in Kozomín


The largest power plant using two-stage gasifiers
in the Czech Republic is run by the company BOR
Biotechnology Inc. in Kozomín (see Tab. 2). This
company operates technology for processing bio-
mass, wood waste (chips) and other woody materi-
als for pelletizing. Kozomín power plant consists
Figure 1. Scheme of two-staged gasifier designed by of five separate units each with one gasifier GP750
Tarpo Ltd. and whole gas treatment line (see Fig 2.). Purified

144
Table 1. Two-stage gasifiers from Tarpo Ltd.

Start up.
type of Nominal electric
Location a gasifier Type of engine output/efficiency
Kněževes (CZ) 2012 ČKD, 2x6S160, 27l, R6 200 kW/27%
GP200
Odry (CZ) 2012/201 Jenbacher 2xJ316, 48l, V16 2x500 kW/32%
2xGP500
Olešnice (CZ) 2013/2014 ČKD, 2x6S160, 27l, R6 200 kW/27%
GP200XL
Handlová (SK) 2014/2015 Guascor FBLD560, 56l 570+430 kW/32%
2xGP750 Guascor FBLD480, 48l
Dobříš (CZ) 2015 Guascor, FBLD560, (56l), 650 kW/32%
1xGP750
Kozomín (CZ) 2014/2015 Jenbacher, 3xJ320, (60l, V20) 3x710 kW/32%
5xGP750 5,1 MWt

Table 2. Basic parameters of Kozomín plant. and cooled gas from all five lines enters one mix
tank. Mixed gas is then used to power three mod-
Parameters Value ern IC gas engines Jenbacher J320 with power
generators each with maximal electrical output of
Number of gasifier (GP750) 5
Number cogeneration(Jenbacher 3
710 kW. Currently three gasifiers GP750 are oper-
J320 GS) ated to produce gas for these three cogeneration
Nominal electrical power output 3*710 KW units. The other two gasifiers were installed to pro-
Fuel (wood chips) 5–60 mm duce gas and heat (steam) for a paper mill near the
Consumption of fuel (abs. dry) max. 550 kg/h power plant. The technological part of the paper
Gas production (0°C, 101, 325 kPa), 1000–1200 m3/h mill is not built yet, and the steam generator is not
Low Calorific value (LHV) 5,5–6,5 MJ/m3 operating. For that reason, only three GP750 gasi-
Electrical efficiency min. 27% fiers are simultaneously operating to power the
Specific fuel consumption (abs. dry) ∼ 0,75 kg/kWh cogeneration units.
Char production rate 20–60 kg/h Kozomín power plant uses wood chips in the
Ash content in char 15–35% wt range of 5 to 60 mm for all five gasifiers. The first
part of the whole technology is feeding wood chips
to the system. Wood chips then enter a magnetic
separator to separate ferrous metals. Then particles
with size over 60 mm are separated to prevent arch-
ing inside the gasifiers. According to total load of
the whole technology, wet chips are then fed to one
or both conveyor dryers. During operation of three
gasifiers only one of two dryers is operating, which
is sufficient do decrease moisture content from up to
50% wt. in input chips to below 10% wt. Dried chips
from both dryers then go through a sieve separating
particles below 5 mm and then are transported by
one feeding line to all five gasifiers. Producer gas
from the gasifier is filtered by hot ceramic candle
filters (550–650°C) and flows to gas/water heat
exchanger. The next parts of the gas treatment line
are contact water cooling in spray tower and fine
1—entry of fuel into the GP750, 2—allothermal pyrolysis
section, 3—autothermal pyrolysis section, 4—POX filters. After the final filtration, producer gas from
section, 5—combustion flare, 6—gas output, 7—hot all five lines enters the mix tank from which it is fed
filters (CERAFIL XS 3000), 8—heat exchangers (gas/ to Jehnbacher cogeneration units.
water), 9—contact water cooling, 10—cooling tower,
A1—primary air inlet, A2—secondary air supply 2.3.1 Fuel parameters and efficiency
Kozomín power plant is capable to use different
Figure 2. Operating scheme f GP750 in Kozomín. types of wooden fuel. Commonly used materials

145
are raw hardwood chips with moisture content were also analyzed via Gas Chromatography (GC)
about 40% wt. to confirm that the online analyzers were working
Currently the gasifiers are operated at average properly as well as to analyze minor gas compo-
electric output of 650 kW each and each gasifier nents. From long term analysis can be concluded
burns about 34,5 tons of biomass (abs. dry) per that the gas composition was mostly steady and
day. Overall efficiency is about 27%. Moreover, the the main gas component was CO with concentra-
gasifiers produce about 1 tonne of biochar per day tion about 25% vol. The second flammable gas with
which is sold as fuel for briquetting. Due to textural high content was H2 with typical content about
properties of produced added value of produced 22% vol. Producer gas also contained inflamma-
biochar will likely be even higher in the future. ble CO2 and low amounts of CH4 of about 1.5%
vol. Even though the gas composition was mostly
2.3.2 Gas composition steady, several fluctuations were observed. During
Detailed analysis of gas composition and tar these fluctuations of gas composition, content of
content were carried out at the UCT, Prague and CO dropped while content of H2 and CO2 rose.
ICPF of CAS, to find out influence of different The fluctuations in gas composition were caused
operational parameters on gas composition. In due to the water gas shift reaction (Equation 1),
Figure 3 the gas composition from long term oper- which shifted the reaction towards products (CO2
ation (30 days) is shown. The content of the main and H2) due to increased water content of the fuel.
components (CO, CO2 and CH4) was measured by During these fluctuations, an increase in CH4 con-
online infra-red analyzer URAS and H2 content tent was observed, which also meant higher tar
was measured by temperature conductivity ana- content.
lyzer Caldos, both from ABB. Several gas samples
Equation 1 CO + H 2O ↔ CO2 + H 2

Table 3. Typical fuel composition after drying. Long-term operation of the GP750 showed
another advantage of the described process - bio-
Mass % Raw Dry char production, which was about 3–4% by weight,
from the input fuel (dry basis). The ash content in
Water content 6,55 0,00 biochar was between 15 and 35% wt. Biochar rate
Combustible 92,36 98,84
production can be controlled by regulating the
Ash content 1,08 1,16
intensity of the generator grating. Specific biochar
Volatile matter 71,05 76,03
features suggest wide possibilities of its usage such
Fixed carbon 21,31 22,81
as high surface adsorbent material or complex fer-
C 46,33 49,58
tilizer for soil quality improvement.
H 5,89 6,30
O 39,65 42,43
N 0,48 0,51 2.4 Comparison of gas quality from different type
S 0,02 0,02 of gasifiers
Lower heating value, [[Link]−1] 16,94 18,31
Different gasifier constructions were designed to
achieve high gasification efficiency and to decrease
tar content in producer gas. In Table 4 in order to
compare different gasifier types, approximate gas
compositions and tar contents of different pro-
ducer gases are listed. Two co-current gasifiers
Imbert with electric output of 100 kW (Beňo et al
2011) and stratified bed gasifier GP300 (Skoblia
et al 2012) are enlisted for comparison with stage-
bed gasifiers.
When using the same fuel and gasifying agent,
in this case wooden chips and air, it is possible
to approximately compare cold gas efficiency
(ηce) based on gas composition. Content of N2 is
directly proportional to the amount of air used for
gasification. The most efficient gas production is
achieved when a lower amount of air is used. The
lowest content of N2 in producer gas was observed
Figure 3. Producer gas composition in CHP plant in in the case of the Viking gasifier (Brandt et al 200),
Kozomín. which uses the waste heat of the flue gas from

146
Table 4. Gas composition from different types of gasifiers.

Gas comp., % vol. Imbert*1 GP300*2 XW twin-fire Viking GP200* GP500* GP750

H2O in Fuel, % wt. <10 <10 <10 35–45 <10 <10 <10
CO 24,6 25,5 22,5 19,6 26,7 25,0 25,3
H2 16,4 17,2 17,6 30,5 23,0 22,3 22,7
CH4 2,2 3,0 2,0 1,2 1,1 2,0 1,3
CO2 9,6 9,6 10,5 15,4 8,0 9,5 9,7
N2 46,1 43,5 45,1 33,3 40,6 41,1 40,9
Rest 1,1 1,2 2,3 0 0,6 0,1 0,1
Tar content**, mg/m3 1300–2000 1000–2000 <100 <5 0,5–2,0 5–40 20–200
Qi (15°C), MJ/m3 5,7 6,3 5,4 5,6 5,9 5,9 5,8
1
Modified “Imbert” gasifier from BossEngineering Ltd.
2
Co-current stratified gasifier from Tarpo Ltd. Used till 2012
*
Air for gasification was preheated
**
Determination of tar was carried out according to Tar Protocol. Given value does not contain toluene, xylenes and
benzene.

engine for pyrolysis and has the highest cold gas be concluded that well-functioning multi-staged
efficiency (ηce = 95%). Low nitrogen content of gasifiers produce lower amount of tar and CO2
the gas is also caused by high fuel humidity, which than co-current gasifiers. Moreover, CO and H2
leads to an increase of total gas production (H2, content is higher due to gasification of carbona-
CO2). It can be presumed that if moisture content ceous material (Skolia et al. 2016).
of used wooden chips is less than 10 wt.%, con-
tent of nitrogen would increase to a value of about
37 vol.%. High efficiency and good gas composi- 3 CONCLUSIONS
tion were achieved in the experimental unit with
electric output of 25 kW. The electrical output of Measurements carried out on different types of
the experimental unit is significantly lower than two-stage gasifiers showed that the composition of
compared to the other presented gasifiers (Knoef producer gas and tar content in producer gas greatly
2012). The lowest cold gas efficiency has a twin depends on the operating parameters of a gasifier.
fire gasifier from the company XyloWatt (www. The main parameters are fuel properties and ratio of
[Link]). Similar gas composition and cold primary (A1) and secondary (A2) air. When oper-
gas efficiency can be achieved by the downstream ated improperly, volatile matter can flow through-
generator GP300 from Tarpo Ltd., which has out the POX zone without tar destruction, which
become obsolete and is out of order since 2012. In may cause an increase in tar content in the producer
comparison with staged generators it can be con- gas. To avoid this negative effect, it is necessary to
cluded that according to available data depicted set optimal ratio of primary and secondary air in
in the Table 4, two-stage gasifiers GP200, GP500 the range from 1:5 to 1:10. Ideal ratio of primary
and GP750 have higher efficiency compared to all and secondary air depends especially on generator
other concepts discussed above with the exception power, fuel moisture and intensity of grating.
of the Viking gasifier. Long term measurement conducted in CHP
The quality of producer gas can be assessed plant in Kozomín proved that gasifier GP750 pro-
directly by tar content and indirectly by the con- duces gas with steady composition. During steady
tent of methane or other hydrocarbons. The lower operation of GP750, main flammable gas com-
the content of hydrocarbons in the producer gas, ponents are CO and H2 with concentration about
the less tar content can be expected in the gas. 25% vol. and 22% vol. respectively. The average
Methane concentration in the producer gas from content of CH4 is 1.5% vol. and tar content is in
two-stage gasifiers is lower than in the case of co- the range from 20 to 100 mg.m−3. It can be con-
current gasifiers. This is caused by partial oxida- cluded, that this type of generator is suitable for
tion of volatile matter in the POX chamber. Due gasification of woody biomass without the need
to high temperatures in the partial-oxidation zone of complex gas treatment. The tar content in pro-
and the reactions of the flue gases (CO2, H2O) with ducer gas rises with gasifier scale-up from 200 to
the charcoal bed material, the CO2 content is lower 750 electric kW. But even in the case of the biggest
and CO content is higher. After comparison of gas gasifier GP750, tar content is suitable for steady
composition from different types of gasifiers can operation of whole plant.

147
When compared to other types of staged and Picek, I. Equipment for multi-stage gasification. UM:
co-current gasifiers, the efficiency of two-stage CZ26592U1, 2013.
gasifiers designed by Tarpo Ltd. is better than most Skoblia, S. et al. 2014. Design and commercial applica-
of the known types of the gasifiers. Only complex tion of two-stage fixed bed gasifier in Czech Republic,
6th International Freiberg Conference Coal Conversion
multi-stage gasifier Viking is more efficient, which and Syngas, Dresden, 19–22 May.
has an electric power output 25 kW compared to Skoblia, S. et al. 2016. Experience with Operation of
200–750 kW in case of Tarpo gasifiers. Multi-Stage (Two-Stage) Fixed-Bed Gasifiers in the
Czech and Slovak Republic, 6th International Freib-
erg Conference Inovative Coal Value Chain, Cologne,
ACKNOWLEDGEMENT 12–16 June [Link]
tions/[Link]
Part of the presented work was accomplished
thanks to the financial support provided by the
technological Agency of the Czech Republic, CONTACTS
under project No. TA04020583.
Skoblia Siarhei, Ph.D.
Department of Gas, Coke and Air Protection,
University of Chemistry and Technology Prague,
REFERENCES Technická 5, 166 28 Praha 5, Czech Republic.
Email: skobljas@[Link]
Beňo, Z. et al. 2011. Výroba elektrické energie z dřevní
štěpky v komplexní kogenerační jednotce, Technical
report. FT-TI1/219. Praha:VŠCHT.
Michael Pohořelý, Ph.D.
Brandt, P. et al. 2000. High Tar Reduction in a Two-Stage Institute of Chemical Process Fundamentals,
Gasifier. Energy Fuels.14 (4): 816–819. Academy of Science of the Czech Republic,
Knoef, H.A.M. (2) 2012. Handbook of Biomass Gasifica- Rozvojová 135, 165 02 Praha 6-Suchdol, Czech
tion. Eschende: BTG. Republic. Email: pohorely@[Link]

148
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Assessment of the possibility of biogas technology development


for farmers in Cu Chi District, Ho Chi Minh City

M.T. Dang, T.L.C. Nguyen, M.H. Le & A.D. Pham


Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: Biogas digesters brought remarkable effect in terms of economic, social and environmental
sustainability. So far, this model continues to be expansion building for farmers and potential demand.
However, when examined in local areas at Vietnam, there are still many issues that need to be addressed.
For the development of biogas technology in Cu Chi District—Ho Chi Minh City, the local officials of
encouraging for agricultural expansion said that the proportion of households using biogas accounted
for about 15–20% of the total number of farms now. This is still a relatively low rate comparison with the
farmer’s application of biogas technology for quite long time. However, the benefits of using biogas gives
it undeniable. Generally, biogas technology has also been updated many new models of digesters from
concrete reactors and plastic bags to composite bags. The concrete reactors and plastic bags have been
used for quite some time by many households but still quite limited, the composite bags are being more
targeted households use. And, this digester selected to assist farmers in major projects. Expected in the
coming years, composite bags will increase due to the livestock movement in Cu Chi tend to grow fatly
and the concern for environmental issues are increasingly being raised currently.

Keywords: biogas technology, digester, concrete reactor, plastic bags, composite bags

1 INTRODUCTION brought about and developed in some provinces


such as Can Tho, Son Tay, Bac Ninh and some
Biogas technology can be produced by anaerobic other areas (Nguyen, Q.D. 2011).
digestion with anaerobic organisms, which digest Particularly in Cu Chi—a suburban district of
material inside a closed system, or fermentation Ho Chi Minh City, had the largest herd of the
of biodegradable materials (National No-Food city, the proportion accounted for 44.2% pigs, and
Crops Centre 2011). Biogas is primarily methane dairy cows accounted for 57.2% of the total breed-
(CH4) and carbon dioxide (CO2) and may have ing households in the city. According to the Cu
small amounts of hydrogen sulfide (H2S), mois- Chi Department of Agriculture and Rural Devel-
ture and siloxanes. The gases methane, hydrogen, opment, this district had more than 6,000 small-
and carbon monoxide (CO) can be combusted or scale farmers, including 161 pig farms and 26 cattle
oxidized with oxygen. This energy release allows farms. According to statistics, there were over
biogas to be used as a fuel; it can be used for any 2,500 household biogas in Cu Chi, the rest did not
heating purpose, such as cooking. It can also be have specific statistics. Therefore the management
used in a gas engine to convert the energy in the of waste from cattle needs a synthesis of techni-
gas into electricity and heat (Global Methane Ini- cal measures, education, environmental policy, and
tiative 2011). economic (HCMC People’s Committee. 2001; Vo
Many rural areas of some countries such et al. 2012).
as India, China, Nepal, Pakistan, Bangladesh, Has been identified as a solution to the best
Thailand has used animal manure (cattle, pigs, …) livestock waste treatment, biogas technology has
to produce methane in service demand for gas been to encourage and support the installation in
and electricity for the home. In Vietnam, biogas the local areas. However, the proportion of house-
technology was implemented since 1960. After holds using this type of biogas technology was
unification (1975) until 1990, this technique was estimated at 15–20% of the total number of farms,
considered to be one of the top priorities of the the application of the biogas reactor technology in
country in research programs to find new energy livestock at Cu Chi today is facing many difficul-
and renewable energy. Technology for producing ties capital, policy support, especially people not
methane gas from livestock manure has also been really have access to new, high effective and low

149
cost technologies (HCMC People’s Committee. such as waste classification, sizes of digesters, types
2001; Vo et al. 2012). of material loading, uses of byproducts; effective-
The assessment of the ability to develop biogas ness of digesters (Nguyen, H.S. 2011; Morup and
technology for farmers in Cu Chi District, Ho Chi Bentzen 2012). There were 75 questionnaires sur-
Minh City were made to the following objectives: veyed in Tan Thanh Dong, An Nhon Tay and Tan
(i) make the correct assessment of the biogas tech- Phu Trung with 25 households for each commune.
nology applications (status and prospect); (ii) con-
tribute to additional documentation as the basis
2.3 Data analysis
oriented building solutions to develop biogas tech-
nology increasingly. The Pearson test (SPSS, version 16.0) was used for
assessment to provide the research subjects. In this
project, the results were selected and expressed as
2 MATERIALS AND METHODS a percentage (%) or the chart depending on the
intended use.
2.1 Study sites
This study was carried out in Cu Chi, namely in
3 RESULTS AND DISCUSSION
three communes of Tan Thanh Dong, An Nhon
Tay and Tan Phu Trung (Figure 1). These were
3.1 Structure of livestock
the typical social development of the district in
agriculture of livestock farm. On the other hand, The survey results on the structure of poultry and
agricultural development in three communes char- cattle in Cu Chi District were presented in Table 1.
acterized by different types as follows: Tan Thanh These results showed that the farmers raised the
Dong with dairy operation and grass plantation; pigs and cows mainly. With the number of pigs
Tan Phu Trung with pig breeding and vegetables accounted for 93% of the total of animals to be
plantation; and, An Nhon Tay with high economic examined and the number of cattle accounted for
efficiency plantations such as rubber and fruit trees. 7% (mainly dairy). For poultry, most of the sur-
With characteristics of agricultural development veyed households these have not got the insignifi-
above, the survey scope could avoid the results of cant numbers. Some households have cultured fish
duplication and more objectivity. (mainly catfish) for the purpose of handling swine
waste.
In three communes in the district of Cu Chi was
2.2 Field surveys
surveyed, Tan Phu Trung has the highest number
The investigation and data collection was done in of pigs with 40% of total households surveyed.
the form of semi-structure interview directly. The Meanwhile, Tan Thanh Dong is dominant in cattle
survey sample was made to meet the data colection, breeding with 4.2% of 7%; the majority of cattle
including general information: the householder, the farmers make use of garden to grow grass to save
main income; the situation of agricultural produc- feed cost for cattle (mainly dairy).
tion and waste disposal; the technical information
3.2 Forms using livestock waste
Forms to use animal waste were shown in Table 2.
According to the survey results, the waste was used

Table 1. Statistics on the number of livestock in study


sites.

Pigs Cows

Study Sites No. % No. %

TTD 1,196 23.9 209 4.2


ANT 1,451 29.1 79 1.6
TPT 3,153 40.0 63 1.2
Total 4,642 93.0 315 7.0

Notes: TTD (Tan Thanh Dong); ANT (An Nhon Tay);


TPT (Tan Phu Trung); percentages (%); number of live-
Figure 1. Study sites in Cu Chi District. stock (No.).

150
Table 2. Forms to use livestock waste in the study sites.

Biogas Fresh Manure Selling Aquaculture Disposal


Study
Sites H % H % H % H % H %

TTD 12 48 11 44 6 24 1 4 0 0
ANT 15 60 7 28 0 0 1 4 4 16
TPT 14 56 9 36 0 0 0 0 1 4
Total 41 54.7 27 36.0 6 8.0 2 2.7 5 6.7

Notes: TTD (Tan Thanh Dong); ANT (An Nhon Tay); TPT (Tan Phu Trung); Number of households (H);
Percenatges (%).

Table 3. Surveyed results of energy using in households.

Biogas Civil gas Charcoal or Firewood

Study Sites H % H % H %

TTD 12 48.0 13 52.0 1 4.0


ANT 15 60.0 10 40.0 4 16.0
TPT 14 56.0 11 44.0 0 0
Total 41 54.7 34 45.3 5 6.7

Notes: TTD (Tan Thanh Dong); ANT (An Nhon Tay); TPT (Tan Phu Trung); Number of households (H);
Percenatges (%).

for biogas mostly with 54.7% of total households combination, therefore the resale livestock waste
surveyed. The farmers used mainly the biogas has been concentrated here.
digesters of concrete reactors, composite bags; The form used for food waste for aquaculture
some households had a large number of livestocks, (mainly catfish) was very little, only 2 households
they used plastic bags which had some advan- with 2.7% total surveyed, but waste was put into
tages because of low cost and large volumes. This fish ponds following residues from biogas. House-
showed that the biogas technology has brought holds using this form have got the much number
practical benefits to the users. of pigs.
In the surveyed results, 36% of households used Some households were discarded directly into
livestock waste for fresh fertilizer purposes. Nor- sumps, canals or the area behind the livestock
mally, households using livestock waste for this sector that did not use for other purposes such as
purpose had combine of animal husbandry and watering plants or feed for fish. The majority of
farming (grass, vegetables or rubber). Released these households were a little of livestock.
waste would be the majority of households col-
lected by sumps then manually crop irrigation;
3.3 Forms of energy
some farmers use waste path to the growing area
directly. Among households using biogas still used A survey of 75 households have obtained the
fresh waste for fertilizer purposes, so the volume results of the energy that households were using.
of biogas reactor was not enough large to contain In addition to the use of electricity for purposes of
all waste. The residual waste would be taken as a indoor lighting and water pumping as biogas, civil
fertilizer for crops. gas, charcoal or firewood was the choice of the
For forms of selling livestock waste, this form household. Depending on the economic condition,
occupied for 8%, mainly raw cow manure. Farm- staying space or living habits that every household
ers usually dried and then packaged and sold to had the choice of energy sources used. The use of
merchants or growers with prices ranging around energy resources was shown in Table 3.
2,000–5,000 VND per Kg. The sale of the cattle According to the survey results in the study
waste depend on the seasons, the dry cow dung sites, 100% of households using biogas reac-
sold for the dry season than this in the wet season. tors would use biogas for cooking purposes in
In the three study sites, the majority of households the family instead of using civil gas. Forms using
in Tan Thanh Dong breeding cattle or cow and pig biogas energy sources accounted for 54.7% of all

151
households were surveyed. This energy not only and has collected many different reasons such as
brought economic benefits, if the construction economic difficulties, inadequate construction
and installation would significantly reduce costs areas, a few livestock, and no demand. Farmers
for fuel used in daily life, but also solved problems with small scale less than 30 individuals, they often
arising in livestock odor. encountered problems in livestock. Therefore, the
Materials, fuel using for domestic purposes in cost of building a biogas digester was difficult for
the households were mainly civil gas and firewood. farmers currently.
Through the survey, the households have not got In total 75 households surveyed, there were 34
biogas reactors, all of them used civil gas (45.3% households have not got biogas reactors. When
of total households) by the advantages of conven- asked about the cost of building the biogas reac-
ience and cleanliness. Type of civil gas cylinder tors, there were some different levels (Table 4).
using in families was kind of 13 Kg, the average
usage time is 2–3 months with a gas price of about
3.4 Effective of current biogas rectors
300,000 VND.
Apart from two energy sources of biogas and There were 41 questionnaires for efficiency using
civil gas, they also used some charcoal and fire- biogas reactors in households including compost
wood as well as raw materials for cooking purposes bags or biogas reactors. The survey results are
by the properties available, easy colection from the detailed as follows:
cultivation process. In particular, many households
in An Nhon have cultivated rubber tree, so the uti- • Classification of biogas reactors
lization of rubber wood for cooking was used here Through field surveys, there were 3 types of
to save more gas products. According to the survey digesters, as follows: concrete reactors, composite
results, there were 4 of 25 households in An Nhon bags, and plastic canvas bags. The types of digest-
Tay used this material. ers is shown in Table 5.
Out of 41 households using biogas digesters, Out of the 41 biogas digesters surveyed, there
2 of 34 remaining households with 5.9% of total were 39 solificated biogas reactors with 95%
were willing to build biogas reactors. The reason (including 29 concrete reactors and 10 composite
was that they expected to expand the scale, increas- bags) and 5% of plastic canvas bags. According
ing the number of livestock and in parallel it was to the survey results, the cost of installing plastic
the impact of policies on communal farming. biogas bags (nylon) was much lower than this in
Accordingly, the subject also found out why farm- concrete digesters. However, the life span of plastic
ers were not ready for the construction of digesters, biogas bags was short at half time comparison with
concrete reactors. The type of composite digesters
were used more in recent years (Figure 2).
Table 4. Statistics on the cost of biogas construction. The chart above showed a clear trend of devel-
opment of all kinds of biogas digesters that used.
Cost of construction Number of Percentage Since 2000, farmers have been approached the
(VND) households (%) biogas reactors in the livestock waste treatment
2,000,000–4,000,000 4 11,8
and biogas production. Types of concrete reactors
4,000,000–6,000,000 13 38,2
and composite bags were used in the first phase,
6,000,000–8,000,000 15 44,1 and then the concrete digesters was developing
>8,000,000 2 5,9 more. However, in the period of 2011–2015, many
farmers used the composite materials digesters,

Table 5. Types of digesters in study sites.

Concrete reactors Composite bags Plastic canvas bags

Study Sites H % H % H %

TTD 9 22.0 3 7.3 0 0


ANT 11 26.8 3 7.3 1 2.5
TPT 9 22.0 4 9.6 1 2.5
Total 29 70.8 10 24.2 2 5.0

Notes: TTD (Tan Thanh Dong); ANT (An Nhon Tay); TPT (Tan Phu Trung); Number of households (H);
Percenatges (%).

152
waste was too liquid and too special also leaded
to no biogas or clogged waste. Additionally, the
untight digesters was caused loss of biogas.
With the type of composite digesters, the user
feedback was good, such as much biogas, less
odorless gas, design architecture. This digester
was used priority at Vietnam in recent years, so it
would tend to develop more in the future.

3.5 Advantages and disadvantages for biogas


development
There were some main advantageous and disad-
vantageous conditions for biogas development in
Figure 2. Tend to use digesters on study sites. Cu Chi District, such as:
• Advantages
With the support of two major projects: (1) The
this was the improved step of this digester compar- project supporting for sustainable livestock devel-
ison with old version. It had air filter and higher opment in the suburban of Ho Chi Minh City was
effective. In addition, some programs or projects funded by the Ho Chi Minh City Department of
such as RRA and LIFSAP selected the composite Agriculture and Rural Development (IMA. 2013);
materials digesters to support for farmers. (2) The project supporting competition of live-
stock industry and food safety in the suburban of
• Capacity of biogas digesters
Ho Chi Minh City was funded by the World Bank
Capacity of digesters was built with different
(IMA. 2013).
sizes, depending on the number of livestock and
Through the communication courses, the farm-
the economic viability of each household. Looking
ers were trained for the biogas quality control.
at the survey results, the highest number focused
There were two companies of biogas development
on the digesters of a capacity of 10–15 m3. Small
(Moi Truong Xanh Co., Ltd. and Hung Viet Trade
farms using digesters usually had number of live-
and Production) who supporting biogas technol-
stock around 50–100 individuals.
ogy of composite bags ().
Currently, the projects of local authorities and
Many households realized high benefits of
other organizations supported the finance and
biogas technology. So they also have voluntarily
technology of composite digesters for farmers to
installed without going through local support.
built biogas digesters in 3 sizes: 7 m3, 9 m3 and 12 m3
• Disadvantages
with prices ranging from 15,000,000–20,000,000
The main reason that farmers have not invested
VND per digester. With such sizes were suitable
capital for the construction and installation of
for pig breeding scale at households, so this type
biogas digesters were economic difficulties. The
was the most preferred choice of the local people.
cost for investment and installation of digesters
The selection of digester capacity normally based
were relatively high, about 15.000.000–20.000.000
on the income of farmers, so many cases with large
VND per digester. Additionally, the loan proce-
herds number had not got enough capacity of
dures of local banks were difficult.
digesters to control waste.
Digesters were not adequately addressed if its
• Effective of biogas digesters volume was not suitable. With the kind of small
Of the 41 households using biogas reactors, digesters with volume 7 m3, then only the breeding
there were 9 digesters of good efficiency, account- number of 15–20 pigs or 6–10 cows were solved.
ing for 22%, and all digesters were the concrete Any residual waste was untreated discharging
reactors. 17 of 41 households received the support directly into the environment.
from local authorities, and work others were built In the process of using digesters, households
by households. have not fully exploited the efficiency of the energy.
When asked about the common issues, there were Most of them used biogas as fuel in cooking
some problem of system congestion, inadequate activities that did not use for other purposes. While
biogas, biogas lost, incident pipeline. Raw materi- there were a variety of devices using biogas energy
als used to load the digesters were completely ani- such as gas lamps, generators, water heaters, gas
mal waste including swine manure, and wastewater cooker, gas stove also.
from cleaning process. The amount of waste were Aside from the few farmers saw great benefits
loaded into the digesters where all the people were of using biogas and manually installed them,
not interested in mixing ratio of raw materials. The other households were not aware of this and

153
environmental awareness was still low. Moreover, ACKNOWLEDGEMENT
the supports and sanctions in the protection of
the rural environment were exposed. In fact, did We would like to thank Dr. Nguyen Thi Mai Linh
not have a legally binding leads to the lack of uni- for helping with the manuscript revision.
formity in the implementation and development of
biogas technology. Last but not least, output for
livestock products was limited, especially on mar- REFERENCES
ket prices were unstable.
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ane: reducing emissions advancing recovery and use
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technology had gradually developed and updated the HCMC People’s Committee.
with the new version technology. Digesters have IMA. World Bank. 2013. Second Ho Chi Minh City Envi-
been built since 2005 was still in use. In recent ronment Sanitation Project. The Investment manage-
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All households using biogas digesters preferred Nguyen, H.S. 2011. Classification and assessment of
using biogas energy instead of civil gas or other the types of biogas digesters. Agricultural Extension
raw materials such as coal, firewood. … The goal Center.
of biogas utilization in local households were used Nguyen, Q.D. 2011. Biogas Development Program for
for fuel purposes but not for other purposes, such livestock sector in Viet Nam 2007–2012, Biogas User
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154
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

An overview of food waste management in Ho Chi Minh City, Vietnam

N.B.D. Thi
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: This review provides the insights of conversion of Food Waste (FW) in Ho Chi Minh
City (HCMC), Vietnam to bio-energy and bio-compost. The evaluations of bio-productions potential
from FW conversion to commercially fulfil energy demands are elucidated. Moreover, an analysis of FW
management system of the city using environmental impact assessment method was applied, and thereby
illustrating which part of the whole management system need to be implemented. Finally, an appropriate
hierarchy of FW management was suggested towards elevating concept of reduce, reuse, recycle, recovery
(4Rs) in the city.

Keywords: anaerobic digestion, bio-compost, bio-energy, food waste, incineration

1 INTRODUCTION industrial enterprises (cafeteria and office), no


infected medical centers (cafeteria, office and
1.1 General introduction about HCMC sickroom) is about 9,000 tonnes per day (HCMC
Department of Natural Resources and Environ-
Ho Chi Minh City (HCMC) is a mega city located
ment 2011). With the rate of increase in quantity
in the South of Vietnam. HCMC has the largest
of about 6–8% per year, municipal solid waste is
second area with 2,095 km2 in comparison with
of primary concern to environment. Food waste
Hanoi, the capital of Vietnam (3,325 km2). HCMC
(or organic waste) is the largest component part of
is the biggest center of socioeconomic, culture,
total amount of municipal solid waste, which have
education, science and technology, international
reported at 60–72% in Phuoc Hiep landfill and
cooperation, trading and industry of the country.
67–75% in Go Cat landfill (HCMC Department of
Population scale of HCMC is about 8,224,400
Natural Resources and Environment 2011a). Those
citizens (Statistical Office in HCMC 2015). How-
organic waste has high concentration of humidity,
ever, this biggest economic city of Vietnam is facing
about 75% (Tran and Ta 2015). The average FW
various serious urban and environmental manage-
rate per capita of Vietnam is lower (0.06 kg/day)
ment issues. Among all environmental issues, food
in comparison with other countries in Southeast
waste management is one of the biggest issues due
Asian area, such as Thailand (0.14 kg/day) and
to its lack of food waste management system and
Malaysia (0.18 kg/day) (Thi et al. 2015). The com-
inefficient implementation of FW policies and
positions of FW were investigated in these landfills
regulations, which currently results in many envi-
is presented in Table 1.
ronmental pollutants (Thi et al. 2015). HCMC is
Leftovers food and biodegradable food scraps are
currently with 2 million of households, more than
the largest portion of FW stream with 64.3–98.3%
10,000 hotels and restaurants, more than 400 mar-
kets (including open and super market), 20,000
office buildings, more than 184 hospitals 600 pub- Table 1. Composition of FW in HCMC (Tran et al.
lic, 600 public health centers and 9,000 clinics, and 2014).
more than 12,000 (including 2,000 big industries
and more than 10,000 small and medium-sized Composition Range of percentage (%)
enterprises). (HCMC Department of Natural
Resources and Environment 2011a). Leftovers food 64.3–98.3
Biodegradable food 53.7–88.2
scraps
1.2 Food waste categories in HCMC Wood shell (coconut, 0–12.4
peanuts)
The number of Municipal Solid Waste (MSW) Animal bone 0–16.7
generated from HCMC’s residential areas, com- Shell/bivalve 0–18.9
mercial areas, organizations, schools, offices,

155
of total FW amount, followed by bivalve shell FW in markets is mostly stored on floor or in
(0–18.9%), animal shell (0–16.7%), and wood shell large size containers (Figure 1b). Due to the weak
such as coconut shell and peanuts shell (0–12.4%). management, most of market’s wastes are dumped
Besides, there are some other inorganic compo- on floor without any covering technique, which
nents mixed in household FW which are plastic consequently results many critical issues as patho-
bags, milk containers; other plastics, ash, ceramic, gens and stinky odour. In HCMC, many restau-
and other non-recyclable wastes. However, most rants have special storage containers of FW to
of household FW is not separated at source, and store FW for utilizing as animal feedstock.
mixed with other solid wastes, which finally results At source, most households separate the valua-
negative effects for the environment such as odour, ble wastes such as cans, plastic, paper, metals from
leachate, spreading of pathogens and related their municipal solid waste and sell to itinerant
factors affecting to community health. buyers. Those recycling activities occur spontane-
ously and unorganized. It is reported that the total
number of recycling rate in HCMC is very low
2 CURRENT FW MANAGEMENT SYSTEM around 10% of all over. There are a participation
AND THE PROBLEMS of private and public sectors in recycling waste that
is around 750 to 800 itinerant private factories, and
2.1 Current FW management system 7 to 9 public recycling plants. The number of itin-
erant people go around to buy recycling materials
The current FW management system is analyzed
of the households is about 18,000 to 19,000 indi-
based on four operations including storing at
viduals (HCMC Department of Natural Resources
source, collecting, transporting and treating FW.
and Environment. 2011b). Figure 1c and 1d show
Currently, FW is conventionally mixed in house-
solid waste collecting activities by private sectors
hold garbage. Household FW is not segregated at
(local solid waste organizations) and public sec-
source, and collector sectors do not separately sort
tors (HCMC urban environment company limited
FW out of municipal solid waste during collection
(CITENCO) and the district public services com-
process.
pany limited in 22 districts of HCMC) (HCMC
FW generation is mostly stored in plastic bags or
Department of Natural Resources and Environ-
plastic containers, the individual and public waste
ment. 2011a). Due to the especial urban planning
collectors will daily come to collect and transport
of HCMC is famous with many passageways and
to transfer station, and then dispose in landfills.
alleys interlacing together, therefore municipal
Since current municipal solid waste management
solid waste is common collected by private sectors.
policy has not been enacted by the government in
The public sectors mostly work on cleaning main
HCMC, therefore, most of HCMC’s citizens do
streets, collection, transport, treatment and dis-
not know how to segregate municipal solid waste
posal of solid waste from household, construction,
at source and utilize FW efficiently. Figure 1 shows
business organizations, and industrial zones.
the way householders store their solid waste at
HCMC is using door-to-door solid waste col-
source.
lection with the total amount of 3000 group, which
is shared with 70% by private groups and 30% by
public groups. Depending on the length and qual-
ity of the transport routes, the capacity of the
trucks can be selected. The private sectors prefer
using handcarts with 1 to 1.5 m3/cart or engine-
handcart (small truck) to transfer solid waste from
household to the gathering points. Then a bigger
truck will transport the waste to transfer stations
or directly to landfills. The public sectors will play
main role in street collection and transferring
MSW from transfer stations to landfills using big
trucks with 4–15 tons/truck which total amount
of 700 trucks (HCMC Department of Natural
Resources and Environment. 2011a). However, the
bottlenecks in collection system are poor in qual-
ity and quantity of collecting equipment (Tran and
Figure 1. a) Storing solid waste at household, b) Stor- Ta 2015). Besides, there are also lacks of collection
ing solid waste at market, c) Collecting municipal solid skills and recycling training in collecting resource,
waste by private sector, d) Collecting municipal solid which could cause fail in source separation of
waste by public sector. waste and reduce collecting efficiency in the whole

156
Table 2. Scoring matrix of environmental impact assessments of HCMC’s FW management system.

Stage of FW management system

Environmental Generation
impact factors and storage Collection Transfer Transport Recycling Treatment

Soil pollution 3 1 0 0 1 2
Groundwater pollution 2 0 0 0 0 2
Spillage of waste during 0 0 1 2 0 0
transfer and transport
Odours or pathogen issues 2 1 1 1 2 3
Landfill leachate release 1 0 0 0 0 3
Air pollution from 2 1 1 1 1 3
incinerator/landfill
Human health affect 1 1 0 0 0 2
Total Impact Score (TIS) 11 4 3 4 4 15
Significant impact Moderate Low Low Low Low High

municipal solid waste management system (Tran • 2: Moderate impact;


and Ta 2015). • 3: High impact.
In HCMC, landfilling is the major MSW
waste treatment method, which is estimated to be The maximum value is 21 Total Impact Score
about 90% of total FW disposal by landfill (Thi (TIS). The potential environmental impacts were
et al. 2015). In fact, landfills practice is not con- then rated as of Low significance (0<TIS≤7),
sidered to be a feasible method for treatment of Moderate significance (7<TIS<14), High signifi-
FW because of its biodegradability, and FW in cance (14≤TIS<21).
landfills can result in disease vectors (Louis 2004). Based on results of Table 2, there are two activi-
Besides, landfilling FW can contribute to green- ties of the whole FW management system caused
house gas emissions at a rate of 8% (Bijava et al. high significant impact, which are generation/
2006). It is around 10% of FW is reused for animal storage FW at source and FW treatment activity.
feeding and composting. However, the recycling of Therefore, some necessary mitigation measures
FW in HCMC is deficient due to some key reasons are required to mitigate the impact magnitude
(1) FW is not separated at source; (2) The fraction and keep environmental qualities within accepted
of FW is complicated and included many useless national standards.
components such as animal bone, chopstick, woody
toothpick causing deficient to use for animal feed- 2.2.2. Stakeholders responsibilities
ing; (3) Most of composting plants in HCMC have A successful FW management system is required
small scale with low technology, resulting in high the responsibilities of local environmental author-
pollutions and easy to be disqualified in compari- ity, public community, and industrial sectors. How-
son with other compost products. ever, the integration among stakeholders in the
whole waste management system were weak, which
causes failures in many programs and projects
2.2 Problems associated with FW management
related to FW management in HCMC (Tran and
2.2.1 Environmental impact assessments Ta 2015).
The used method of environmental impact assess-
ment is based on the official environmental impact
assessment report of Golder Associates (Marioni 3 APPROPRIATE APPROACH TO FW
2014) [9], which uses a scoring matrix to illustrate MANAGEMENT IN HCMC
the significant of environmental impact assessments
through the whole HCMC’s FW management sys- 3.1 Evaluating bio-productions potential
tem. The table 2 showed the environmental impact from FW
assessments of current issues associated with FW
3.1.1 FW to energy
management in HCMC.
There are two forms of FW-to-energy methods
Scoring system for evaluating impacts is below:
are reviewed in this study are bio-treatment and
• 0: No impact; thermal-treatment. In commercially, anaerobic
• 1: Low impact; digestion is the most popular method to convert

157
Table 3. Potential energy generation of HCMC’s FW with regards to energy generation by bio-treatment and
thermal-treatment.

Anaerobic digestion Incineration

Electricity Sharing Electricity Sharing


potential percentage potential percentage
Total from FW in total Total from FW in total
Total potential conversion national potential conversion national National
amount bio- per capita energy bio- per capita energy energy
of FW energy (KWh/ consump- energy (KWh/ consump- consumption
Population (tonne) (TWh) capita) tion (%) (TWh) capita) tion (%) (TWh)

8,224,400 2,299,500 0.72 87.4 0.55 0.68 82.7 0.52 130

bioenergy from FW, while incineration is the Vietnamese Dong (VNĐ) for each tonne of treated
favorite method for treating MSW to generate elec- FW, while the economic benefits of bio-compost
tricity. It is reported that one tonne of FW could product from FW is evaluated about 0.6 million
generate about 296 KWh of electricity by incinera- VNĐ for each tonne of treated FW (Hitachi Zosen
tion [10], while using anaerobic digestion to treat Corporation 2014; SACO. 2016).
FW could generate up to 313 KWh of electricity
(Thi et al. 2016a). The prediction of bioenergy
3.2 Elevating concept of reduce, reuse, recycle,
potential of HCMC’s FW is shown in Table 3.
recovery (4Rs)
3.1.2 FW to bio-compost The suggested actions to reduce avoidable FW and
Developing country such as Vietnam, where elevate concept of reduce, reuse, recycle, recovery
economy is largely based on agriculture, hence (4Rs) in HCMC are below:
FW recycling activities for providing bio-compost
need to be encouraged. Especially, bio-compost is • Set up targets to reduce FW for the city
also considered as a friendlier product from treat- • Educating and training on costs of food waste
ing FW, which requires low cost investments and for citizens
operational costs compared to other processes • Encourage purchase planning
(Jeffrey 2007). Composting provide fertilizer, con- • Operate general awareness campaigns on avoid-
sidered to be environmentally friendly product. able FW prevention
Many countries have specific forms of legislation • Freezing and storage routines
to enforce composting FW for FW treatment (Thi • Training on environment awareness and sorting
et al. 2016b). It is revealed that HCMC has just waste
recycled 600 tonnes of FW per day to produce bio- • Encourage hospitality sectors such as hotels, res-
compost (Louis 2004). Theoretically, it is predicted taurants and markets do assessing and measur-
that HCMC could utilized 6,300 tonnes of FW per ing the FW/avoidable FW
day to produce about 1,575 tonnes of bio-compost • Routines on excess food for distribution to other
(rate of 1 tonne FW produces 0.2 tonne of bio- people with needs
compost) (SACO. 2016). However, in fact, there • Encourage hospitality sectors review legislative
still remain some inefficiencies of composting requirements and routines taking avoidable FW
production caused by unpurified waste feedstock, issue into account
which results from the incomplete source separated • Routine of reuse excess food production and
FW system. As a result, the composting-market is leftovers for animal feeding
weak, and FW-composts need to compete with • Routine of recycle sorted FW for composting.
various chemical fertilizers that cause dilemmas Besides, the role of city government is needed on
for the operations and investments of composting possible instruments and actions to be undertaken.
facilities (Thi et al. 2015). For example, the most needed popular instrument
is Governmental financial support to campaigns
3.1.3 Economic value assessment and training.
The economic value of HCMC’s FW is assessed
base on predicted electricity potential and bio- • Regulative instrument: Ban on avoidable FW
compost products. In which, if electricity-based • Legislative instrument: Implement legislation
FW has sale price about 10.05 cent/kWh, it would and provide incentives for FW management in
bring an economic benefit is around 0.66 million the city

158
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Tough Face Tough Bijaya, K.A., Suzelle, B., José, M. 2006. Predicted growth
Face Tough of world urban food waste and methane production.
Waste Manage Res. 24:421–433.
Department of Environment and Natural Resources
Face Tough in Ho Chi Minh city. 2011. Municipal Solid Waste
System in Ho Chi Minh city (In Vietnamese). p.66.
Department of natural resources and environment of
ChildrenFace Ho Chi Minh city people committee. 2011. Sustain-
Face Tough able intergrated system for solid waste management in
Ho Chi Minh city, Vietnam. Workshop Kitakyushu,
Japan, p.6.
Figure 2. Sustainable hierarchy of FW management in Hitachi Zosen Corporation. 2014. Satisfactory Interna-
HCMC. tional. Introduction of Energy-from-Waste Project in
Ho Chi Minh City. 2014.
Jeffrey, M. 2007. Measuring the Benefits of Composting
• Regulative instrument: Same practice for FW Source Separated Organics in the Region of Niagara.
management’s campaign/project whole city Washington, The United States, p.44.
• Economic instrument: Financial support to Louis, G.E. 2004. A historical context of municipal
campaigns and training solid waste management in the United States. Waste
• Economic instrument: Financial support to Manage Res, 22:306–322.
research and projects Marioni, D. 2014. Environmental impact assessment for
sasol PSA and LPG project. Waste impact assess-
• Economic instrument: Taxes on avoidable FW.
ment. Report Number: 1302793-10712-10 (Eng).
Lastly, in order to enhance 4Rs concept for FW Mozambique, p.158.
management in HCMC, the sustainable hierarchy SACO. 2016. Success in treating food waste to compost (in
of FW management in HCMC is suggested in Vietnamese), [Link]
cong-trong-xu-ly-rac-thai-sinh-hoat-thanh-phan-
Figure 2.
compost/ (Access on 19 July 2016).
Statistical office in Ho Chi Minh City. 2015. Economic
and Social Report of Ho Chi Minh city in December
4 CONCLUSIONS 2015. (In Vietnamese).
Thi, N.B.D., Kumar, G., Lin, C.Y. 2015. An overview
This paper elucidated that HCMC could recover of food waste management in developing countries:
various benefits from utilizing its FW in a proper Current status and future perspective. Environ
way by enforcing the strict laws and regulations. Manage, 157:220–229.
As mentioned, FW could be used as a source of Thi, N.B.D., Lin, C.Y., Kumar, G. 2016a. Electricity
generation comparison of food waste-based bio-
energy and compost, which are highly economi-
energy with wind and solar powers: A mini review.
cal and open new commercial ventures in the Sustainable Environment Research, 26:6.
city. Ultimately, an appropriate approach to FW Thi, N.B.D., Lin, C.Y., Kumar, G. 2016b. Waste-to-
management was suggested for HCMC in light of wealth for valorization of food waste to hydrogen and
elevating concept of 4Rs (reduce, reuse, recycle, methane towards creating a sustainable ideal source of
recovery), which could be the feasible approach bioenergy. J Clean Prod.
by far. Tran, T.M.D., Le, M.T., Nguyen, V.T. 2014. Composi-
tion of food waste component. Int J Environ Prot, 4:
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ACKNOWLEDGEMENTS
lengies to Approach Zero-Disposal of Biodegradable
Organic Domestic Solid Waste in Ho Chi Minh City,
The author gratefully acknowledges the financial Vietnam. Int J Innov Sci Eng technol, 2:668–765.
supports by Ton Duc Thang University for this
study.

159
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Pyrolysis technologies and energy recovery from waste


in the Czech Republic

V. Lapčík
Faculty of Mining and Geology, VSB—Technical University of Ostrava, Ostrava, Czech Republic

ABSTRACT: The main aim of the work is to characterize possibilities of energy recovery from waste
(in this case from waste tyres and municipal waste free of the biodegradable component and inert mate-
rial). The attention is paid to currently prepared advanced technology plants for energy recovery from
waste. The following are the characteristics of the planned plants for energy recovery from tyres and
municipal waste in the Czech Republic. In described case all these plants operate essentially on pyrolysis
principle. Pyrolysis is the thermal decomposition of organic materials in the absence of oxygen-containing
media (air, carbon dioxide, water vapour) which leads to the formation of gaseous, liquid and solid frac-
tions. This process is an alternative to combustion. The essence of this method is that organic compounds
are less stable at higher temperatures. High molecular substances are decomposed to low molecular ones,
which leads to their breakdown into volatile products and coke. Pyrolysis is carried out at the tempera-
tures ranged from 150°C to 1,000°C. The article includes a section dealing with the results of emission
measurements of pyrolysis plant PTR 1000 for energy recovery from municipal waste free of the biode-
gradable component and inert material and waste tyres. The conclusion of this contribution discusses the
situation in environmental impact assessment of pyrolysis technologies for energy recovery in the Czech
Republic.

1 INTRODUCTION content, but produces pollutants like nitrous and


sulphur oxides, dust, hydrocarbons, and dioxins,
At present, a number of energy recovery pyrolysis which have highly negative bearing on the envi-
plants are being prepared in the Czech Republic ronment. On the other hand, this combustion of
(CR), which are to process predominantly waste wastes destroys completely an important resource,
tyres, plastics, or municipal waste free of the bio- as wastes organic content are converted only into
degradable component. CO2 a H2O.
Both tyres and plastics (in this case from munic- Pyrolysis technology applied to these wastes may
ipal waste) have been used in modern societies in have an important role in future, as it may allow
almost everything, which have created increasing the conversion of these residues into economical
amounts of wastes with negative impact on envi- valuable products, which can be used as fuels or as
ronment. Due to the fact that the main solutions, feedstock in petrochemical industry.
used so far, to deal with these wastes present several
problems and do not seem to be the right ones, to
2 PYROLYSIS AND ENERGY RECOVERY
decrease, in an effective way, the increasing amount
FROM WASTE
of wastes produced all over the world. Landfilling
of tyres and plastics residues is not a solution,
2.1 Pyrolysis technologies
because it has been increasingly difficult to find
suitable places for building technically adequate Pyrolysis is the thermal decomposition of organic
landfills due to the danger of leaching and soil materials in the absence of oxygen-containing
impregnation, with the subsequent contamination media (air, carbon dioxide, water vapour) which
of underground waters. Apart from this, landfill- leads to the formation of gaseous, liquid and
ing does not allow the recovery of organic content solid fractions. This process is an alternative to
of these wastes that should be part of the organic combustion.
lifetime cycle (Miranda et al. 2003). In addition to The essence of this method is that organic
that landfilling of municipal waste in the Czech compounds are less stable at higher temperatures.
Republic will be over since 2024. Incineration has High molecular substances are decomposed to low
the advantage of taking profit of wastes energetic molecular ones, which leads to their breakdown

161
into volatile products and coke. Pyrolysis is carried
out at the temperatures ranged from 150°C to
1,000°C. According to the temperatures (Obroučka
2001), we distinguish:
• Low-temperature pyrolysis (reaction tempera-
ture up to 500°C),
• Medium-temperature pyrolysis (reaction tem-
perature from 500°C to 800°C),
• High-temperature pyrolysis (reaction tempera-
ture above 800°C).
Advantages of pyrolysis processes (CENIA
2005):
• Easier and less capital-intensive plants.
• There is only a small fraction of gaseous prod-
ucts of incineration compared to the same
amount of fuel.
Figure 1. Discontinuous pyrolysis plant XY-8 (batch
Disadvantages of pyrolysis processes: process) of company Shangqiu Jinpeng Industrial
• More expensive operation. Co., Ltd.—reactor or rather rotary pyrolysis kiln
• A problem to remove the pyrolysis residue as for is (photo—author).
not clean (pyrolysis coke), liquid hydrocarbons.
8 and 10 tons (at most about 30 tons per batch)
Pyrolysis can be used in addition to the thermal
of different capacity. Unfortunately, emission val-
treatment of municipal waste (free of the biode-
ues measured on this pyrolysis equipment by an
gradable component) and treatment of plastic
accredited laboratory are not available.
waste and used tyres also to decontamination of
Another facility sold as PTR 1000 (= engl.
soils, treatment of sewage sludge and treatment for
STD—slow thermal decomposition) is from Czech
the substance utilization of cable waste, metal and
firm Hedviga Group plc and it is capable of energy
plastic materials.
recovery from waste rubber, tyres and municipal
For a long time, the pyrolysis technologies are
waste as well as a whole number of other waste
considered to be very promising also in the field of
(sewage sludge, oil waste, plastics, biomass)
energy recovery from waste. Although research in
(Hedviga Group 2012).
this area is quite wide and technological develop-
The PTR principle (= STD—slow thermal
ment is well advanced, neither of these technologies
decomposition) is based on the principles of pyrol-
is still established in the waste area so that the future
ysis, however it is modified. Unlike the standard
operator in the Czech Republic could get it complete,
pyrolysis process, the qualitative technical and
as we say “turn-key”. This is currently a big problem,
technological shift with the PTR technology is
because there is nothing in this field in the Czech
the following (Hedviga Group 2012; Lapčík 2013;
Republic the entrepreneurs could equipped with the
Lapčík 2014):
intended operations for treatment of waste (tyres,
municipal waste) that they would like to operate as a − it is low-heat decomposition with the tempera-
plant for waste energy recovery (Lapčík 2011). ture below 480°C with a higher efficiency of
It shows that promising are the batch pyroly- energy use for heating without chimney waste,
sis facilities. In the neighbouring countries, e.g. − it is a slow process (slow thermal decomposi-
Poland, a batch pyrolysis facility by the Chinese tion); thermal decomposition has therefore suf-
company Shangqiu Jinpeng Industrial Co., Ltd. is ficient time (in terms of tens of minutes) for a
well-established. complete separation of fractions and conse-
This company offers both continuous and dis- quently for a higher efficiency of creation of gas
continuous (batch type—Fig. 1) pyrolysis plant and liquid products. The yield on these products
(Shangqiu Jinpeng Industrial Co., Ltd. 2015). from comparable raw materials is about 5 ÷ 8%
The facilities can recycle and utilize waste plastics, higher than bibliography mentions (measured
waste rubber, tyres and waste engine oil. According for decomposition of tyres at the temperature of
to the actual situation in every country and district, up to 480°C),
it was developed by company Shangqiu Jinpeng − the process starts with slow heating in terms of
Industrial Co., Ltd. series of machine for disposing minutes when fine separation of fractions hap-
scrap tyre and plastics that includes 4 tons, 6 tons, pens without formation of crust on the surface,

162
− it is a batch process which itself is not continu- furnace, two in the exchanger, two being cooled
ous, therefore the slowness of the process allows and two being filled.
a complete separation of products and control Fuel element or fuel cell is filled from the top
of the temperature increase in the raw material with ground raw material which is transported
according to temperature curve without thermic from the mill by means of a conveyor belt. The ele-
shock, ment is manipulated by a radial crane which places
− the slowness of the process allows to collect it on the rails in front of the furnace. The element
all gas products into tanks and to use them to enters the furnace (the thermal module) on the
operate a cogeneration unit without discharging rails. After finishing a cycle, the hot element is
exhaust gases into the air. As a result, no emis- pulled out on the rails by means of a magnetic lock
sions happen (except the outlet from the cogen- and is then left in a thermal exchanger with a newly
eration unit). filled element. After cooling (approx. 6 hours), the
element is lifted by a crane and the carbon rest is
The PTR unit consists of two modules: the dumped into a container.
thermal (heating—see Fig. 2) and the cooling one. The fuel cells have a cylindrical shape in the
Both modules have a shape and size of a 20-foot innovated facility PTR 1000 kW6 (see Fig. 3).
transport container for the capacity of 1 ton per They comprise of a lid and vessel made of stain-
hour. less steel of class 17, they are equipped with a set
The thermal module is built on the basis of of sensors, including a combined magnetic and
an electric chamber furnace with side heating by pneumatic actuating system. Heating, decomposi-
resistance bars and a maximum input of 200 kW. tion and subsequently cooling of the feed material
The furnace is bricked with fireclay bricks in the occurs in the cells under a slow thermal reaction
floor and heat insulation on the basis of fibreglass and temperature range from 20°C to 500°C.
in the walls. In the upper part of the furnace there The PC 1000 kW6 fuel cell volume is 1.5m3. The
are three ventilators allowing for stable heat con- fuel cells are gas-tight. The overall number of fuel
vection and speed of flowing around fuel elements. cells for one PTR unit is 18 pieces to ensure the
Raw material is put in the furnace in steel compart- continuous mode.
ments, fuel elements (cells) made of stainless steel
of the class 17 with the thickness of the wall of 5 ÷
10 mm with three outlets for gas products and with
bayonet valves for raw material in the upper and
side part of the cell with the diameter of 50 ÷ 80 cm
with insulation that prevents air from getting into
the compartment. The fuel cells are gas-tight. The
fuel cell is transported to the furnace on rails. As
to the manipulation with fuel cells, the PTR unit
needs 8 fuel cells for its operation, two being in the

Figure 2. Pyrolysis plant PTR 1000 (Hedviga Group


plc)—thermal module (photo—author) (Lapčík 2013 a Figure 3. Pyrolysis plant PTR 1000 (Hedviga Group
2014). plc)—cylindrical fuel cell (photo—Hedviga Group plc).

163
The cooler of the PTR process is placed in a municipal waste free of the biodegradable com-
20-foot container and has two circuits with a total ponent and inert material, and other materials.
length of 84 metres. Each circuit of the cooler is Fuel dosage is discontinuous, i.e. batch-based. In
attached individually on one fuel element. The addition to other products, pyrolysis gas is pro-
input temperature of gases entering the cooler is duced from the fuel inside the reactor. The gas is
on average 450°C and the output temperature is then cooled down, purified and captured in a gas
80°C. The cooling liquid is water with ethyleneg- pressure reservoir. The stored gas is brought to a
lycol (in a closed circuit). Hydrocarbons and oil vacuum reservoir through a reducing valve, where
fractions condense in the cooler and pyrolysis oil from it is taken further and combusted in the
occurs. Its composition depends on the composi- cogeneration unit Tedom Cento T 180. The waste
tion of the raw material. Oil from the process is gas (combustion products) is discharged into the
accumulated at the outlet of the cooler in its bot- surrounding air through a damper and a flue with
tom part. The gas is subsequently treated, i.e. dried an output above the roof of the hall. Cogeneration
and purified (Hedviga Group 2012; Lapčík 2013; unit is equipped with a catalyst at the waste gas
Lapčík 2014). output.
The weight balance of the fraction production The measurement was performed as author-
from the PTR 1000 process differs according to ised measurement for the purposes of Act No.
the raw material: approx. 330 kg of gas, 450 kg of 201/2012 Coll. on air protection, in the scope of
pyrolysis oil and 220 kg of the carbon rest is pro- Decree No. 415/2012 Coll. of the Ministry of the
duced from 1,000 kg of tyres (raw material). Environment.
It should be also noted that the waste energy The measurement was performed in the scope
recovery saves e.g. an equivalent of the brown below:
coal volume, which would otherwise have to be
extracted and consumed in power plants and heat- • Air-conditioning parameters were determined.
ing plants. • Concentrations of solid contaminating sub-
The technology PTR is connected with the stances were determined.
Tedom Cento T 180 (Czech Republic) cogenera- • Concentrations of oxygen and carbon dioxide
tion unit which produces heat and electric current (O2, CO2) were determined.
from the formed pyrolysis gas. Solid outputs will • Concentrations of gaseous contaminating sub-
be subject of commercial sale. stances were determined.
More problems, including those with state • Results were evaluated and the report was
authorities, are associated with the pyrolytic oils. prepared.
It comes as a surprise because in the neighbouring
EU countries (e.g. in Poland) there are a number
of pyrolytic plants processing, for example, waste 3 RESULTS
tyres, and their basic final product is pyrolytic oil
sold to refineries (Poland). The Energy Research Centre at VSB–Technical
Some operators of future pyrolysis plants may University of Ostrava measured emissions (certifi-
dispose of pyrolytic oil in cogeneration units cates of accredited tests No. 03/13 and No. 06/13
that combust pyrolytic oil, or a mixture of pyro- of 18th February 2013—pyrolysis of municipal
lytic oil and gas. This option is also offered by waste free of the biodegradable component and
Hedviga Group plc, which successfully tested the inert material) in the premises of company Hedviga
facilities VOPTRA C 220 and C 250 Dual (VOP & Group plc in the Czech Republic on 23rd January
Hedviga). 2013 using facility PTR 1000 combined with a
cogeneration unit Tedom Cento T 180. Table 1
gives an extract of the taken emission values for
2.2 Measurement of emissions from pyrolysis of
the cogeneration unit (pyrolysis of municipal waste
tyres and municipal waste without biomass
free of the biodegradable component and inert
The purpose of the measurement of emissions was material).
to use accredited and authorised emissions meas- The values in Table 1 imply that the over-
urement methods and procedures to determine whelming majority of the taken emission values
output concentrations and mass flows for contam- of pollutants comply with the set specific limits.
inants specified below in waste gas at the output In accordance with Article 2.3, Section I, Appen-
of cogeneration unit Tedom Cento T 180 during dix 4 to Regulation 415/2012 Coll., the specific
combustion of pyrolysis (synthetic) gas produced emission limits (for PCDD/F, Hg, Cd, and Tl)
at the PTR unit. are fully complies with; in case of Cd, Tl, Hg and
The PTR 1000 facility has been designed for PCDD/F they are two orders of magnitude lower.
pyrolysis of rubber pulp from recycled tyres, In line with Article 2, Section II, Appendix 2 to

164
Table 1. Measured emission values—pyrolysis of municipal waste free of the biodegradable component and inert
material. Pyrolysis plant PTR 1000 (manufacturer Hedviga Group plc, Czech Republic), certificates No. 03/13 and No.
06/13 of 18th February 2013.

Average mass
concentration Emission
Pollutants of pollutants limits Remarks
3 3
NOx 284 mg/Nm 500 mg/Nm Emission limits for cogeneration units
CO 800 mg/Nm3 1300 mg/Nm3 (Appendix 2 to Regulation 415/2012
Coll., as amended, Section II,
Article 2, Table 2.2)
PM (Solid pollutant) 1.05 mg/Nm3 10 mg/Nm3 Emission limits for incineration of
HF 0.09 mg/Nm3 1 mg/Nm3 waste (Appendix 4 to Regulation
HCl 0.17 mg/Nm3 10 mg/Nm3 415/2012 Coll., as amended, Section
SO2 135 mg/Nm3 50 mg/Nm3 I, Article 1, Table 1.1
TOC 179 mg/Nm3 10 mg/Nm3
PCDD/F 0.00167 ng/Nm3 0.1 ng/Nm3 Emission limits for incineration of
(Σ TEQ) waste (Appendix 4 to Regulation
Hg metals 0.00027 mg/Nm3 0.05 mg/Nm3 415/2012 Coll., Section I, Article 2.3)
Cd metals 0.00061 mg/Nm3 Σ 0.05 mg/Nm3
Tl metals 0.00046 mg/Nm3
PAH 0.000023 mg/Nm3 1 mg/Nm3 Emission limit (EU)

the Regulation (i.e. the EL for NOx and CO), the are fully complies with; in case of Cd, Tl and Hg
emission limits fall behind 1.6 times (CO) to 1.8 they are two orders of magnitude lower. In case
times (NOx). The remaining pollutant limits for of PCDD/F the measured emission values are
which the Appendix 4, Article 1.6 of Act 201/2012 16.8 times lower than the given Emission Limit
Coll., on the protection of air, prescribes continu- (EL). In line with Article 2, Section II, Appendix
ous measurements of emissions (the EL for PM, 2 to the Regulation (i.e. the EL for NOx and CO),
TOC, chlorine as HCl, fluorine as HF, and SO2) the emission limits fall behind twice (NOx) to 25
are met in the majority of cases with reserve for times (CO). The remaining pollutant limits for
the emissions limits for thermal processing of which the Appendix 4, Article 1.6 of Act 201/2012
waste according to Section I, Article 1, Table 1.1 Coll., on the protection of air, prescribes continu-
of Appendix 4 to Regulation 415/2012 Coll. For ous measurements of emissions (the EL for PM,
example, the measured emissions of HCl are 58.8 TOC, chlorine as HCl, fluorine as HF, and SO2)
times lower than the set emission limit, the emis- are met in the majority of cases with reserve for
sions of HF are 11.1 times lower than the EL, the emissions limits for thermal processing of
and the emissions of PM are 9.5 times lower than waste according to Section I, Article 1, Table 1.1
the EL. The emission limit (meant for the ther- of Appendix 4 to Regulation 415/2012 Coll. For
mal processing of waste) will be exceeded for SO2 example, the measured emissions of HCl are 333.3
and TOC. times lower than the set emission limit, the emis-
The Energy Research Centre at VSB–Technical sions of HF are 50 times lower than the EL, the
University of Ostrava also measured emissions emissions of SO2 are 1.52 times lower than the EL,
(certificate of accredited test No. 46/13—pyrolysis and the emissions of PM are 1.44 times lower than
of waste tyres) in the premises of company the EL. The emission limit (meant for the ther-
Hedviga Group plc in the Czech Republic on 03rd mal processing of waste) will be exceeded only
June 2013 using facility PTR 1000 combined with for TOC.
a cogeneration unit Tedom Cento T 180. Table 2 Considering the above mentioned facts the facil-
gives an extract of the taken emission values for the ity under assessment may be used in practice as
cogeneration unit (pyrolysis of waste tyres). higher emissions values were measured only in SO2
The values in Table 2 imply that the over- and in TOC (pyrolysis of municipal waste free of
whelming majority of the taken emission values the biodegradable component and inert material)
of pollutants comply with the set specific limits. and again in TOC (pyrolysis of waste tyres). For
In accordance with Article 2.3, Section I, Appen- such substances it is the relevant regional authority
dix 4 to Regulation 415/2012 Coll., the specific that may stipulate higher specific emission limits in
emission limits (for PCDD/F, Hg, Cd, and Tl) a source operation permit. This solution is viable

165
Table 2. Measured emission values—pyrolysis of tyres. Pyrolysis plant PTR 1000 (manufacturer Hedviga Group plc,
Czech Republic), certificate No. 46/13.

Average mass
concentration Emission
Pollutants of pollutants limits Remarks

NOx 244 mg/Nm3 500 mg/Nm3 Emission limits for cogeneration units
CO 52 mg/Nm3 1300 mg/Nm3 (Appendix 2 to Regulation 415/2012 Coll.,
Section II, Article 2, Table 2.2)
PM (Solid pollutant) 6.94 mg/Nm3 10 mg/Nm3 Emission limits for incineration of waste
HF 0.02 mg/Nm3 1 mg/Nm3 (Appendix 4 to Regulation 415/2012 Coll.,
HCl 0.03 mg/Nm3 10 mg/Nm3 as amended, Section I, Article 1, Table 1.1
SO2 33 mg/Nm3 50 mg/Nm3
TOC 71 mg/Nm3 10 mg/Nm3
PCDD/F 0.00594 ng/Nm3 0.1 ng/Nm3 Emission limits for incineration of waste
(Σ TEQ) (Appendix 4 to Regulation 415/2012 Coll.,
Hg metals 0.00062 mg/Nm3 0.05 ssmg/Nm3 Section I, Article 2.3)
Cd metals 0.00019 mg/Nm3 Σ 0.05 mg/Nm3
Tl metals 0.00017 mg/Nm3
PAH 0.000014 mg/Nm3 1 mg/Nm3 Emission limit (EU)

as it is not the case of waste incineration plants, As mentioned above, authorities are highly dis-
but stationary sources thermally processing waste, trustful of the application of pyrolytic oil. A poten-
other than waste incinerators, cement kilns and tial pyrolysis plant operator is a priori suspected of
stationary combustion sources (in line with Article breaching safety regulations when pumping the oil
2.3, Section I, Appendix 4 to Regulation 415/2012 into tanks, and thus contaminating the ground water
Coll.), where mostly emissions of PCDD/F, Hg, and the rock environment. In addition, there is a
Cd, and Tl, are observed. In the given case, the lack in faith in the question of potential customers
emissions are fully complied with and they range for pyrolytic oil, even if abroad pyrolytic oil is a basic
in very low values (see Table 1 and Table 2). In final product sold to refineries under advantageous
other pollutants the set specific limits of general conditions. Therefore, when implementing the waste-
emission limits, the values of which are high, need to-energy pyrolysis technologies in the CR the major-
not be used. ity of prospective investors considers the construction
of further cogeneration units to combust the pyrolytic
oil and generate energy, even if the sales of pyrolytic
4 DISCUSSION oil to refineries would be more advantageous.

As it has been mentioned above, the overwhelming


majority of the taken emission values of pollutants ACKNOWLEDGEMENT
comply with the set specific limits. In accordance
with Article 2.3, Section I, Appendix 4 to Regu- This work was financially supported by the Minis-
lation 415/2012 Coll., the most important specific try of Education, Youth and Sports of the Czech
emission limits (for PCDD/F, Hg, Cd, and Tl) Republic in the “National Feasibility Program I”,
are fully complies with; in case of Cd, Tl, Hg and project LO1406.
PCDD/F they are two orders of magnitude lower.
Considering the above mentioned facts the facility
under assessment may be used in practice. REFERENCES
Still, taking other aspects into account, the situ-
ation in the Czech Republic is not simple within the Integrated prevention and reduction of pollution:
framework of environmental impact assessment of Reference document on best available technologies
pyrolytic technologies for energy recovery. of waste incineration. 2005. Prague: CENIA, Czech
Some regional authorities that are competent Information Environmental Agency [online], [accessed
on 2012-04-24]. Available at [Link]
to administer the environmental impact assess- www/webpub2.° (in Czech)
ment proceedings regarding such facilities require Lapčík, V. 2011. Expert Report for Environmental
certain construction and operational details of Impact Assessment Documentation as of Appendix 5
the planned pyrolysis plants which are not later to Act No 100/2001 Coll., as amended, for the project
included in the given project documentation. Municipal-Waste-to-Energy Plant Chotíkov (ZEVO

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Chotíkov). Prepared for the Regional Office of the Obroučka, K. 2001. Thermic waste disposal and energy
Plzeň Region. Ostrava. 98 p. (in Czech) recovery. 1st edition. Ostrava: VŠB—Technical
Lapčík, V. 2013. Environmental Impact Assessment Noti- University Ostrava. 140 p. ISBN 80-248-0009-8. (in
fication as of Appendix 3 to Act No 100/2001 Coll., as Czech)
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ery from waste—Hodonín-Pánov. Ostrava. 105 p. (in Shangqiu Jinpeng Industrial Co., Ltd. 4 p. Materials
Czech) from Hedviga Group plc, Vratimov, Czech Republic,
Lapčík, V. 2014. Environmental Impact Assessment 2012. (in Czech)
Documentation as of Appendix 4 to Act No 100/2001 Record of Authorised Emissions Measurement and of
Coll., as amended, for the project Technology of the Accredited Test Number°03/13. 2013. Ostrava:
energy recovery from waste—Tušimice. Ostrava. 127 p. VŠB—Technical University of Ostrava, Energy
(in Czech) Research Centre. 32 p. (in Czech)
Miranda, M., Costa, P., Pinto, F., Gulyurtlu, I., Cabrita, Record of Authorised Emissions Measurement and of
I. 2003. Pyrolysis of Plastics and Tyres Wastes. In: the Accredited Test Number°46/13. 2013. Ostrava:
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167
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Environmental impact assessment in branch of wind energy


in the Czech Republic

V. Lapčík
Faculty of Mining and Geology, VSB—Technical University of Ostrava, Ostrava, Czech Republic

V. Lapčík Jr.
Faculty of Law, Masaryk University, Brno, Czech Republic

ABSTRACT: The introductory part of paper describes so-called anti-fossil act, which is prepared in
the Czech Republic. It is clear that meeting the aims of the act may significantly contribute to the devel-
opment of wind energy in the Czech Republic as in 2040 the share of renewable energy sources on the
so-called energy mix shall reach 25% (nowadays ca. 13%). The article includes a section dealing with the
overall development trend in the newly installed facilities intended for the generation of electric power,
which in 2015 clearly pointed at a wider exploitation of wind power in Europe. In 2015 the wind power
plant technology recorded an increase of 6.3% in the installed capacity as opposed to 2014. As a sum, we
speak of an output of 12,800 MWe in the newly installed wind power plants. Next part of paper deals with
environmental impacts of wind power plants on the environment. During assessing the environmental
impacts of wind energetics projects the following factors (noise, impacts on the face of the landscape,
impacts on the migration routes and bird nesting, impacts on the fauna, flora and ecosystems, shadow
flicker, impacts on the soil, surface water and ground water, other impacts) are taken mainly into consid-
eration. The conclusion of paper discusses the current trends in the wind power-engineering in Europe
and the situation in environmental impact assessment of wind farms in the Czech Republic.

1 INTRODUCTION Among the most important countries exploiting


wind energy in Europe there is Germany (with the
In the Czech Republic (the CR) the so-called highest installed capacity of 44,946.1 MW), Spain,
anti-fossil act is being prepared and it should be Great Britain, France, Italy, Sweden, Poland,
brought into the Chamber of Deputies of the Portugal, Denmark, the Netherlands, Romania,
Parliament of the Czech Republic in September etc. (EWEA 2015). Globally, the end of the 20th
2016. This act is a declaratory form of statute that century witnessed an increase in the wind power
should include the aims of energy and raw material plant outputs and innovations in the constructional
policy of the Czech Republic by 2050. The act may parts and electronic systems carried out in order to
arguably provide more certainty than the govern- reach the maximum exploitation of wind energy.
ment materials of State Energy Concept and State The overall development trend in the newly
Raw Material Policy. The major aim of the act will installed facilities intended for the generation of
be a gradual reduction in emissions by 2050 with electric power in 2015 clearly pointed at a wider
regular checks every five years. It is expected that exploitation of wind power in Europe. In 2015 the
in 2040, about 17% (a range of 11 to 21% is also wind power plant technology recorded an increase
mentioned) of generated of electric power shall of 6.3% in the installed capacity as opposed to 2014.
come from conventional heat-power engineering, As a sum, we speak of an output of 12,800 MWe
58% from nuclear energy, and 25% from renewable in the newly installed facilities, which amounts to
energy sources. 44.2% of the total newly installed capacity in 2015.
It is clear that meeting the aims of the act may Out of that, 9,766 MW were installed onshore and
significantly contribute to the development of 3,034 MW offshore (in EU the total installed capac-
wind energy in the CR as in 2040 the share of ity of wind power plants in 2015 was 131,000 MW
renewable energy sources on the so-called energy onshore and 11,000 MW offshore) (EWEA 2015).
mix shall reach 25%, as mentioned above. It is wind In 2015 the participation of renewable energy
power-engineering that should gradually increase sources in the total newly installed capacity was
its proportion within the generation of electric 77% (22,300 MW out of the total newly installed
power from renewable energy sources in the CR. capacity 29,000 MW) (EWEA 2015). Wind power

169
plants thus became the third most important mainly into consideration (Lapčík, 2009; Lapčík
source of energy used in the European Union (the 2011b):
EU), with the total share of 15.6% on the total
1. noise,
installed electric output. On the other hand, the
2. impacts on the face of the landscape,
use of conventional sources of energy, such as fuel
3. impacts on the migration routes and bird nesting,
oil and coal, has been significantly reduced.
impacts on the fauna, flora and ecosystems,
In the CR the major producers of electric power
4. shadow flicker,
are facilities exploiting non-renewable energy sources.
5. impacts on the soil, surface water and ground
Nevertheless, in 2040 only about 17% of generated
water,
of electric power should be made from coal, 58%
6. other impacts.
from nuclear energy, and 25% from renewable energy
sources. The renewable energy should be more and
2.1 Noise
more covered by wind energy, the exploitation of which
is rather low when compared with other European Operating a wind farm two types of noise arise.
countries. Let us look at the situation in the CR. It is a mechanical noise, the source of which is a
Following the rapid, and in many respects prob- machine room (a generator including a ventilator,
lematic (and at present low desirable), growth in the gearbox, rotation mechanisms or a brake). The
installed capacity of photovoltaic power plants in the amount of noise emitted into the environment
CR (from 462.92 MWe by the end of 2009 it has grown depends on the construction quality of the indi-
to 2,124.02 MWe), it is necessary to determine other vidual components (e.g. gearwheels) of the overall
feasible paths to meet the renewable energy source machine as well as on the placement and enclosure
aims mentioned above. It appears that biomass and of the overall machinery. All the stated parameters
biogas are not much considered. Apart from water of the currently lot produced wind turbines are
sources, only wind energy remains. By the end of optimized. Except for small deviations when turn-
2009 the installed capacity of wind power plants in ing the gondola, the noise is stable.
the CR was 192.86 MWe, as of 1st December 2010 it Certain noise impacts result from the blades
was 212.57 MWe, 259.7 MWe by 2012, 269 MWe by passing the wind turbine tower. In the past, pole
2013, 281.5 MWe by 2014 and 281.5 MWe by 2015, vibrations appeared in some wind turbines, which
which represents a rather small or zero (in 2015) has been overcome by modern technologies (Štekl
increase in the output (EWEA 2015). 2007). Next, it is an aerodynamic noise that arises
On the other hand, in the majority of the neigh- due to the interaction of flowing air and the rotor
bouring European countries the installed capacity airfoil and whirl winds relaxing behind the blade
of wind power plants is rather high. For example, edges. Its frequency spectrum is very balanced and
by the end of 2015 the wind power plant installed falls with a rise in frequency. Aerodynamic noise
capacity was 2,411.5 MWe in Austria, 5,100 MWe is reduced by the state-of-the-art constructions of
in Poland, 44,946.1 MWe in Germany (the highest rotor blades or rotor types when at the expense of
installed capacity in Europe). In Slovakia it was a slight fall in the generator’s output the noise lev-
only 3.1 MWe (EWEA 2015). els are reduced.
In a locality selected for the implementation The noise spreads from the point source in
of a wind farm, the average wind velocity at the dependence on the direction and speed of air flows,
height of 10 m should range from 5 to 6 m.s−1. At in dependence on the intensity of vertical mixing
the height from 100 to 200 m, the wind velocity is of air (below the temperature inversion the trans-
higher (Lapčík, 2009). fer of noise is prevented in the vertical direction),
There are about 29% of areas with such or faster on the shape of the earth surface and on the exist-
wind velocities in the CR. As the majority of them ence of obstacles to the noise spread. The noise
are covered with forests (higher mountains) or nat- spreading from the point source subdues along
ural preserves, wind farms cannot be situated eve- with the distance. A simplified version deals with a
rywhere. Due to the natural preserves or forests, the drop in the acoustic pressure along with a distance
size of the suitable area is reduced by 69%, and thus logarithm as a wind speed function. Mostly, this
the theoretical exploitability of the country for wind simplified version of the calculation (i.e. without
power-engineering is about 9% (Lapčík, 2011a). the influence of the wind rose, relief shape, temper-
ature layers, etc.) is used in model calculations to
define a noise field in the surroundings of a wind
2 ENVIRONMENTAL IMPACTS OF WIND farm (Lapčík, 2011b).
FARMS The intensity of the perception caused by noise
is greatly influenced by the proportion between its
Assessing the environmental impacts of wind ener- intensity and the intensity of other noises labelled
getics projects the following factors must be taken as the background noise. It is known that a noise

170
caused by a viscous and turbulent friction of air of wind farms mostly shows in the day in the
and the earth surface reaches high values, espe- surroundings of the access road to the site. As the
cially in the mountain conditions. points for calculations, for which the calculation
Government Decree No. 272/2011 Coll. on of noise from stationary sources is carried out,
health protection against negative impacts of noise are often far away from the road, it is important
and vibrations sets the top admissible level of to describe changes in the noise situation in a noise
acoustic pressure outdoors at 50 dB during the day study changing the equivalent noise levels in a
(06 ÷ 22 hours) and at 40 dB at night. However, this standardized distance from roads (e.g. 7.5 m from
decree does not consider the circumstances when the axis of the closest lane).
the background noise exceeds the noise produced
by a wind farm.
2.2 Impacts on the face of the landscape
The own assessment of acoustic situations is car-
ried out by means of a noise study which assesses A term of the face of the landscape has been intro-
the noise near the nearest built-up area. It happens duced by Act 114/1992 Coll. on the conservation
that the admissible equivalent noise level is not of nature and landscape. Therein, the face of the
observed in the loudest night hour in the outside landscape is defined (§ 12) as a natural, cultural
protected area. In such cases, the wind farm regime and historic characteristics of a particular site
is required to be limited via reducing the output, or region. The face of the landscape is protected
which thus results in lowering the acoustic output against activities degrading its aesthetic and natural
(e.g. from 107.5 dB to 104.5 dB). In some cases it value. Interference with the face of the landscape,
is though necessary to switch off several machines particularly as for locating and approving struc-
at night—See Fig. 1 (Lapčík, 2016). For example, tures, may occur only with regard to keeping sig-
in Germany it is recommended to construct wind nificant landscape elements, especially protected
farms more than 300 m from a single residence areas, cultural dominant features of the landscape,
and more than 500 m from an end of a settlement. harmonic criteria and relations in the landscape.
Nevertheless, the experience of the monograph Talking of the impacts on the face of the land-
author is that the minimum distance of wind farms scape, in case of complying with measures con-
from any housing development should be 575 to nected with the interests of health protection
600 metres (Lapčík, 2009). against unfavourable impacts of noise and the
Traffic noise arising in the time of construction interests of the nature conservation, the impact
and operation of a wind farm is time limited and on the face of the landscape may be defined as a
usually negligible. In the time of construction it dominant aspect in connection with the assessed
is important to ensure disposal of the spoil in the type of project.
volume of about 1,000 m3, delivery of concrete in There is no doubt that the erection of wind farms
the volume of about 900 m3 per one machine and embodies a highly visible interference with the face
delivery of the own technological facility (Lapčík of the landscape. As for the protection of the face
2016). In the time of operation, there are only one of the landscape it is vital to find out if the planned
or two vans per week. structure does not interfere with any natural park.
The impact of traffic noise and its changes in Stipulated by law, a natural park represents one
connection with construction and later operation of the most sensitive areas in the protection of
the face of the landscape and a construction of
a wind farm should not be implemented there.
Natural parks are landscapes with concentrated
significant aesthetic and natural values for the con-
servation of which they have been established (in
accordance with § 12 art. 3 of Act No. 114/1992
Coll. on the conservation of nature and landscape,
as amended). It is solely the protection of the face
of the landscape which makes the core of their
protection.
Visualization of wind farms is usually processed
by means of computer visualization and mak-
ing use of photographs of the existing landscape
in order to assess the impacts on the face of the
landscape—See Fig. 2 (Lapčík, 2010).
Figure 1. Equivalent levels of noise—night operation The site of the face of the landscape affected
of wind farms (wintertime). Check point of noise—points by the assessed wind farm plans (i.e. an area
No. 1–8 (Lapčík, 2016). from where wind farms can be potentially seen)

171
face of the landscape in smaller machines would
be identical. The facilities would only appear to
be located further away from the observer than
in case of higher facilities (higher pole and wider
rotor diameter).

2.3 Impacts on the migration routes and bird


nesting, impacts on the fauna, flora and
ecosystems
The literature does not report any significant nega-
tive impacts of wind farms on birds. The results of
a wind farm impact research on the avifauna in the
Netherlands (Winkelman, 1992) imply that no veri-
fiable impacts on nesting birds or birds perching
for food into the vicinity of wind farms have been
Figure 2. A view of photo-visualized wind farm. registered. A long-term observation of 87,000 birds
in the vicinity of wind farms show that the majority
of birds completely avoided the wind farms (97%)
is usually a vast territory. The site of the face of and only a fraction chose to fly through a rotor.
the landscape, i.e. an area which may be visually This usually results in a clash with a blade. Despite
influenced by the assessed structure, is considered being hit by the blade there is no inevitable rule of a
in terms of distance views as far as 2 to 5 km in serious injury or death of the bird. The existence of
case of a strong visibility range and as far as 10 km a pressure field in front of the rotating blade forms
in case of a clear visibility range—by course of a barrier which often repels the birds.
a Methodical Direction 8/2005 (Ministry of the Experience from the observation of bird behav-
Environment of the CR 2005). Areas which are iour close to wind farms has also been gained
shaded by forming the georelief are excluded from in the Czech Republic. For example, in the Ore
the ranges (Mana 2013; Lapčík 2014). Mountains in the surroundings of the municipal-
There is a frequent question whether it would be ity of Dlouhá Louka a detailed research in nesting
possible to generate an identical volume of electric bird associations in three most significant biotopes
power by wind farms even at possible lowering of (in the forest, on the meadow and cottage settle-
their towers and reducing the rotor diameters as ment) was carried out in 1993 and 1994 (Šťastný,
in this manner the face of the landscape would be Bejček 2000), i.e. prior to and after the construc-
less altered. The calculations may be carried out on tion of a wind farm. The results presented in the
the grounds of known relations for the calculation study document that the operation of the wind
of wind (PS) and consequently electric (Pel) power farm does not affect nesting of bird associations in
(Lapčík, 2009). a significant manner.
The calculation results though imply that short- Based on surveys, possible risks connected with
ening the wind turbine hub height from 100 metres wind farm operation (particularly collisions of
to 70 metres (at wind speeds c = 8.5 m/s and birds and bats with the facility) are greater than
c = 6.5 m/s) and using a rotor of 90-metre diam- those related to an operation of other similar
eter, the electric power fell from 100% (hub height structures (high towers, high voltage wires, roads,
of 100 m) to 45% (hub height of 70 m). Using a etc.). Moreover, it may be said that in the majority
rotor of 50-metre diameter (instead of 90 m) the of cases applying suitable technical solutions there
electric power would drop to 31% (hub height of is no reason to expect distinct degradation of the
100 m) or to 14% (hub height of 70 m) (Lapčík, conditions of the site suggested for the construc-
2006b; Lapčík, 2009). tion of wind farms from the environmental point
It is thus clear that lowering the hub height or of view.
reducing the wind turbine rotor diameter there Nevertheless, it is convenient for wind farms to be
would be a considerable loss in the gained elec- located outside important birds’ migration routes
tric power and practically an analogous facility and breeding places. This may be checked prepar-
with all its negative environmental impacts would ing a study which assesses impacts of planned wind
have to be constructed (noise, land required for farms on birds and other vertebrates.
the machine’s foundations, access roads, energy The wind farm structures are mostly situated
infrastructure, etc.) as if implementing a wind tur- outside the component parts of the ecological
bine of 100-metre-high pole and 90-metre rotor stability zoning system, outside areas of higher
diameter. At the same time, the impact on the degrees of ecological stability, or outside localities

172
with near nature ecosystems. Also, a possible for possible agricultural purposes. The consoli-
impact on especially protected areas and biotopes dated access roads may be further used to access
of specially protected animal species is negligible. the adjoining pieces of lands from the neighbour-
In order to exclude unfavourable impacts on the ing roads.
flora and fauna it is advisable to process a biologi- It is possible to be economical with the land
cal (floristic and faunistic) assessment of the locali- resources even when constructing the underground
ties in question. electric power lines to connect the wind farms and
the switch room. It is possible to use a cable-laying
plough (see Fig. 3) to avoid excavations. This method
2.4 Shadow flicker
is very friendly with respect to the conservation of
In older wind power plants flashlights used to soil quality due to minimum interference with the
occur on the rotor blades, the so-called disco effect, ground (the plough leaves a very thin cut on the sur-
which is eliminated in the modern wind power face, which is finished by a roller). Cables should be
plants due to the matt finish of the rotor blades laid along the existing roads as much as possible.
(in grey colour). The operation of wind turbines does not pro-
The stroboscopic effect (optical illusion) is an duce any technological water or sewage. The
effect when revolving objects lit by periodically rainwater from the stabilized access road areas is
variable light do not appear to be in motion. mostly drained gravitationally into the surround-
The so-called shadow flicker arises under con- ings and the ditches.
current three conditions: The impact on the surface and ground water is
not expected implementing such projects, but it is
• the wind power plant is in operation—the wind
important to adhere to all the relevant safety meas-
is blowing;
ures. The wind turbine facilities do not influence
• the wind power plant is in operation—the sun is
surface water or the quality, water level or flow direc-
shining;
tions of the ground water, both during construction
• the wind power plant rotor is situated perpen-
and own operation. However, during construction
dicularly to the objects in question.
of service roads and the wind turbine facilities it is
The shadow flicker may be observed at opti- important to take such measures to prevent changes
mal lighting conditions in the range of ca. 250 to or worsening of water discharge, the occurrence of
300 m from the wind power plant. Further away the manifestations of erosion or to limit the pollu-
the shadow flicker is practically negligible. Consid- tion and soil drag into influent stream beds to mini-
ering the fact that the majority of assessed wind mum in course of construction.
power plants are located over 500 m from residen-
tial areas, this phenomenon appears to be insignifi-
2.6 Other impacts
cant (Lapčík, 2015).
The shadow flicker at least manifests when wind Within the winter operation there may be a situa-
power plants are situated northwards, or north- tion when ice or ice fragments fall off the blades.
eastwards and north-westwards from a municipal- New wind turbines are expected to be equipped
ity (no sun can shine through the wind power plant with signalling which recognizes ice in time or the
rotors from the north). wind turbine is shut down.

2.5 Impacts on the soil, surface water and ground


water
Usually 2 400 m2 of agricultural land are required
for one wind power plant, where the built-up area
for one turbine is ca. from 450 m2 (Lapčík, 2016).
The new types of tall wind farm columns, the so-
called hybrid columns or hybrid towers, are from
80% built from concrete, and 20% from steel. They
may be mounted using a special crane anchored
into the wind power plant foundations. Via this
solution it is possible to reduce the land require-
ment from 2,400 m2 to 1,200 m2. Mostly it is the
case of agricultural land with below-average pro-
duction capacities and limited protection. Having
terminated the operation of wind farms, the land
is expected to be reclaimed in the majority of cases Figure 3. Cable-laying by plough method (Lapčík, 2016).

173
In general, the majority of wind power plant This confirms the fact that wind power plants may
producers try to produce rotor blades from such be fully removed, if necessary, from the locality
materials that prevent ice sticking to the blades. after their working life (Lapčík, 2015).
Nevertheless, such measures are sometimes insuffi-
cient. Certain producers thus offer wind power plants
with heated blades for cooler climates. The heating is 4 ENVIRONMENTAL IMPACT
ensured by hot air or via electric resistance heating. ASSESSMENT OF WIND FARMS
A minimum measure in this respect is an instal-
lation of panels warning about a possible risk of Wind farms of a total installed capacity higher
injury due to falling ice off the rotor blades in a than 500 kWe or with tower height exceeding
sufficient distance from wind farms (about 250 m) 35 meters are classified according to the Appendix
(Lapčík, 2009). 1 to Act 100/2001 Coll., as amended, into the cat-
egory II (projects requiring rogatory proceedings),
article 3.2 (the project is administered by Regional
3 THE CURRENT TRENDS IN THE WIND Offices). This implies that the majority of the
POWER-ENGINEERING designed wind farms in the Czech Republic nowa-
days must undergo rogatory proceedings.
In the countries where wind power-engineering As a rule, a number of studies make parts of
thrived in the past (e.g. Germany), the so-called re- the notification processed according to Appen-
powering is on the programme, i.e. older wind farms dix 3 to the Act. For example, they are a noise
with lower outputs (e.g. 1.66 MWe) are dissembled study, assessment of impacts on the face of the
and replaced by taller machines of a higher output landscape, assessment of wind turbine impact on
(e.g. 3.3 MWe). The replacement of the wind tur- birds and other vertebrates, or the project’s impact
bines goes hand in hand with building new founda- assessment on Europe’s outstanding localities and
tions for the wind farms as the different turbines birds’ territories according to §45i of Act 114/1992
must be located further away from one another Coll. on the conservation of nature and landscape,
due to higher turbines and bigger rotor diameters as amended. Certain notifications also contain
(the common rule is that the distance between the health risk assessments, which are required by the
turbines should equal about the quintuple of the law processing the documentation according to
rotor diameter). Otherwise, the efficiency of the Appendix 4 to Act 100/2001 Coll. on environmen-
individual turbines would fall (they would steal tal impact assessment, as amended.
wind from one another). The new foundations Nevertheless, despite the complications (the
are usually heavier (the weight of the foundations notification actually takes the form of documen-
should approximately equal the tenfold weight tation) in the majority of cases the process of
of the wind power plant nacelle weight) and are impact assessment for wind farms is not currently
located, as mentioned above, elsewhere than the discontinued within the rogatory proceedings (in
original wind power plant foundations. For this the so-called shortened proceedings), but it must
reason, the original foundations must be com- be continued in the full extent (documentation
pletely removed (Fig. 4) and all the waste recycled. compilation, opinion elaboration, public hearing),
often with repeated supplements to the documen-
tation before the opinion is elaborated.
This is caused by the negative attitude of the
regional offices as well as of the public to wind
energetics, who mostly hold a negative attitude
to this renewable source of energy. Nevertheless,
it must be said that the public comments are fre-
quently presented in a very general manner and
still certain types of criticisms reappear even if
those have already been discussed and disproved.

5 CONCLUSION

Several years ago the construction of many wind


Figure 4. Removal of wind power plant foundations. power plants and wind farms was being prepared
The condition of the land having removed the wind in the CR. At present, much fewer projects are
turbine foundations with the steel column (photo—Lapčík, under approval. It is likely caused by a transfer of
jr. 2015). capital investments into another area of renewable

174
energy sources, i.e. photovoltaic power plants. It Lapčík, V. 2010. Environmental Impact Assessment
shows that it was not a good solution. However, Documentation as of Appendix 4 to Act No 100/2001
the implementation of already approved projects Coll., as amended, for the project Wind Park
is rather slow. Partutovice. Ostrava. 223 p. (in Czech).
Lapčík, V. 2011a. Environmental Impact Assessment
With regard to the above mentioned attitude of (monograph). VŠB-Technical University of Ostrava,
the public and regional authorities to wind power Ostrava, Czech Republic. 217 p. (in Czech).
plants, the environmental impact assessment proc- Lapčík, V. 2011b. Wind Farms and Their Impact on the
ess in such facilities is long and problematic. In the Environment (chapter in book). In: Wind Farm—
majority of cases it is important to count with the Technical Regulations, Potential Estimation and Siting
full approval process (processing of a notification, Assessment/Book 1 (book edited by Gastón Orlando
declaratory proceedings, processing of documen- Suvire). Croatia, Austria: InTech, pp. 141–162 (22 p.).
tation, processing of an expert statement, public ISBN 978-953-307-483-2. ([Link]
hearing), even if according to the legislation a com/books/show/title/wind-farm-technical-regulations-
potential-estimation-and-siting-assessment).
project may be subjected to the so-called declara- Lapčík, V. 2014. Environmental Impact Assessment
tory proceedings and thus the environmental Notification as of Appendix 3 to Act No 100/2001
impact assessment process may be executed in the Coll., as amended, for the project Wind Park Střížovice.
so-called summary proceedings. Ostrava. 119 p. (in Czech).
Lapčík, V. 2015. Environmental Impact Assessment
of Wind Generators. Životné prostredie, No 1(49),
ACKNOWLEDGEMENT pp. 29–33. (in Czech).
Lapčík, V. 2016. Environmental Impact Assessment
This work was financially supported by the Minis- Notification as of Appendix 3 to Act No 100/2001
Coll., as amended, for the project Wind Park Měčín.
try of Education, Youth and Sports of the Czech Ostrava. 125 p. (in Czech).
Republic in the “National Feasibility Program I”, Lapčík, V., jr. 2016. Wind Generators and Their Impact
project LO1406. on the Environment. Bachelor´s Thesis, VSB-Technical
University of Ostrava, Ostrava. 67 p. (in Czech).
Mana, V. 2013. Expert Report in Branch of Assessment
REFERENCES of Impacts on the Face of Landscape—Wind Park
Střížovice. 30 p. (in Czech)
EWEA. 2015: The European Wind Energy Association: Methodical Instruction of Ministry of Environment of
Wind in power: 2015 European statistics. [online]. 2015 the Czech Republic. 2005, No 8, Figure 6. pp. 14–26.
[cit. 2014-02-07]. (in Czech).
Lapčík, V. 2006a. Environmental Impact Assessment Štekl, J. et al. 2007. Renewable Energy Resources and
Notification as of Appendix 3 to Act No 100/2001 their Possibilities of Utilization. ČEZ, a.s. Prague,
Coll., as amended, for the project Wind Park Potštát— pp. 79–112. (in Czech).
Lipná. Ostrava. 75 p. (in Czech). Šťastný, K. & Bejček, V. 2000. Red List of Birds of the
Lapčík, V. 2006b. Expert Report for Environmental Czech Republic. In: Hora J. (ed.), 2000: Directive
Impact Assessment Documentation as of Appendix 5 EC on protection of freely living birds in the Czech
to Act No 100/2001 Coll., as amended, for the project Republic. Czech Ornithological Company, Prague. (in
Větrný park Rudná pod Pradědem. Prepared for the Czech).
Regional Office of the Moravian-Silesian Region. Winkelman, J. E. 1992. The Impact of the Sep Wind Park
Ostrava. 41 p. (in Czech). near Oosterbierum, the Netherlands, on Birds. RIN
Lapčík, V. 2009. Industrial Technologies and Their Impact Rep. 92. DLO Instituut voor Bosen Naturonderzoek,
on Environment (monograph). VŠB-Technical Univer- Arnheim. 78 p.
sity of Ostrava, Ostrava, Czech Republic. 362 p. (in
Czech).

175
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

A comparison of catalyst activity for methanation reaction

V. Šnajdrová, T. Hlinčík & K. Ciahotný


Department of Gaseous and Solid Fuels and Air Protection, University of Chemistry and Technology, Prague,
Czech Republic

ABSTRACT: The catalytic hydrogenation of carbon dioxide to methane, has been known for more than
a hundred years. Its importance has increased significantly in recent years particularly for the production
of Synthetic Natural Gas (SNG) in order to utilize excess electricity from renewable energy sources (e.g.
wind, water or solar power). Excess electricity generated could be used for the electrolytic production of
hydrogen. The produced hydrogen would then react with carbon dioxide obtained from flue gases of fos-
sil fuel power plants. In this paper a comparison of the activity of nickel, cobalt and molybdenum based
catalysts is presented. The catalysts were prepared by co-precipitation method and were supported on
γ-alumina, which here acts support. In the laboratory apparatus the catalysts were tested at different pres-
sures (2, 4 and 6 MPa). The relation between catalyst activity and deactivation was also tested.

1 INTRODUCTION also great potential in astronautic. The National


Aeronautics and Space Administration (NASA)
In recent year efforts to reduce carbon dioxide emis- is currently developing a device for recycling the
sions into the atmosphere (due to climate change) atmosphere on board or in the construction of a sta-
while reducing dependence on the fossil fuels, whose tion. This equipment should recycle carbon dioxide
supplies are limited, have led to an increasing inter- and produce from it again hydrogen (Moore 2010).
est on the further development of renewable energy
sources. Due to the constant increase of carbon diox-
ide emissions from anthropogenic possibilities for its 2 THEORY OF METHANATION
recyclation and utilization are being explored. One of
the possible approaches to the issue of carbon diox- Catalytic hydrogenation of carbon dioxide with
ide emissions from stationary sources such as power hydrogen to methane is known for more than a hun-
plants is Carbon Capture and Storage (CCS) and its dred years as the Sabatier reaction, which is shown
subsequent use as feedstock. The recycled carbon in equation (1). The first experiments were con-
dioxide is considered a sustainable raw material for ducted with a nickel catalyst. The reaction started
chemicals and fuels production. The conversion of at temperatures ranging from 190–230°C [4].
carbon dioxide as the only reactant is very difficult.
However, in the presence of hydrogen reacts easily. 4H2 2 C 4 2 H 2O (1)
An important process is the catalytic hydrogenation ΔH 0 165kJ mol 1
of carbon dioxide to methane, which is known as
Sabatier reaction (Mills and Steffgen 1974). The methanation reaction is reversible, which
In recent years carbon dioxide methanation has means that at different reaction rates occur
been incorporated on the concept Power-to-Gas. simultaneously direct and reverse reaction. If the
The concept Power-to-Gas connects the power grid reaction rates are the same, the reaction is in equi-
to a pipeline network so that it converts excess elec- librium i.e. is in a state, where in the system are
trical energy to chemical through a two-stage proc- present reactants and products, but their quantity
ess. In the first stage, hydrogen production by water does not change. The reaction enthalpy is negative
electrolysis takes place. In the second stage hydro- and therefore the reaction is exothermic (when it
gen conversion with external sources of carbon takes place heat is released). According to the Le
dioxide to methane via the Sabatier reaction takes Chatelier principle an increase in temperature
place. The produced methane is referred to as Syn- causes an equilibrium shift in the direction of the
thetic Natural Gas (SNG) and its biggest advantage reactants. The methanation efficiency is influenced
is the unlimited applicability in gas infrastructure by the molar ratio of H2:CO2. In order to achieve
(Šnajdrová, Baraj and Hlinčík, 2016). Methana- the highest yields and the best selectivity for meth-
tion of carbon dioxide has besides energy recovery ane formation the ideal molar ration of 4:1, which

177
is the same as the stoichiometric ratio of reaction catalyst have very hight tolerance to sulfur com-
(Tsuji, M., et al. 1996). pounds, mainly hydrogen sulfide, which is a well-
known catalytic poison (Tada and Shimizu 2012).

3 METHANATION CATALYSTS
4 EXPERIMENTAL
Catalytic hydrogenation of carbon dioxide to meth-
4.1 Laboratory apparatus for catalytic activity
ane was from its discovery gradually examined using
measurements
different catalysts. Among the most active catalysts
are, nickel, ruthenium or rhodium. Nickel is the most The methanation activity of various catalyst for a
selective of all catalysts to methane. Methanation feed gas consisting of carbon dioxide and hydro-
using a nickel based catalyst forms almost no higher carbon was tested in laboratory apparatus set up
hydrocarbons and only very small quantities of car- in UCT Prague. The apparatus was designed to the
bon monoxide. Its catalytic activity is very high, reaction at various temperatures up to 500°C and
although noble metals (Rh, Ru) are more active, but various pressures up to 8 MPa. Laboratory appara-
due to their high cost, are not widely used. Nickel tus scheme configuration is depicted in Figure 1.
catalysts, is most often supported in supports such The apparatus was connected to two cylinders.
as γ-Al2O3 or SiO2. The main disadvantage of nickel The first cylinder contains pure nitrogen, which
based catalysts is that they are very susceptible to served as the inert gas flowing through the appara-
deactivation due to sulfur compounds. Sulfur is a tus during the heating and purging. The second cyl-
catalyst poison for most catalysts, however, nickel inder containe a gas cylinder mixture consisting of
is particularly susceptible to deactivation (Vance, 80 mole % H2 and 20 mole % CO2. The pressure of
C.K. and C.H. Bartholomew 1983). gas exiting the cylinder was reduced with a reducing
Another catalyst used in Sabatier works is valve located on the cylinder. The pressure inside
cobalt. Cobalt based catalysts are not as selective the apparatus was controlled to the desired value by
to methane. The most important application is in the electronic controller in the range of 0,6–8 MPa.
the low temperature Fischer-Tropsch synthesis. Gas flow was measured by thermal mass flowmeter
Cobalt, like nickel, is supported mostly on γ-Al2O3 in the range 0–10 [Link]-1 (100 kPa, 25°C).
and SiO2 (Marwood 1997). The reaction mixture before entering the reac-
A molybdenum based catalysts is most used in tor was preheated in the preheater tube, which was
process, where there are sulfur compounds. It is placed inside a furnace. The furnace temperature
due to the high tolerance of cobalt based catalyst was controlled. After preheating, the reaction
to sulfur compounds. Therefore are mainly used in mixture was conducted in the methanation reactor.
desulfurization of natural gas or petroleum prod- The height of the reactor is 15 cm, an inner diam-
ucts. Molybdenum based catalysts have low activity eter of 3 cm and a wall thickness of 4 mm making
as compared to nickel, cobalt, ruthenium or iron for a total volume of 106 ml. Inside the reactor was
based catalysts. Another disadvantages, is higher placed the activated catalyst. The reactor is exter-
selectivity to higher hydrocarbons formation. How- nally protected by two stainless steel tubes, into
ever is should be noted that molybdenum based which is inserted a programmable heater.

Figure 1. Laboratory apparatus for CO2 and H2 methanation.

178
The gas mixture subsequently flowed via the air and H2. After measurement, was carried out ele-
cooler into the condenser where water condensa- mentary analysis of the catalyst.
tion took place. Water is a methanation byproduct.
From the condenser via a capillary equipped with 4.5 Products analysis
a ball valve condensate could be collected.
The gas flow through the apparatus was adjusted Gaseous product were analyzed via a Gas Chro-
with the help of a needle valve, which was placed matograph (GC) coupled with a standard Flame
at the end of the apparatus. The gas volume exiting Ionization Detector (FID) and a standard Ther-
the apparatus was measured with a diaphragm gas- mal Conductivity Detector (TCD). The GC was
meter. At the end trait leading to a gas meter was fitted with these two independent channels in order
placed an additional capillary which was used for to make possible the analysis of both organic and
produced gas sampling. Samples of the produced inorganic gaseous products in the produced gas.
gas, were sampled in sampling bags and analyzed The FID channel permitted the determination
via Sewerin and GC-FID/TCD. of the organic products while the TCD chan-
nel permitted the determination of the inorganic
products.
4.2 Preparation of catalysts
The catalysts were prepared by co-precipitation
method. 250 ml of 20 wt.% solution of nickel 5 RESULTS AND DISCUSSION
nitrate and 250 ml of 20 wt.% solution of cobalt
nitrate (ammonium molybdate) were prepared. 5.1 Catalyst characterization before measurement
Both solutions were mixed and heated to 70°C X-ray fluorescence analysis of the nickel-cobalt cat-
and after reaching the desired temperature 100 g alyst showed that its major components were 5,45
γ-Al2O3 were added. This mixture was kept at 70°C wt.% NiO, 3,58 wt.% Co3O4 and 82,0 wt.% Al2O3.
for 90 minutes. Next, the solution was filtered and The analysis of the nickel-molybdenum catalyst
dried at 105°C. The dried catalyst was calcined at showed that its major components were 2,85 wt.%
500°C for 4 hours. NiO, 7,21 wt.% MoO3 and 79,44 wt.% Al2O3.
BET analysis of nickel—cobalt catalyst before
4.3 Catalytic activity measurement catalytic tests was 245,2 m2/g and total pore vol-
ume were 0,4109 ml/g. BET analysis of nickel-
In the reactor was places 50 g of nickel-cobalt molybdenum catalyst was 234,25 m2/g and total
(nickel-molybdenum) catalyst. Subsequently using pore volume were 0,4079 ml/g.
a hydrogen flow the catalyst was reduced in its
active form. Reduction of the catalyst was carried
5.2 Catalyst characterization after measurement
out for 3 hours using hydrogen at a pressure of 0,5
MPa and flow rate of 4,7 [Link]−1 (100 kPa, 25°C) at X-ray fluorescence analysis of the nickel-cobalt cat-
500°C. After reduction the apparatus was purged alyst after experimental tests showed that its major
with nitrogen. After purging the apparatus was components were 5,24 wt.% NiO, 3,29 wt.% Co3O4
warmed up to 120°C using N2. Once the required and 87,82 wt.% Al2O3. While nickel-molybdenum
temperature was reached the model gas mixture catalyst showed that its major components were 2,71
(80 mole % H2 and 20 mole % CO2), at a flow rate wt.% NiO, 7,45 wt.% MoO3 and 82,0 wt.% Al2O3.
of 6,5 [Link]−1 was turned on. Experiments took BET analysis of nickel—cobalt catalyst before
place at pressure of 2, 4 or 6 MPa overpressure. catalytic tests was 245,2 m2/g and total pore vol-
Samples of the product gas were taken and ana- ume were 0,4109 ml/g. BET analysis of nickel-
lyzed at intervals of 20°C. When produced gas was molybdenum catalyst was 204,68 m2/g and total
sampled also water condensate was collected. pore volume were 0,4048 ml/g.
Elementary analysis after measurement of the
nickel-molybdenum catalyst shown an elementary
4.4 Catalyst characterization
composition of 0,34 wt.% C, 0,58 wt.% H2, 0 wt.%
Elemental analysis was performed via X ray fluo- N2, 0,10 wt.% S2 and 98,98 wt.% O2.
rescence. Surface area and total pore volume were
measured by N2 adsorption and desorption iso-
5.3 Product analysis
therms at—196°C. Samples were degassed at 13 Pa
and 150°C overnight. The model BJH was used for 5.3.1 Products when using nickel-cobalt catalyst
BET isotherm measurement. Both XRF and BET In Figure 2 the composition of the produced gas
surface are measurements were performed on the depending on the reaction temperature when using
clean catalyst, on the catalyst after measurements the model gas mixture containing 20 mole % CO2
with the model gas mixture containing only CO2 and 80 mole % H2 at pressures 2, 2 (after reduction

179
was carried out at 2, 4 and 6 MPa overpressure, and
temperature ranging from 100°C to 500°C.
While testing nickel-cobalt catalyst has been
found that reduction of the catalyst with hydro-
gen has a significant effect on the conversion of
methane. When comparing the results at pressures
(2 MPa) with and without reduction was observed
an increased conversion from 1,4 to 4,1 mole %
after catalyst reduction. The highest methane con-
version rate producing 4,6 mole % was reached at
468°C at pressure 6 MPa. Comparing, pressures 2
and 6 MPa shows that indeed increasing pressure
Figure 2. Methane content in the produced gas at dif- promotes greater product formation.
ferent pressures for feed gas. When testing nickel-molybdenum catalyst, the
catalyst have been reduced with hydrogen prior to
the reaction. At pressure 2 MPa achieved the largest
conversion of methane 19,88 mole % was reached at
471,9°C. In test at pressures of 4 and 6 MPa there
was a sharp drop in the conversion of methane to
4,89 mole % and 3,22 mole %, respectively. After
completion of the tests at 4 and 6 MPa by elemen-
tary analysis was found the formation 0,34% of
carbon present in the catalyst. From the result it is
evident that during the reaction there surface carbon
formation took place clogging the catalyst and as a
result causing rapid decrease of catalyst activity.
The results showed despite the low activity of
Figure 3. Methane content in the produced gas at dif- both nickel-cobalt and nickel-molybdenum cata-
ferent pressure for feed gas. lysts they are active in the methanation reaction.
In future works the issue of low catalyst activity
will be further examined as well as carbon deposit
at hydrogen) and 6 MPa analysed via GC-FID/ in the catalyst surface.
TCD, are depicted.
The highest methane conversion rate of 1,4%
was reached at 487°C at pressure 2 MPa, at pres- REFERENCES
sure 2 MPa after reduction with hydrogen 4,1% was
reached at 471°C. The highest methane conversion Marwood, M., Doepper, R. and Renken, A. In-situ surface
was at pressure 6 MPa, when 4,6% was reached at and gas phase analysis for kinetic studies under transient
468°C. conditions. The catalytic hydrogenation of carbon diox-
ide. Applied Catalysis A: General, 1997. 151: pp. 223–246.
5.3.2 Products when using nickel-molybdenum Mills, G.A. and F.W. Steffgen, Catalytic Methanation.
catalyst Catalysis Reviews, 1974. 8 (1): pp. 159–210.
In Figure 3 the composition of the produced gas Moore, C.L, Technology development for human explo-
depending on the reaction temperature when using ration of Mars. Acta Astronautica, 2010. 67: pp.
1170–1175.
the model gas mixture containing 20 mole % CO2 Sabatier, P.S., J.B., New synthesis of methane. Comptes
and 80 mole % H2 at pressures 2, 4 and 6 MPa ana- Rendus Hebdomadaires des Seances de l´Academie
lysed via GC-FID/TCD, are depicted. des Sciences, 1902. 134: pp. 514–516.
The highest methane conversion rate of 19,88% Šnajdrová, V., Baraj, E. and Hlinčík, T, Power-to-Gas.
was reached at 471,9°C at pressure 2 MPa, at pres- Plyn/Gas, 2016. 2: pp. 35–40.
sure 4 MPa 8,72% was reached at 360,9°C and at Tada, S., Shimizu, T. Ni/CeO2 catalysts with high CO2
pressure 6 MPa 3,22% was reached at 399,6°C. methanation activity and high CH4 selectivity at
low temperatures. International Journal of Hydrogen
Energy, 2012. 37(7): pp. 5527–5531.
Tsuji, M., et al., Preparation and CO2 Methanation
6 CONCLUSIONS Activity of an Ultrafine Ni(II) Ferrite Catalyst. Jour-
nal of Catalysis, 1996. 164(2): pp. 315–321.
Carbon dioxide and hydrogen methanation on nickel- Vance, C.K. and C.H. Bartholomew, Hydrogenation of
cobalt and nickel-molybdenum catalysts under labora- carbon dioxide on group viii metals: III, Effects of sup-
tory conditions were performed. The gas feed consisted port on activity/selectivity and adsorption properties
of 80 mol % H2 and 20 mole % CO2. The reaction of nickel. Applied Catalysis, 1983. 7(2): pp. 169–177.

180
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Evaluation of rice husks qualified for energetic utilization in Vietnam

V.M. Duong & F. Skácel


University of Chemistry and Technology, Prague, Czech Republic

ABSTRACT: As the common crop residues in Vietnam, rice husks can be a technically efficient,
economically viable and environmentally sustainable bio-energy option, release a potential heat for
thermo-chemical conversion systems. The report provides a comprehensive evaluation in the nature,
physio-chemical property, fuel characteristic, ash composition and transformation phenomena of this
biofuel. Analysed results show significant calorific value (16–17 MJ/kg), high ash and volatile contents,
low Ca, S and high Si contents. Ash softening and fusion processes were determined with heat generated
continuously at constant rates (maintained at 550 ± 10°C for 120 minutes, at 850 ± 10°C for 240 minutes).
First signs of deformation were recorded at temperature above 1450°C, whereas volume expanding and
bursting of internal gas bubbles were not presented. Further elemental determination of ash compositions
explains the decomposition of ash-forming elements (Fe, Cl, S, Al, Na), by further oxidation (to higher
oxidation states) and partial losses of volatile inorganic compounds.

1 INTRODUCTION The popular use of solid biofuel is direct com-


bustion for heat, which is the most common tech-
In the global context, there is a growing interest nical option with the low efficiency. In practice,
in the diversification of biomass targeted to bio- households use various fuels in combination not
energy production, gradually replacing conventional just one type of fuel, in which only 7% of them
energy sources. Among the agricultural residues, use rice husks as a bio-energy. However, after
rice husks and straws are important biomass source pre-drying, rice husks and straws can be effectively
for heat and electricity generation due to their com- burned with relatively weak environmental impacts.
modity vary widely (Chungsangunsit et al. 2004). The use of rice husks for brick kiln (25%) and other
In Vietnam, large amount of rice husks and straws industrial purposes (10%) is rapidly spread because
have been main field based residues of rice produc- of lower prices, local availability and reliability of
tion for centuries. Recently, the use of rice husks supply. A higher efficiency alternative is using the
and straws is highlighted as a potential non-woody gases synthesized from rice husk in a gasification
biomass resource (Vietnam I.E. 2004, 2006). system, such as CO, H2 and volatile hydrocarbons
More than sixty-five percent rice crops of for electricity generation followed by internal com-
which takes place in Vietnam, mainly in three bustion engines and generators. Pyrolysis is becom-
dynamic harvests (Nguyen et al. 2009), starting ing more important with high potential of energy
from February to April (the winter-spring sea- recovery process which generates char, oil and gas
son), followed by the summer-autumn harvest products, all of which was applied at the industrial
(June to August) and respectively from October to production scale. Moreover, the utilization of rice
December (the autumn-winter season). The total husks and electrical production shifting increase
quantity of rice husks in Vietnam was estimated the efficiency of energy saving, and hence secure
at 7.5 million tons per year (t/y), of which 52.5% power supply.
was generated during the winter-spring season Therefore, the thermo-chemical conversion of
(Pham et al. 2011). The availability of rice husks rice husks is an option to advance the eco-friendly
supply depends on the rice production, harvesting and efficient production of heat and power, as
episode, proportion in a paddy and bio-energy use well as the generation of valuable products for
schedule. Previous studies have summarized that the chemical industry based on renewable carbon
the proportion of rice husks and straws to rice is sources. A large number of research works, pre-
approximately one. Particularly, rice straw is gen- feasibility studies and pilot projects were carried
erally placed in a field for drying 3–5 days remain out to install power plants in the Mekong river
used non-commercially in traditional applications delta. The co-firing of rice husks in the combus-
(such as cooking stoves); when its moisture con- tion systems can be an innovative option with the
tent could be around 10–12%. aim of achieving more effective utilization. As the

181
first relevant issue for all types of thermo-chemical Table 1. Physic-chemical properties of rice husks.
conversion technologies, the physio-chemical char-
acterization of rice husks must be analyzed in Content Value Unit
order to evaluate their ash fusion. The obtained
C 43,16 w% db
values define the behavior of the fuel during the H 5,18 w% db
pyrolysis, gasification and combustion stages, and N 0,47 w% db
thus support the proper design and operation set- S 0,06 w% db
ting (Schmid et al. 2016). Cl 0,09 w% db
Moisture 7,44 w%
Ash 14,99 w% db
2 FUEL ANALYSIS Volatile 68,5 w% db
Higher heating value 16929 kJ/kg db
The nature and efficiency of any thermo-chemical Lower heating value 15791 kJ/kg db
conversion process depends strongly on fuel prop-
erties, and hence influences the end-use applica-
tions. In practice, the whole process of biomass
utilization including material supply, fuel analysis, the process control during combustion, gasification
application design, system testing, gaseous emis- and pyrolysis. Pellets moisture content specifies a
sions, etc., depends on the physical characteristics considerable influence in the combustion behavior;
and chemical composition. The medium and large the volume of flue gas produced and average resi-
scale systems are suitable to combust low-quality dence drying time before gasification takes place.
fuel, while the smaller combustion plant demands Carbon and hydrogen, which are the main com-
higher fuel quality concerning the homogeneity. ponents of solid biofuel, explain the low calorific
The qualities of biomass pellets vary widely, value of rice husks, in comparison to other biofuel.
influenced mainly on the pre-treatment technologies High amount of volatile matter in rice husks caries
applied. Figure 1 shows the use of 8-mm diameter between 68.5% (ÖNORM CEN/TS 15148) indicates
pellets with the moisture content between 8–10% major part of this fuel is vaporized before homoge-
(ÖNORM CEN/TS 14774-2) is always the first step neous gas phase combustion reactions take place
to reduce the bulky volume of raw materials during strongly influences the thermal decomposition and
transportation and increase the heat exchange effi- combustion behavior (Wopienka et al. 2014). Nitro-
ciency. Physical parameters are particle dimensions, gen oxides, HCl, Cl2, alkali chlorides formation, gas-
bulk and energy density, gross and net calorific eous compounds of SO2, SO3 and alkali sulphates
value and moisture content. Depending on the fuel released during the combustion process are impor-
preparation process, the particle size distribution is tant not only for emission control but also in cor-
normally homogeneous, appropriate for small-scale rosion processes (Permchart et al. 2004). Emission
fuel-feeding system and combustion units. and environmental issues can be controlled with
Table 1 summarizes the important values the adequate concentration of nitrogen (ÖNORM
of investigated fuel. Recorded calorific values CEN/TS 15104), chlorine and sulphur (ÖNORM
(ÖNORM CEN/TS 14918) approximately 16 MJ/kg CEN/TS 15289) reported in the rice husks pellets.
indicate a potential heat release and the influence

3 ASH MELTING BEHAVIOR

Several authors reported the thermo-chemical con-


version technologies involve a number of physical
and chemical aspects of high complexity. Particu-
larly, ash transformation during combustion of
biomass is a very complex phenomenon, which
can exhibit many essentially different scenarios
(Bostrom et al. 2012). The ash content value indi-
cates a considerable influence on the technology
applied, de-ashing process, transport, storage, utili-
zation and disposal of the produced ash (Natarajan
et al. 1998). Each sample of rice husks was ana-
lysed at least twice at the standard condition 550°C
for 120 mins (specified in CEN/TS 14775) and the
Figure 1. Available sample size of 8-mm for rice husks average value of the ash content is presented in
pellets. mass percentage referring to the dry sample.

182
ter emission, as an influence on the heat exchanger
design, cleaning system and dust control technol-
ogy. Figures 4 shows the remarkable changes in ash
characteristic and melting tendency between tested
materials. The observed volume shrinking at 1000°C
can be explained by the decomposition of major
ash-forming elements (Fe, Mn, Ca, K, Cl, S, P, Al,
Mg, Na and especially Si), by further oxidation (to
higher oxidation states) and partial losses of volatile
inorganic compounds. This phenomena practically
recovered in the fly ash, and the decomposition of
Children Face Tough Issues carbonates forming CO2 mainly be released with
other gaseous compound in the flue gas.
Figure 2. Ashing and conditioning of test portions in Rice husks specimens showed first signs of
the different empirical conditions. deformation at temperature above 1450°C which is
higher than the critical values for the classic com-
bustion or gasification processes in a fluidized bed.
High ash-melting point characterize rice husks as
good solid biofuel for the modern combustion/
gasification technologies, in terms of avoiding the
sintering factors, decrease emission, minimize cor-
rosion, maintain the operational safety control.
Volume expanding and bursting of internal
gas bubbles were not presented in the test pieces.

Face Tough

Figure 3. Test pieces observed (from left to right) in


initial, shrinkage and deforming states.

Ash softening and fusion processes were deter-


mined by optical standard lab-scale testing method
according to DIN 51730. Different sets of ashes were
conditioned (maintained constantly at 550 ± 10°C Children Face Tough Issues
for 120 min and at 850 ± 10°C for 240 min) as
showed in Figure 2. Test pieces were pressed to the Figure 4. Observed difference in ash melting tendency.
small geometric bodies while heat was generated
continuously at the constant rates, then the changes
in shapes were simultaneously recorded.
Beside the standard analyses methods to bio-
fuels, the X-ray spectrometry on samples of con-
ditioned ashes was applied for major and minor
element analyses (according to ÖNORM CEN/TS
15290 and ÖNORM CEN/TS 15297).

4 RESULTS AND DISCUSSION

The recorded value 14.99% in ash content indicates


a considerable influence on the combustion technol- Children Face Tough Issues
ogy applied, de-ashing process, transport, storage,
utilization and disposal of the produced ash. The Figure 5. Ash elemental compositions in the tested
high value usually lead to higher particulate mat- specimens.

183
High concentration of major cations and ash- Armesto, L. et al. 2002. Combustion behaviour of rice
forming elements especially Si, Ca, Mg, K, Na and husks in a bubbling fluidised bed. Biomass and Bio-
P were determined. Figure 5 shows the significant energy 23(3):171–179.
alkali contents in rice husks while the obtained Si Bhattacharya, S. C. et al. 1984. Some aspects of fluidi-
zed bed combustion of paddy husk. Applied Energy
value was relatively high. The low alkali content is 16(4):307–316.
responsible for the high ash softening temperature, Bostrom, D. et al. 2012. Ash transformation chemistry dur-
which in practical avoids the agglomeration of ing combustion of biomass. Energy & Fuels 26:85–93.
bed materials, minimize the risk of breakdown of Chungsangunsit, T. et al. 2004. Environmental assess-
the fluidized bed system and stop a combustion/ ment of electricity production from rice husks: a case
gasification test at an early stage. study in Thailand. Proceedings of international confer-
ence on electricity supply industry in transition: Issues
and prospect for Asia. Bangkok, Thailand.
5 CONCLUSIONS Fang, M. X. et al. 2004. Experimental study on rice husk
combustion in a circulating fluidized bed. Fuel Proc-
ess Technology 85:1273–1282.
The paper provides a comprehensive evaluation Islam, M. et al. 2000. Techno-economics of rice husks
in nature, physio-chemical property, fuel char- pyrolysis, conversion with catalytic treatment to pro-
acteristic, ash composition and transformation duce liquid fuel. Bioresour Technol 73(1):67–75.
phenomena of rice husks. As a common source of Mansaray, K. G. et al. 1999. Air gasification of rice husks
biomass in the Vietnam, one of the world leading in a dual distributor type fluidized bed gasifier. Bio-
countries in rice production, they can be quali- mass and Bioenergy 17(4):315–332.
fied as solid biofuels for energetic use. Significant Natarajan, E. et al. 1998. Overview of combustion and
calorific values provide a potential heat release for gasification of rice husks in fluidized bed reactors.
Biomass and Bioenergy 14(5):533–546.
industries, utilities, communities and households Nguyen, N. & Duong, H. M. 2009. Economic potential
if appropriate bio-energy technologies applied. of renewable energy in Vietnam’s power sector. Energy
This biofuel shows high ash softening temperature, Policy 37(5):1601–1613.
which is the advantage to avoid the technical issues Nguyen, V. H. & Nguyen, V. S. 2006. Clean development
in the thermo-chemical conversion systems. Spe- mechanism project design documents for pilot grid
cific elemental determination in the compositions connected rice husk fueled bio-power development
of ashes is further recommended to avoid conse- projects in Mekong Delta. EEPSEA, Vietnam.
quences related to slag formation and corrosion in Permchart, W. & Kouprianov, V. I. 2004. Emission per-
the equipment. formance and combustion efficiency of a conical
fluidized-bed combustor firing various biomass fuels.
Comparative analyzed results outlined an Bioresour Technol 92:83–91.
extensive principal baseline for further empirical Pham, T. M. T. et al. 2011. Greenhouse gas emission miti-
investigation, co-firing of rice husks and other gation potential of rice husks for An Giang province,
biofuel, innovative combustion technology, better Vietnam. Biomass and Bioenergy 35(8):3656–3666.
efficiency performance. The shift to modern appli- Schmid. J. C. et al. 2016. Steam gasification of exhausted
cation using these biofuels should be performed olive pomace with a dual fluidized bed pilot plant
corresponding to emission characteristic of solid at TU Wien. Technical report PHENOLIVE FP7-
and gaseous pollutants. Highlighting the benefits SME-2013-1-605357.
of greenhouse gas (GHG) reduction, rice husks Vietnam, I. E. 2004. Demonstration of rice husks fired
power plant in An Giang province: a pre-feasibility study
can be a technically efficient, economically viable, report. Vietnam Institute of Energy. Hanoi, Vietnam.
and environmentally sustainable option, partly Vietnam, I.E. 2006. Bagasse and other biomass-fired
replaces conventional fuel. power plant in Ben Tre sugar company: a pre-feasibility
study report. Vietnam Institute of Energy. Hanoi,
Vietnam.
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ging behavior of ashes from small-scale biomass com-
Abe, H. et al. 2007. Potential for rural electrification bustion. Dissertation. TU Wien, Austria.
based on biomass gasification in Cambodia. Biomass
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Aigner, I. et al. 2009. Gasification of biomass and coal
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Germany.

184
Water resources management
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Ecological health monitoring used for river ecosystems in Vietnam:


Challenges and prospects

A.D. Pham, T.M.L. Nguyen & T.T.H. Nguyen


Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

T.S. Dao
Faculty of Environment and Resources, Ho Chi Minh City University of Technology, Vietnam National
University, Ho Chi Minh City, Vietnam

ABSTRACT: This paper discussed on status and prospect of ecological health monitoring used for river
ecosystems. In Vietnam, phytoplankton, zooplankton and benthic macroinvertebrates have been used the
most common bioindicators in ecological health monitoring, which have been used simultaneously in the
environemntal monitoring framework of the Vietnam Environment Administration (VEA) and provin-
cial environmental protection agencies as well. Their importances in the ecosystems and advantages for
ecological health monitoring in Vietnam have been described in detail. Common methods used for eco-
logical health monitoring have included diversity, biotic indices, multimetric approaches and Functional
Feeding Groups (FFGs). Among these techniques, diversity and biotic indices were most frequently used
to evaluate the ecological health of streams and rivers. However, multimetric measures have been increas-
ingly applied in recent years to reflecting ecological integrity and integrated ecological health assessment
as well. The review reflected that biomonitoring especially ecological health monitoring on Vietnam river
systems is not only challenges but prospects as well.

Keywords: ecological health monitoring, river ecosystems, bioindicators, ecological integrity, review

1 INTRODUCTION establishment of the framework as well as methods,


e.g. biomonitoring method, for the aquatic envi-
One of the major challenges that human society ronmental impact assessment and protection.
faces today is achieving those Millennium Devel- In biomonitoring, the bioindicator groups
opment Goals that relate to the use of water (phytoplankton, zooplankton, macroinvertebrates)
resources (Revenga et al. 2005). However, the pol- provide a broad categories of the ecological health
lution, degradation and overexploitation of water, of river systems, in which each biological group
especially inland water resources have resulted in has its own distinct advantages. The various ana-
severe problems among the environmental issues lytically biological approaches (e.g. richness, abun-
in the world (Corvalan et al. 2005; Li et al. 2010). dance, and pollution tolerance) together with the
Most aquatic ecosystems have been vulnerable to physical and chemical measurement, provide valu-
a wide range of human activities. Especially, river able information for ecological health and environ-
ecosystems were rapidly disturbed by heavy pol- mental assessment (MRC 2010; Kim & An 2015).
lution sources from industrial effluents (Kim & The endpoints of measurement used for river
An 2015). In addition to the challenges posed by ecosystems could be selected from any level of
landuse change, environmental pollution, and biological organization (cellular, organ, individual,
water diversion, aquatic systems were expected to population, community, and ecosystem) (Li et al.
soon begin experiencing the added stress of glo- 2010). However, the historical focus has been on
bal climate change (Poff et al. 2002). Therefore, ecological methods and higher levels of organi-
the water resource management has been one of zation, e.g. species, populations, communities,
the most significant natural resource management and ecosystems (Li et al. 2010). Regarding the
issues of all countries, particularly related to how biological methods, two main approaches have
to find an appropriate balance between ecosystem been used based on community structure, and
health and economic development. Furthermore, “indicator” organisms. An indicator organism was
many countries have focused on building up the a species selected for its sensitivity or tolerance

187
(more frequently sensitivity) to various kinds physical and chemical conditions which are strongly
of pollution or its effects, e.g. metal pollution or influenced by anthropogenic factors (Pourriot &
oxygen depletion (Chapman 1992). The methods Meybeck 1995). The zooplankton communities,
to describe community structure or explain the dif- very sensitive to environmental modifications, were
ference between communities has been a primary important indicators for evaluating the ecological
focus of ecological research, e.g. phytoplanktonic status of aquatic ecosystems (Magadza 1994; MRC
groups, zooplanktonic groups, benthic groups 2010). They did not only form an integral part of
(Cairns et al. 1982). the lentic community but also contributed sig-
The bioindicators should have the characteristics nificantly, the biological productivity of the fresh
of (a) taxonomic soundness; (b) wide distribution; water ecosystem (Wetzel 2001). The presence and
(c) low mobility; (d) well-known ecological char- predominance of various copepod species have
acteristics; (e) numerical abundance; (f) suitability been used to characterize the trophic conditions
for laboratory experiments; (g) high sensitivity to of aquatic ecosystems (Park & Marshall 2000;
environmental stressor; (h) high ability for quan- Bonecker 2001). Herbivorous zooplankton was rec-
tification and standardization (Rosenberg & Resh ognized as the main agent for the top-down control
1993; Füreder & Reynolds 2003; Li et al. 2010; of phytoplankton, and the grazing pressure exerted
Osuji 2014). Biomonitoring involves the use of by cladocerans and copepods on algae and cyano-
indicators, indicator species or indicator communi- bacteria was sometimes an important controlling
ties. Generally algae, protozoa, macroinvertebartes factor of harmful algal blooms (Boon 1994).
and fish are used. There are advantages and dis- For macroinvetebrates, these assemblages were
advantages to each. Macroinvertebrates are most made up of many species among which there was
frequently used (Rosenberg & Resh 1993). a wide range of trophic levels and pollution tol-
In this paper, we reviewed the history and devel- erances (France 1990; Bartram & Balance 1996),
opment of biological monitoring in Vietnam, pro- hence providing strong information for interpret-
vided the choice of study organisms; provided the ing cumulative effects. Community structure of
importances in the ecosystems and advantages for macroinvertebrate assemblages frequently changed
biomonitoring; provided the approaches of eco- inresponse to environmental disturbances in pre-
logical health monitoring. Among the many bio- dictable ways, which was the basis for develop-
indicators of biomonitoring in rivers, streams and ment of biocriteria to evaluate human influences
lakes, phytoplankton, zooplankton and benthic (Emery et al. 2003). In stream sand rivers polluted
macroinvertebrates have been the major groups by organic matters or trace metals (De Paw et al.
commonly used for biomonitoring in Vietnam. 1996; Pham 2014), species richness and diver-
First of all, changes in the phytoplankton com- sity of the macroinvertebrates strongly reduced
munity and biomass greatly affected the rest of the under the direct and indirect impact of contami-
pelagic system as well as the benthic community nants. For example, Chironomidae commonly
(Hoglander et al. 2013). The biomass of phyto- possessed the dominant status at the expense
plankton affected the light climate for benthic of other more sensitive groups, such as mayflies
macrophytes as well as the nutrient availability (Ephemeroptera), stoneflies (Plecoptera) and cad-
and oxygen conditions for benthic macrophytes disflies (Trichoptera). Benthic macroinvertebrates,
through their sedimentation (Fox et al. 2010). especially aquatic insects, have been traditionally
High phytoplankton production could lead to high used in the biomonitoring of stream and river eco-
sedimentation rates, resulting in plenty of food systems for various environmental stress types, such
for benthic communities (Hoglander et al. 2013). as organic pollution, trace metals contaminations,
Sedimentation of phytoplankton and subsequent nutrient enrichment, acidification, sediments, and
degradation by bacteria also leaded to increased toxicants and general stressors (De Paw et al. 1996;
oxygen consumption and the risk of oxygen deple- Pham 2014). Indeed, the macroinvertebrate assem-
tion for the benthos (Gihring et al. 2009). Phyto- blages constituted the basis of most biomonitoring
plankton could also affect water quality, by giving program currently in Europe and North America.
water a bad odour when found in high abundances Many countries (or states or water authorities)
or by producing toxins that could be released into even have developed their own biotic indices.
the water when the phytoplankton degraded or
was accumulated in other organisms feeding on the
phytoplankton (Zigone & Oksfeldt 2000). Some 2 BIOINDICATORS USED FOR
phytoplankton species caused damage to fish gills, ECOLOGICAL HEALTH MONITORING
resulting in the mortality of wild fish and, for exam- IN RIVER ECOSYSTEMS IN VIETNAM
ple, salmonids in fish farms (Rodger et al. 2010).
Besides, the zooplankton communities in aquatic The biomonitoring used the species richness and
ecosystems are regulated by the variations of the density of phytoplankton, zooplankton and

188
benthic macroinvertebrates were inluded in the However, publications on interaction between
national monitoring program by the VEA. Addi- phytoplankton and environmental parameters and
tionally, the above biological groups have been water quality based on phytoplankton from rivers
used to monitor the water quality in Vietnam. in Vietnam were limited (Dao & Bui 2016). Dao
However, other aquatic organism groups such as and Ho (2015) applied the species richness and
fish and aquatic macrophytes were rarely used for density of phytoplankton to evaluate the water
the biomonitoring in Vietnam. quality of Thi Vai River. Besides, the authors
Their efficiency when used separately has been reported there was a significant relation between
demonstrated by many studies, e.g., Whitton and phytoplankton abundance and inorganic nitrogen
Rott (1996), Vis et al. (1998), Potapova (1999), and water temperature (Dao & Bui 2016).
Coste et al. (2008), Li et al. (2010), and Dao and
Bui (2016) for phytoplankton; Thorp et al. (2005),
2.2 Zooplankton
Nguyen (2007), Ferdous et al. (2009), and MRC
(2010) for zooplankton; Rosenberg and Resh Zooplankton have an intermediate position in
(1993); Lenat and Barbour (1994), Statzner et al. the food web, concerning phytoplankton and
(2001), Li et al. (2010), MRC (2010), and Pham animals of higher trophic levels in food chain
et al. (2015) for benthic macroinvertebrates. such as shrimps and fishes. Zooplankton are
generally small, with little ability to swim against
water currents. They include representatives of
2.1 Phytoplankton
almost every taxon of the animal kingdom and
Phytoplankton were among the most common occur in the pelagic environment either as adults
organisms on the earth and widely distribute in (holoplankton) or eggs and larvae (meroplankton)
many different environmental conditions such as (Goswami 2004; MRC 2010). Changes in the water
water, soil, air, on trees (Dao & Bui 2016). How- quality as well as zooplankton quality were indica-
ever, they mostly presented and well developed in tors of rate and magnitude of cultural eutrophi-
aquatic habitats including lakes, ponds, reservoirs, cation (Kulshrestha et al. 1989; Chari & Abbasi
rivers, streams and oceans (Horne & Goldman 2003) (Figure 2).
1994). Phytoplankton were good indicators of So far, several investigations on zooplankton
environmental status and quality due to their quick from Vietnam have been published on morpho-
response to changes in environmental pressures logical biodiversity of zooplankton (Hamon
such as nutrient availability (Figure 1). 1956; Shirota 1966; Alvarino 1967; Shirota 1967a;
In Vietnam, a variety of investigations have Shirota 1967b; Nguyen 2007). The motioned
been conducted focusing on morphological diver- zooplankton publications described the zooplank-
sity of phytoplankton (Pham 1969; Nguyen 1997; ton community in Vietnamese waters and reported
Nguyen 2003; Phung et al. 1992; Nguyen et al. the abundance, composition, biomass and their dis-
2007; Dao et al. 2012; Dao & Nguyen 2013). tribution. Besides, cephalopod paralarvae would

Figure 1. Phytoplankton in freshwater bodies of Vietnam used as bioindicators for water quality of oligotrophic
(a, Micrasterias foliacea), mesotrophic (b, Aulacoseira granulata) and eutrophic conditions (c, Eudorina elegans). Scale
bars = 20 μm.

189
Figure 2. Zooplankton in freshwater bodies of Vietnam used as bioindicators for water quality of oligotrophic
(a, Diaphanosoma excisum), mesotrophic (b, Brachionus calyciflorus) and eutrophic conditions (c, Moina dubia). Scale
bars = 100 μm.

Figure 3. Benthic macroinvertbrates in freshwater bodies of Vietnam used as bioindicators for water quality of
oligotrophic (a, Dromogomphus sp.), mesotrophic (b, Filopaludina (F.) filosa) and eutrophic conditions (c, Limnodrilus
hoffmeisteri). Scale bars = 1 mm.

be concentrated. And, some of investigations macroinvertebrates have the ability to integrate


have been conducted focusing on biodiversity of the effects of short-term environmental variations
zooplankton (Pham et al. 2000, 2003; Berge et al. (Figure 3).
2006). However, information and understanding In Vietnam, biomonitoring based on benthic
on the interaction between zooplankton and envi- macroinvertebartes was considered and imple-
ronmental parameters and water quality based on mented (Dang et al. 1980; Nguyen 1985, 1995;
zooplankton from rivers in Vietnam was limited Berge et al. 2006; Pham et al. 2000, 2003, 2010).
(Pham et al. 2010). Nguyen et al. (2000, 2003) developed the biological
surveillance of freshwater using macroinvertebrate.
This was a practical manual and identification key
2.3 Benthic macroinvertebrates
for use in Vietnam and studied the macroinver-
Macroinvertebrates were organisms which did tebrates for assessing the water quality in Nhue
not have a backbone and were large enough to be River. These methods were applied for fresh
seen without a microscope. Aquatic macroinverte- water assessment in North Vietnam. In Dong Nai
brates live in water during some period of their life. River and Mekong River Delta, based on the over
These organisms, including insects, crustaceans, 10-year-data collection from many years together
worms, leeches, and mollusks, occupy a variety with physicochemical indicators, Mien et al. 2003
of niches in the aquatic community (MRC 2010; has established the group of phytoplankton, zoo-
De Paw et al. 1996; Pham 2014). Many countries plankton, and macroinvertebrates such as bioindi-
had a long history of using macroinvertebrates to cators in the water quality assessment that reflected
monitor the ecological status of river ecosystems essentially characteristic of regions with their dif-
(Hallawell 1986). With the sensitive life stage and ferent environment (Pham & Le 2004). In fact, the
relatively long life span (Hutchinson et al. 1998), Lower Dong Nai River and Mekong River Delta

190
have been strongly influenced by tide amplitudes Index (Stiling 2002). Although diversity indices are
(2.5–4.0 m) form South China Sea to the inland, applicable to a variety of aquatic environmental
consequently there had multiple species from both situations which have not been thoroughly tested
the sea water and fresh water (Pham & Le 2004). for biological relevance. Nevertheless, such indices
However, publications on interaction between ben- could be used until other methods or systems have
thic macroinvertebartes and water physicochemical been adequately field tested or developed (Chapman
parameters from rivers in Vietnam were limited. 1996). Up to now, this method is widely used in the
Some articles found the variation of species rich- environmental monitoring programs of the govern-
ness and abundance with physicochemical vari- ment or the provinces in Vietnam. Specifically, the
ables in both dry and rainy seasons (Le et al. 2012; environmental experts and authorities have applied
Pham 2013; Pham 2014a; Pham 2014b; Pham & this method to assess the ecological health moni-
Dang 2014; Pham & Le 2012; Pham et al. 2015); toring programs, for examples the Environmental
which were used to develop the biological indices Monitoring Program of Dongnai River Basin, the
of benthic macroinvertebrates for water quality Environmental Monitoring Program of Mekong
assessment (Pham & Le 2011; Pham et al. 2012). River Basin or the Vietnam Environmental Moni-
Besides, Pham & Nguyen (2010) developed the toring Programs were managed by the Provincial
rapid assessment of ecological health based ben- Authorities or the Vietnam Ministry of Natural
thic macroinvertebrates and environmental vari- Resources and Environment… (Pham 2014a).
ables in Dongnai River Systems.
3.2 Biotic indices
3 COMMON METHODS USED FOR Biotic indices were usually specific for certain types
ECOLOGICAL HEALTH MONITORING of pollution since they were based on the presence
OF RIVER ECOSYSTEMS IN VIETNAM or absence of indicator organisms (bioindica-
tors), which were unlikely to be equally sensitive
There were several different biomonitoring to all types of pollution. Such indices often used
approaches currently employed in river ecosystems macroinvertebrate populations because they could
(Reece & Richardson 1999). The selection of an be more easily and reliably collected, handled and
appropriate approaches depended on the issues identified. In addition, there was often more eco-
being addressed and available resources. Potential logical information available for such taxonomic
biomonitoring methods included diversity indi- groups (Chapman 1996, Li et al. 2010). In order to
ces, biotic indices, multimetric approaches, mul- limit the taxonomic requirement of earlier biotic
tivariate approaches, Functional Feeding Groups indices to identify organisms to species level, some
(FFGs), and multiple biological traits (MRC 2010; alternative indices have been developed which used
Li et al. 2010). However, the techniques of multi- only the family level of identification (Hellawell
variate approaches and multiple biological traits 1986). Commonly used biotic indices for macroin-
have been started to apply in not more than two vertebrates in Vietnam are BMWPVIET (Nguyen
studies on river ecosystems in Vietnam. et al. 2000); Po Index (Pham 2004); TUCH Index
(Pham & Nguyen 2010). In reference to the
BMWP used in the UK and the BMWPThai, a sys-
3.1 Diversity indices
tem of BMWP score that was suitable for macrob-
Stable ecosystems were characterized by a great enthos fauna and natural conditions of Vietnam
diversity of species, most of which were represented was established and therefore called the BMWP
by relatively few individuals. The community struc- Vietnam score. This BMWPViet and the ASPT were
ture approach examined the numerical abundance performed to assess the quality of some lotic water
of each species in a community. The methods bodies in northern Vietnam such as Tam Dao and
widely used to assess aquatic environmental pol- Da Lat Cities. From biological data collection over
lution were based on either a diversity index or a 10 years together with physicochemical indicators,
similarity index (Chapman 1996, Li et al. 2010). As the Po Index was based on errant polychates and
traditional biomonitoring methods, many diversity sedentaria polychaetes such as bioindicators in the
indices have been developed to describe responses of water quality assessment that reflected essentially
a community to environmental variation, combin- characteristic of southern regions with their dif-
ing the components of community structure, taxa ferent environment. The TUCH Index was set up
richness, evenness and abundance such as Jaccard based on the ratio of species composition of tubi-
Index (Chapman 1996), Simpson Index (De Paw fids and chironomids comparison with all species
et al. 1996), Margalef Index (De Paw et al. 1996), for water quality assessment. In addition, some
Shannon-Wiener Index (De Paw 1996, Stirling others have still used the alternative approaches
2002), Eveness Index (Stiling 2002), Begger-Parker to the Saprobic Index which have been developed

191
by Pantle and Buck (1955), Zelinka and Marvan biological traits were related to habitat character-
(1961), Liebrmann (1962), Woodiwiss (1964), istics and the biological and ecological functions
Granham (1965), Cairns et al. (1968), Sladecek of species, thus permitted a view into the function
(1973), (Chapman 1996, Pham 2014a). structure of biocoenosis (Haybach 2004; Li et al.
2010). Multiple biological traits of aquatic in the
context of environmental constraints have been
3.3 Multimetric approaches
recently developed for freshwater biomonitoring
Multimetric indices represented a means to inte- (Bonada et al. 2006; Li et al. 2010). However, these
grate a set of variable or metrics, which represented approaches for water quality assessment and eco-
various structural and functional attributes of an logical health monitoring have been applied very
ecosystem (such as taxa richness, relative abun- few in Vietnam. For examples, Pham et al. (2012)
dance, dominance, functional feeding groups, studied the multivariate approaches for water qual-
pollution tolerance, life history strategies, disease, ity assessment based on the benthic macroinverte-
and density). Therefore they provided robust and brates in Lower Dongnai River System.
sensitive insights into the responses of an assem-
blage to natural and anthropogenic stressors
(Carvalho 2002; Li et al. 2010; Vandewalle et al. 4 PROSPECTS IN ECOLOGICAL HEALTH
2010). Nowadays, multimetric approaches for ben- MONITORING OF RIVER ECOSYSTEMS
thic macroinvertebrates have been the most widely IN VIETNAM
used approaches for river biomonitoring in USA
and other parts of the world (Sivaramakrishnan By now, diverse biomonitoring techniques have
et al. 1996; Thorne & Williams 1997; Vlek et al. already been developed to quantify the human
2004; MRC 2010). However, these approaches impacts on the aquatic ecosystems. However,
have been used only in some projects to evaluate because of the new trends in environmental poli-
the ecological health of rivers in Vietnam (Pham & cies, ecologists are facing to new demands of effec-
Nguyen, 2008; MRC, 2010; Pham, Nguyen, 2010). tive tools for the ecological health evaluation and
environmental management for conservation and
restoration (Corvalan et al. 2005; Li et al. 2010).
3.4 Functional Feeding Groups (FFGs) Besides using professional methods to assess eco-
Analyses of Functional Feeding Groups (FFGs) logical health and water quality in river systems,
were the key components of river continuum con- the techniques of rapid assessment have been
cept (RCC; Vannote 1980) and have been applied developed also (Pham 2014a). Moreover, the eco-
to assess ecosystem-level processes in rivers and logical health monitoring based on three organ-
wetlands (Flotemersch et al. 2010; Li et al. 2010; ism groups of phytoplankton, zooplankton and
Zhang et al. 2014). In river biomonitoring, FFGs benthic macroinvertebrates have been used widely
measures have been used in the forms of single to monitoring the ecological status and the water
feeding groups (as absolute or relative abundance), quality of running waters. Addtionally, the other
ratios between two groups, or composite index that aquatic organism groups such as macrophytes,
included several trophic aspects (Pavluk et al. 2000; meiobenthos or fish are highly suggested to include
Li et al. 2010). In Vietnam, some Master thesis of into the biomonitoring to fully evaluate the aquatic
aquatic ecology have applied the FFGs to evalaute ecological health and environmental quality.
the river ecology and functions in the north and the
south of Vietnam. For examples, Bui et al. (2015)
considered the FFG structure of aquatic insects in ACKNOWLEDGEMENT
upstreams of Da Nhim River to understand the
ecological functional groups in the watershed. The authors thank Prof. Le Vinh Danh, Rector of Ton
Multivariate approaches have been initially Duc Thang University, Vietnam, for his support and
introduced to assess the biological status of rivers encouragement. We sincerely acknowledge Mr. Pham
within the UK, with the development of RIVPACS Van Mien, Institute of Environmental Science and
(River Invertebrate Prediction and Classification Development, Vietnam for providing specific papers.
System) (Li et al. 2010; ECETCO, 2011). This
adopted statistical analyses to predict site-specific
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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Possibilities for drinking water supply in periods of drought


in the Czech Republic

Miroslav Kyncl & Silvie Heviánková


Faculty of Mining and Geology, VSB—Technical University of Ostrava, Ostrava, Czech Republic

ABSTRACT: Changes in climate result in extreme hydrological situations, such as floods or droughts.
Frequency and intensity of droughts has been considerably increasing. The last such case in the Czech
Republic was the drought in 2015. Models of climatic changes prove a long-lasting tendency in growth
of air temperature. This poses a threat for continuous water supplies. The paper is based on experience
obtained during the droughts in past years. A specific site was chosen and investigated with respect to
supplies of drinking water from surface sources in 2015 where the purpose is to show how critical periods
of drought might be managed in the future. The paper investigates into those sources and proposes the
drought management measures. The sources might be connected with each other in the region, and prefer-
ence should be given to take-off of water for water supplies.
The advantage is that production of drinking water now is 60% of past production. This is the conse-
quence of reduced consumption of drinking water after introduction of market economy and, in turn,
higher prices paid for drinking water.

1 INTRODUCTION Many governments and international institutions


have been dealing with consequences of climatic
The Czech Republic is located in the moderate cli- changes. This is a global problem that comprises
mate zone on the northern hemisphere. Ocean and technical, organisational, legal, economic, political
continental influences co-exist there. The continen- and environmental aspects (Massey et al. 2015).
tal weather is slightly prevailing. Typical winds are Regarding the sources of water, three types of meas-
west ones and cyclone activities are rather inten- ures should be considered in water management:
sive. The average annual temperature in January
1. Measures aimed at reducing demand for water
ranges between −5°C and −1°C. Precipitation on
sources. This might include improved efficiency
most of the territory is 500–700 mm per year. In
in water management, water-saving technolo-
some, rather wet places, the precipitation ranges
gies, or a well-thought financial policy.
between 700 and 1000 mm per year. In mountains,
2. Measures aimed at controlling demand for
the maximum precipitation might be 1,700 mm.
water sources in drought. Drought manage-
In the driest locations the precipitation is 410 mm
ment plans, operative management, forecast
only (Tolasz et al. 2007).
and warning systems.
Changes in the climate as a consequence of
3. Measures aimed at improved capacity of water
global warning have been for a rather long time
sources. Construction of water ponds, transfer
among issues addressed by IPCC (Intergovern-
of water between sources, increase in capacity
ment Panel on Climate Change) (IPCC 2007).
of groundwater, infiltration artificial.
Warming of the Earth influences, in turn, changes
in the climate, which become more and more sig- This paper uses the experience obtained dur-
nificant. They influence both the water cycle and ing the drought in 2015 and in past periods of
water management. Direct consequences include droughts to evaluate options that will make it
variation in rainfall and increasing temperatures. possible to manage the drought in the future. The
The reason is a decrease in river flows, less snow, preferred solution territory in the north-west of
intensive thawing and fast runoff from water- Bohemia and possible supplies of drinking water
sheds. Filling up of groundwater supplies is limited based on the experience from the in the drought
only. This may result in lack of water in sources management is continuous supplies of drinking
that are used for drinking water supplies. Another water Attention is paid to a specific drought in
threat is worse quality of water that is used for pro- 2015. That territory has been suffering for a long
duction of drinking water (Howard et al. 2010). time from rather low average rainfall.

197
2 DROUGHT FORECAST IN THE CZECH drought. Two-year or three-year drought occurred
REPUBLIC as well. The two-year drought was reported once
in 10 years. The three-year draft occurred once
According to the forecast issued by the Czech in twenty years. A period which would last more
Hydrometeorological Institute (Pretel et al. 2011) it occurred in exceptional cases only. Since 1950
is expected that average temperatures of air during there have been 26 episodes of drought. The past
a year will increase by 1.4°C up to 1.8°C between 50 years can be regarded as the most dry years in
2021 and 2050. In the period between 2071 and 2100 the past 500 years. Intensity of the drought on the
the temperature should increase by 3.3°C–3.7°C entire territory was not always same. There were
(if compared with the reference period 1961–1990). considerable local deviations.
Those changes will result in more rainfall in What is important for obtaining information
winter and spring, while less rainfall is expected about drinking water supplies is the new episodes
in summer. Extreme phenomena will also occur of drought. For instance, between 1982 and 1984
more often. On one hand, torrential rains are more the territory was not affected equally—it was the
likely, while on the other hand, periods of drought north-east that suffered most.
are probable in summer. Precipitation was only 74% of the long-lasting
In one hundred years (1906–2005) the tempera- average. On that territory, the year 1983 was
ture in the world increased by 0.75°C on average. In regarded as the warmest year in the 20th century.
past 25 years the Earth has warmed by 0.18°C which In those days, drinking water from public water
is 2.5 times more than during the one hundred year networks was supplied to 78% of population. The
period (Pretel et al. 2011). Simulations of future main source of water was surface water taken from
changes of average monthly temperatures indicated rivers. It was stored in water reservoirs and treated
that not only the temperatures will change: it is also in water treatment plants for drinking water
the character of the temperature changes which will production.
alter. In summer, it is expected that occurrence of The drought resulted in considerable drop of flow
tropical days and nights will increase while in winter in rivers, lack of water in water wells used for local
there will be less arctic days. Those climate changes, suppliers, and decrease in groundwater yield in some
particularly the drought, pose a problem for water sources. The main problem was a permanent drop
supplies. The Czech Republic depends entirely on in water quantity in water reservoirs. Using the data
rainfall in its hydrological balance—this is the con- about water volumes in water reservoirs in 2013, it
sequence of the Czech Republic’s position. was calculated that the continuing drought would
Regarding changes in the total precipitation, the result in empty water reservoirs by the end of the
situation is even more complicated. The simulation year. The only possible measure was to reduce con-
expects that there will be less precipitation in winter sumption of drinking water. People were encouraged
(as much as 20 per cent drop in some places), while in to save drinking water and not to use it for water-
spring there will be more precipitation (between 2 and ing their gardens, washing their cars and for similar
16 per cent). In spring and autumn the situation will purposes. Industrial plants were provided a limited
be different in different parts of the Czech Republic. access to drinking water: first, the supply was lim-
In autumn, there will a small drop of precipitation in ited by 30%, later by 50%. In those days, the indus-
some places—by several per cent, while in other parts try consumed more than 50% of produced drinking
of the Czech Republic, the precipitation will increase water. It should be pointed out that consumption
by as much as 20–26 per cent. In summer, some places of water was rather high, because the price of water
will witness a slight drop in the precipitation, while was very low—this resulted in non-economical
in other places there will be as much as 10% increase water management. Thanks to the restricting meas-
in precipitation (Ministry of the Environment 2014). ures, the consumption dropped by 20% which made
This means, the precipitation will be very different for it possible to overcome the drought.
various parts of the Czech Republic. Next periods of drought were in 1992 and 2003.
The precipitation models indicate considerable Those periods, however, did not affect too much
fluctuation of precipitation in territories. This the drinking water supplies. The periods were
means, lack of water needs to be addressed on a rather short, but consumption of drinking water
local basis. dropped as well. After 1990, market economy was
introduced in the Czech Republic. Before that, the
water tariff was subsidised by the state and was
3 PAST PERIODS OF DROUGHT AND very low. After that, the water tariff was based
DRINKING WATER SUPPLIES on costs and was rather high. Since then, the con-
sumption of water has been going down, while the
In past centuries, the number of dry years was water tariffs have been increasing. The final drop
fluctuating—there were 4 up to 17 episodes of in consumption is such that now it is sufficient to

198
Figure 1. Production of drinking water in the years
1989–2013. Figure 2. The course of rainfall since the beginning
of 2015 in comparison with the course for the period
1981–2010.
produce a half of quantity of drinking water. For
details about production see Chart 1 above.
5 POSSIBLE ALTERNATIVES FOR WATER
SUPPLIES IN LONG-LASTING PERIODS
4 HYDROLOGICAL DROUGHT IN OF DROUGHT
2015 AND WATER SUPPLIES
The climate changes and periods of droughts
The year 2015 has been the warmest year in past 134 should be, on the basis of forecasts, more intensive
years, since start of the measurements. There were and rather long. It is necessary to prepare meas-
36 tropical days and most meteorology stations ures based on the current knowledge in order not
reported temperatures exceeding the maximums. to restrict drinking water supplies in the future.
The very warm and dry weather lasted until the Experience obtained during the drought in 2015
end of October 2015. Rainfall was at its minimum was used as the basis for assessment of duration
after the winter in 2014/2015. The drop in rainfall of water sources in drought. The location that
is evident since the end of February. From the start was chosen ranks among very dry locations in the
of the year until end of October, the rainfall was Czech Republic.
less by 30% (165 mm). For the cumulated rainfall It is located in the north-west of Bohemia, in the
compared with the long-termed values see Figure 2 rain shadow of Krušné hory (Ore Mountains). The
(Czech Hydrometeorogical Institute 2015). Žatec district, which is the driest area in the Czech
Flow rates in streams and rivers were very low. Republic, is located there too. The average rain-
Typically, they ranged between 10% and 50% of the fall is between 450 mm and 550 mm per year. The
typical flow rate of that part of the year. In some rainfall is higher than average only in tops of the
river profiles, the minimum flow rate was reached mountains. 83.8% people are connected to public
for certain days during the observation period. The water networks there. Water is mostly taken from
drought affected also the level of groundwater. The surface sources—the water reservoirs.
level was considerably below the regular level in as It is treated for production of drinking water in
many as 40% of drilled wells. The situation was water treatment plants. The water reservoirs are
more favourable in water reservoirs in rivers. The located in Přísečnice, Fláje and Žlutice.
storage volume was filled up mostly up to 40%– The level of water in those water reservoirs in
60%. The drought influenced continuity of the October 2015 was taken as a reference level for
drinking water supply to a certain extent only. The investigation of drinking water supplies in the
main reason was much excess of water sources over forecast period. The drought lasted for more than
water consumption. Now, the average storage in 8 months. Impacts of climatic changes on water
sources is almost 50%. While 1,250 million m3 was management were considered for the forecast
produced in past, 600 million m3 only is produced (Pretel et al. 2011). According to the scenarios,
now. Experience obtained in 2015 proved that the the short-termed drop in average outflow from all
year-long drought almost did not influence conti- watersheds is ca. 7–15%, while the long-termed drop
nuity of water supplies with take-off from surface (2055–2085) should be between 25% and 35%.
sources of water. Problems were reported with The tables below list the number of days
some small sources of ground water. Rather big during which the water reservoirs would be able
problems were faced in sites where the public water to supply water continuously. Results were also
network was not available and water was supplied calculated for the case then there is a zero inflow
from local sources. because of the drought—the minimum outflow

199
should, however, exist. The calculation used both free water surface and rainfall, if any, were not
the full and current volumes of water in the stor- considered.
age reservoir at the end of 2015. The calculation The total volume of the Přísečnice water res-
took into account the average water take-off and ervoir is 54.7 mil.m3, while its storage volume
calculated the time during which the volume in is 46.7 mil.m3. The maximum water take-off is
the reservoir would drop down to the permanent 960 l/s. The existing water take-off is 498 l/s., which
storage level. In each case, evaporation from is 51.9% of the maximum possible take-off. The

Table 1. Days available for continuous supply of water from the water reservoir in Přísečnice.

Total take- Storage


Storage Water off from the in the
volume take-off Outflow Inflow Difference reservoir reservoir
Přísečnice mil. m3 m3/day m3/day m3/day m3/day m3/day days

Minimum outflow/zero inflow and 45.67 43,076 4,320 0 −4,320 47,396 963
full storage
Minimum outflow/zero inflow and 38.80 43,076 4,320 0 −4,320 47,396 818
current storage
Minimum same inflow and outflow 45.67 43,076 4,320 4,320 0 43,076 1,060
and full storage
Minimum same inflow and outflow 38.80 43,076 4,320 4,320 0 43,076 900
and current storage
Reality 38.80 43,076 7,776 8,640 864 4,212 919

Table 2. Days available for continuous supply of water from the water reservoir in Fláje.

Total take- Storage


Storage Water off from the in the
volume take-off Outflow Inflow Difference reservoir reservoir
Fláje mil.m3 m3/day m3/day m3/day m3/day m3/day days

Minimum outflow/zero inflow 19.5 33,209 6,480 0 −6,480 39,689 491


and full storage
Minimum outflow/zero inflow 9.5 33,209 6,480 0 −6,480 39,698 239
and current storage
Minimum same inflow and 19.5 33,209 6,480 6,480 0 33,209 587
outflow and full storage
Minimum same inflow and 9.5 33,209 6,480 6,480 0 33,209 286
outflow and current storage
Reality 9.5 33,209 8,640 9,504 864 32,345 294

Table 3. Days available for continuous supply of water from the water reservoir in Žlutice.

Storage Water Total take-off Storage in


volume take-off Outflow Inflow Difference from the reservoir the reservoir
Žlutice mil.m3 m3/day m3/day m3/day m3/day m3/day days

Minimum outflow/zero 10.46 7,455 19,008 0 −19,008 26,463 395


inflow and full storage
Minimum outflow/zero 6.22 7,455 19,008 0 −19,008 26,463 235
inflow and current storage
Minimum same inflow and 10.46 7,455 19,008 19,008 0 7,455 1,403
outflow and full storage
Minimum same inflow 6.22 7,455 19,008 19,008 0 7,455 834
and outflow and current
storage
Reality 6.22 7,455 22,464 24,192 1,728 5,722 1,086

200
minimum long-term outflow, 50 l/s, should be would be sufficient to 2 years. These are prelimi-
always maintained. nary calculations only. The problem is that it is not
It follows from the table if there is no inflow into possible to forecast duration of the drought. It will
the water reservoir in Přísečnice, volume of water be necessary to plan and prepare regulatory meas-
should be sufficient for two years. This is very ures in order to decrease gradually consumption of
favourable. The reason is that the storage volume drinking water by customers.
is full more than at 84%. If there is no inflow for a The purpose is to ensure continuity in drinking
long time, the quality of water may become worse. water supplies because any interruption in the con-
The similar calculation was carried out for tinuous water supply results, finally, in even bigger
the water reservoir in Fláje. Its total volume is losses of water. It will be also necessary to check
23.1 mil.m3, while its storage volume is 19.5 mil.m3. technical.
The maximum water take-off is 510 l/s. The current
take-off of water is 498 l/s. The minimum outflow
of water into a river is 75 l/s. 7 CONCLUSION
If the inflow is same as the outflow, the water in the
reservoir will be sufficient for 286 days with the current Experience resulting from the recent periods of
volume. This is considerably less than in Přísečnice drought and the expected changes in dry periods
because the storage in Fláje is full at 48% only. prove that it is necessary to prepare measures in
The total volume of the Žlutice water reservoir is order to manage the situation. The purpose of
15.6 mil.m3, while its storage volume is 10.4 mil.m3. the drought management measures and actions is
The maximum water take-off is 190 l/s, while the to minimise negative impacts for drinking water
current take-off is 86 l/s. The minimum required supplies. Technical and regulatory measures should
outflow from the reservoir into the watershed is be prepared at the level of each location. Possible
220 l/s which is quite a lot for the reservoir volume. deficits in sources should be identified and mana-
If the inflow into the Žlutice reservoir is zero gement methods should be suggested for specific
and the required maintained outflow is main- situations. Other measures, such as legislative and
tained, the quantity of water is enough for economic ones, should be prepared jointly for the
239 days with the current average daily take-off entire territory.
and with the current volume of water in the res-
ervoir. The problem is that the permit outflow
into the watershed is rather high, because water REFERENCES
is used there for generation of electricity. In peri-
ods of drought, the situation is Fláje and Žlutice Czech Hydrometeorogical Institute 2015. http://
is not so favourable for drinking water supplies as [Link]/files/portal/docs/meteo/ok/SUCHO/
in Přísečnice, If the drought in 2015 continues, the zpravy/2015/[Link] (in Czech).
Howard, G., Charles, K., Pond, K., Brookshaw, A.,
water would be sufficient for 8 months only and Hossain, R., Bartram, J.: Securing 2020 vision for 2030:
this would require special measures aimed at regu- climate change and ensuring resilience in water and
lated take-off of water. sanitation services. Journals Water and Climate changes,
volume 1, number 1, March 2010, pages 2–16.
IPCC Climate Change, 2007. The Psysical Science Basic.
6 DROUGHT MITIGATION MEASURES Contribution of Working Group I to the Fourth
PROPOSED FOR THE TERRITORY Assessment.
Massley, E. D. Huitema, H. Garrelts, K. Grecksch, H.
Features of the water treatment plants because Mees, T. Rayner, S. Storgjörk, C. Termeer & M. Winges.
2000. Handling adaptation policy choices in Sweden,
quality of water may deteriorate in periods of Germany, the UK and the Netherlands. In Journal of
droughts The forecast drought may last rather Water and Climate Change 06. 1.
long, even three-year periods cannot be excluded. Ministry of the Environment, 2014. Strategies to adapt to
In order to improve the situation there, a solution climate change in the Czech Republic (in Czech).
would be to connect the water system in Přísečnice Pretel, J. et al. 2001. Specification of existing estimates of the
with those in Fláje and Žlutice. In that case, the impacts of climate change in the sectors of water, agricul-
total storage of water in those three water reser- ture and proposals for adaptations. Final report on the
voirs would be enough for 15 months. This would project VaV SP/1a6/108/07 for the period 2007–2011.
need a rather long preparation and investments, Report of the Intergovernmental Panel on Climat
Change (Solomon, S., D. Qin, M. Manning, Z. Chen,
but that measure might be suitable for the future. J. Marquis, K.B. Averyt, M. Tignor and H.L. Miller.
Another emergency measure would be to decrease Cambridge University Press, Cambridge, United
the outflow from the Žlutice reservoir down to Kingdom and New York, NY, USA, 996 p.
100 l/s or even down to 50 l/s as in Přísečnice. This Tolasz et al. 2007. Climate atlas of Czechia. Český
would improve the situation and water supplies hydrometeorologický ústav Praha 256 p. (in Czech).

201
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Benthic macroinvertebrates from Dongnai estuaries


in Southern Vietnam

M.T. Dang & A.D. Pham


Faculty of Environment and Labor Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

T.S. Dao
Faculty of Environment and Resources, Ho Chi Minh City University of Technology,
Vietnam National University, Ho Chi Minh City, Vietnam

V. Lapčík
Faculty of Mining and Geology, VSB—Technical University of Ostrava, Ostrava, Czech Republic

ABSTRACT: In this study, the variables of benthic macroinvertebrates and water quality were
investigated in Dongnai Estuaries, Southern Vietnam. Benthic macroinvertebrates were monitored in
April and September 2015 at 10 sampling sites in the river. Some basic environmental parameters were also
tested including pH, Total Suspended Solid (TSS), Dissolved Oxygen (DO), Biological Oxygen Demand
(BOD5), NH4+ (inorganic nitrogen), PO43− (dissolved phosphorus), and coliform. The biodiversity index
of benthic macroinvertebrates were applied for water quality assessment. The results showed that pH
ranged from 6.9–7.5 during the monitoring. The TSS concentrations were in between 50–78 mg/L. The
DO and BOD5 ranked from 3.4–6.1 mg/L and 3.5–13.2 mg/L, respectively. The NH4+ and PO43− concen-
trations were from 0.57–1.44 and 0.13–0.43 mg/L, respectively. The coliform number ranked between
4.3 × 103 – 2.3 × 104 MPN/100 mL. The analyses of benthic macroinvertebrates showed that there were
51 species of polychaetes, gastropods, bivalves, ophiuroids, and crustaceans. Of which, species of poly-
chaetes were dominant in species number. Density of benthic macroinvertebartes ranged from 133–459
individuals/m2 with the main dominant species of Nephthys polybranchia, Neanthes caudata, Prionospio
sp.; Owenia fusiformis, Bispira polymorpha, Tachaea sp. (April); Prionospio sp., Owenia fusiformis, Bispira
polymorpha, Grandidierella lignorum, Tachaea sp., Apseudes vietnamensis (September). The values of bio-
diversity index during the monitoring were from 1.39–2.43 characterized for light pollution (oligotrophic
to mesotrophic) to low moderate pollution (mesotrophic) conditions of the aquatic environment. Besides,
species richness strongly correlated with only pH, DO, BOD5, NH4+, PO43−, and coliform while densities
of benthic macroinvertebrates got positive correlation with only pH and coliform. The results confirmed
the advantage of using benthic macroinvertebrates and their indices for water quality monitoring.

Keywords: Dongnai Estuaries, Benthic macroinvertebrates, Water quality, Biological index

1 INTRODUCTION as leaves and algae. Other higher order organisms


such as birds, fish and larger insects then feed on
Aquatic macroinvertebrates are organisms that live aquatic macroinvertebrates (Carmen et al. 2015).
in the water, are visible with the naked eye > 0.2 mm Littoral macroinvertebrates occur in areas near
without the use of a microscope, and lack an inter- the shoreline, while benthic macroinvertebrates
nal skeleton. Examples of aquatic macroinver- live in the deeper-water areas away from the shore-
tebrates include insects, worms, snails, mollusks, line (MRC 2010). Benthic macroinvertebrates are
and crustaceans. Aquatic macroinvertebrates are widely used to monitor and assess water quality in
typically found living under rocks or logs or liv- streams. They are animals found on the bottom of
ing in congregated leaf packs (Carmen et al. 2015). a water body that are large enough to be seen with
Aquatic macroinvertebrates are an integral part of the naked eye and lack a backbone and internal
the food chain. Without these creatures, a stream’s skeleton. They are relatively sedentary and wide-
entire aquatic food web would collapse. Many spread, with varying tolerances to changes in water
macroinvertebrates feed on organic material such and sediment quality (EcoSpark 2013). Moreover,

203
macroinvertebrate populations in streams and industrial, agricultural, aquaculture and domestic
rivers can assist in the assessment of the overall activities by human beings (Pham 2004).
health of the stream (Rosenberg and Resh 1993). In Dongnai Estuaries, samples of qualitative
In Vietnam, a variety of investigations have and quantitative benthic macroinverbrates, and
been conducted focusing on morphological bio- water qualtiy at 10 sites were collected in April and
diversity and ecological conditions of benthic September 2015 (Figure 1; Table 1) (MRC 2010).
macroinvertebarates (Pham 2004; Pham et al. The samples for water quality analysis in the field
2012; Pham et al. 2015). However, publications on were collected according to the Operational Guide
interaction between benthic macroinvertebartes (3rd Ed.), UN Environment Programme (1992)
and environmental parameters and water quality (UNWP.—GEMS/Water 1992). The samples were
based on benthic macroinvertebartes from rivers
in Vietnam are limited. Pham et al. found the vari-
ation of benthic macroinvertebartes abundance
between dry and rainy seasons, and the classifi-
cation of water quality levels in Lower Dongnai
River System (Pham 2004; Pham et al. 2015). In
this study we investigated the variation of ben-
thic macroinverbrates as well as the water quality
based on benthic macroinvertebartes in Dongnai
Estuaries, Southern Vietnam.

2 MATERIALS AND METHODS

2.1 Study area and sample collection


Data from over 700 Km2 Dongnai Estuaries were
used as a representative example for rivers in estuary
areas of Dongnai River System. It located in Ho
Chi Minh City and apart of Dong Nai, Ba Ria—
Vung Tau, Long An and Tien Giang Provinces,
Southern Vietnam. Dongnai Estuaries plays a key
role in ecological and environmental services, and
navigation as well. Currently, Dongnai Estuaries Figure 1. Dongnai estuaries with 10 sampling sites
has been received many different effluents from (HL1–HL10).

Table 1. Coordinates and locations of the sampling sites.

Sites Local names Longitude (N) Latitude (S)

HL1 Nha Be River at Binh Khanh Ferry 106°46'24.04"E 10°40'14.92"N


HL2 La Canal at Rach La Bridge 106°47'17.82"E 10°38'45.42"N
HL3 Nha Be River at Hiep Phuoc 106°45'12.21"E 10°38'48.88"N
Indutrial Park
HL4 Soai Rap River at Soai Rap River 106°44'55.41"E 10°28'51.12"N
Mouth
HL5 Vam Sat Canal at Confluence of 106°47'43.90"E 10°32'14.43"N
Vam Sat Canal and Lo Ren River
HL6 Mui Nai River at Core of Can Gio 106°55'57.78"E 10°36'04.54"N
Magrove
HL7 Long Tau River at Tam Thon Hiep 106°53'03.39"E 10°34'33.36"N
Commune
HL8 Dong Tranh River at Conflunce 106°51'51.59"E 10°29'38.48"N
of Dong Tranh River and Ba
Gioi River
HL9 Nga Bay River at Confluence of 106°55'09.01"E 10°31'51.64"N
Dua River and Nga Bay River
HL10 Cai Mep River Mouth 107°00'35.84"E 10°31'00.21"N

204
taken in April and September of 2015. Sample collected are identified and counted under a
locations at each site were taken in the right and compound microscope (with a magnification of
left parts of the river with depth layer of surface 40–1200x) or a dissecting microscope (16–56x).
water from 30–40 cm. The water samples were Polychaeta, Gastropoda, Bivalvia, and Crustacea
collected in 2 liter plastic bottles and kept at 2°C are generally identified to species level. The results
temperature (UNWP.—GEMS/Water 1992). were recorded on data sheets and specimens are
Before sampling benthic macroinvertebartes at kept at the Ton Duc Thang University, Ho Chi
each site, the equipment is washed to remove any Minh City, Vietnam (Pham 2004; MRC 2010;
organisms and other matter left from the previous Pham et al. 2015).
site. Sampling locations at each site are selected in
the right and left parts of the river at 2–3 m depth.
2.3 Data analysis
Samples are taken at five locations at each of the
two parts of the river. More samples are required at For all sites sampled in April and September 2015
sites with higher inter-sample variability, such as in the following metrics were calculated (i) taxonomic
the Dongnai Esturies, than in sites with lower vari- richness (i.e. number of taxa); (ii) abundance (i.e.
ability. At each sampling location, four sub-samples numbers of individuals per site); (iii) the Shannon-
are taken with a Petersen grab sampler and com- Wiener Diversity Index (Stiling 2002). The Pearson
posited into a single sample, covering a total area of test (SPSS, version 16.0) was used for calculation
0.1m2. Grab contents are discarded if the grab did on the correlation between benthic macroinverte-
not close properly because material such as wood, brates species number, abundance and biodiversity
bamboo, large waterplants, or stones jammed the index) and environmental parameters in Dongnai
grab’s jaws. In these cases the sample is retaken Estuaries. The three metrics were tested for their
(Pham 2004; MRC 2010; Pham et al. 2015). potential as indicators of human impact by
Each sample is washed through a sieve (0.3 mm regressing values for two seasons of 2015 (20 sam-
mesh) with care taken to ensure that macroinver- pling events for 10 sites) against the water quality
tebrates did not escape over the sides of the sieve. variables (pH, TSS, DO, BOD5, NH4+, PO43−, and
The contents of the sieve are then placed in a white coliform). For each metric examined against these
sorting tray and the material (including the ben- variables, p values and r2 values were calculated
thic macroinvertebrates) is dispersed in water. All from regression analyses.
the animals in the tray are picked out with forceps
and pipettes, placed in jars, and fixed with 10% for-
maldehyde to a final concentration of 5%. Alter- 3 RESULTS
natively, 95% ethanol can be used. It is crucial that
the final alcohol concentration after specimens are The pH values of surface water during the monitoring
added never falls below 70% or the specimens will times ranged from 6.9–7.5, neutral indicator among
deteriorate and not be identifiable. Samples of less the sampling sites and through out the year (Table 2).
experienced sorters are checked by an experienced The TSS highly fluctuated from 50–78 mg/L. In
sorter (Pham 2004; MRC 2010; Pham et al. 2015). rainy season, the TSS concentrations in Dongnai
The sample jar is labelled with the site name, Estuaries were higher than these in dry season. The
the location code, the date, the position within the DO and BOD5 values were from 3.4–6.1 mg/L and
river, and the sample replicate number. The sam- 3.5–13.2 mg/L, respectively. The NH4+ and PO43−
pling location conditions, collector’s name and concentrations in Dongnai Estuaries fluctuated from
sorter’s name are recorded on a field sheet. Some- 0.57–1.4 mg/L and 0.13–0.43 mg/L, respectively. And,
times, samples cannot be sorted on site because the the coliform values were from 4.3 × 103 – 2.3 × 104
boat is poorly balanced, a very large number of MPN/100 mL in Dongnai Estuaries (Table 2).
animals are collected, there is insufficient time at a During the two monitoring times, there were 51
site, or because the presence of lumps of clay cause species of benthic macroinvertebrates belonging
the samples to cloud continually. In these cases, the to 5 groups of polychaetes, gastropods, bivalves,
entire sample is preserved and sorted in the labora- ophiuroids, and crustaceans in the studied area.
tory (Pham 2004; MRC 2010; Pham et al. 2015). Among the benthic macroinvertebrates groups,
polychaetes were dominant in species number with
28 species in total, gaining around 54.9% of total
2.2 Physical, chemical and benthic
(Table 3). In each monitoring, species number of
macorinvertebrate analysis
benthic macroinvertebrates ranged from 48 (in
The aquatic environmental parameters (pH, April) to 50 (in September).
TSS, DO, BOD5, NH4+, PO43−, and coliform) All species and genera of benthic macoinver-
were analyzed according to standard methods tebrates recorded in the Dongnai Estuaries were
(APHA-AWWA-WEF 1998). All individuals originated from the estuary or coastal region.

205
Table 2. Physical, chemical and microbial parameters from Dongnai Estuaries during 2015. Data were presented as
minima to maxima values.

TSS DO BOD5 NH4+ PO43– Coliform


Sites pH mg/L mg/L mg/L mg/L mg/L MPN/100mL

HL1 7.1–7.2 52–72 5.2–5.9 5.3–7.3 1.15–1.27 0.21–0.24 2.3 × 104


HL2 6.9–7.0 50–68 3.4–4.8 7.9–13.2 1.28–1.44 0.32–0.43 1.1 × 104−2.3 × 104
HL3 7.0–7.3 53–71 5.3–5.9 5.0–5.9 0.83–0.84 0.19–0.20 9.3 × 103−1.1 × 104
HL4 6.9–7.3 54–73 5.6–6.1 4.9–5.6 0.76–0.78 0.18–0.19 9.3 × 103−1.1 × 104
HL5 7.1–7.3 54–78 5.0–5.7 4.3–5.4 0.77–0.86 0.18–0.19 4.3 × 103−1.1 × 104
HL6 7.3–7.5 51–64 5.9–6.1 3.5–3.9 0.57–0.69 0.13 4.3 × 103
HL7 7.2–7.4 54–70 5.3–5.9 4.6–5.7 0.81–0.82 0.15 9.3 × 103
HL8 7.3–7.5 53–57 5.6–5.9 4.7–5.4 0.89–1.07 0.16 9.3 × 103
HL9 7.4–7.5 57–70 5.8–6.0 4.0–4.8 0.88–1.13 0.15–0.16 4.3 × 103−9.3 × 103
HL10 7.3–7.4 58–70 4.5–5.3 7.4–9.6 1.35–1.60 0.30–0.33 9.3 × 103

Table 3. Structure of benthic macroinvertebrates com-


munities from Dongnai estuaries during 2015. Numbers
in the table indicated the species number of each benthic
macroinvertebrates group.

Macroinvertebrates April September Total %

Polychaeata 25 27 28 54.9
Gasatropoda 4 4 4 7.8
Bivalvia 5 5 5 9.8
Ophiuroidea 1 1 1 2.0
Crustacea 13 13 13 25.5
Total species number 48 50 51 100 Figure 2. Density of benthic macroinvertebrates from
Dongnai estuaries during 2015.

Table 4. Biodiversity index values (H’) of benthic macroinvertebrates from dongnai estuaries during 2015.

H’ HL1 HL2 HL3 HL4 HL5 HL6 HL7 HL8 HL9 HL10

04/15 1.78 1.39 2.09 2.18 1.75 2.33 2.21 2.24 1.97 1.81
09/15 1.71 1.50 2.10 2.07 1.93 2.43 2.15 2.26 1.98 1.52

A number of the species that were widespread The values of benthic macroinvertebrates
were Nephthys polybranchia, Neanthes caudata, biodiversity index during the monitoring in 2015
Prionospio, Bispira polymorpha, Grandidierella ranged from 1.39–2.43 (Table 4). In Dongnai
lignorum, Tachaea sp., Mesopodopsis slabberi Estuaries, the values of biodiversity index at the sites
(April); Nephthys polybranchia, Neanthes cau- of Can Gio Mangrove (HL6, HL7, and HL8) were
data, Bispira polymorpha, Grandidierella lignorum, higher than these in the disturbed sites (HL1, HL2,
Tachaea sp., Alpheus bisincisus (Septemeber). HL5, and HL10). The biodiversity values were not
Density of benthic macroinvertebrates ranged much different between two seasons (Table 4).
from 133–459 individuals/m2, lowest at the sam- The statistical data treatment showed that spe-
pling site 4 (Soai Rap River at Soai Rap River cies number of benthic macroinverbrates strongly
Mouth) and highest at the site 3 (Nha Be River correlated with almost environmental variables
at Hiep Phuoc Indutrial Park, Fig. 2). The domi- of pH, DO, BOD5, NH4+, PO43−, and coliform in
nant species in the monitored area were Nephthys water (r = 0.4075–0.6166; Figure 3). While, density
polybranchia, Neanthes caudata, Prionospio sp.; of benthic macroinvertebrates positively correlated
Owenia fusiformis, Bispira polymorpha, Tachaea sp. with only pH and coliform (r = 0.1434–0.1471;
(April); Prionospio sp., Owenia fusiformis, Bispira Figure 4); and negatively correlated with DO,
polymorpha, Grandidierella lignorum, Tachaea sp., BOD5, NH4+, and PO43− concentrations in water
Apseudes vietnamensis (September). (r = 0.0008–0.0433). Besides, the biodiversity of

206
Figure 3. Species richness of benthic macroinverbrates strongly correlated with all environmental variables of pH,
DO, BOD5, NH4+, PO43–, and coliform.

benthic macroinverbrates highly correlated with


almost environmental variables of DO, BOD5,
NH4+, and PO43− in water (r = 0.5507–0.6725).
However, the biodiversity negatively correlated
with TSS (r = 0.0028).

4 DISCUSSION

As a running water body, Dongnai Estuaries had


the pH of neutral water (Table 2) and was similar
the pH in sites of Thi Vai River and Ganh Rai Bay
(Pham 2004; Pham et al. 2012). In the rainy season,
the TSS concentrations were high than these in the
dry season because of strong flows.
The NH4+ and PO43− concentrations in Dongnai
Estuaries were lower than these inorganic nitro-
gen and dissoved phosphorus concentrations from
Thi Vai River, fluctuated from 1.8–3.7 mg/L and
0.34–1.01 mg/L (Pham 2004, Pham et al. 2012),
and not as high as that in inside canals of Ho
Chi Minh City, ranging from 3.2–4.0 mg/L and
Figure 4. Density of benthic macroinverbrates posi- 1.20–1.34 mg/L (Pham et al. 2012). Therefore, the
tively correlated with all environmental variables of pH Dongnai Estuaries should be characterized for
and coliform. high mesotrophic condition in the dry season and

207
low mesotrophic level in the rainy season, in term water. Besides, the biodiversity index of benthic
of NH4+ and PO43− during the monitoring in 2015. macroinverbrates highly correlated with environ-
Pham at al. (2012) recorded from 47–54 species of mental variables of DO, BOD5, NH4+, and PO43− in
benthic macroinvertebrates during 6 year monitoring water. However, the biodiversity index negatively
in Can Gio area in which polychaetes contributed correlated with TSS.
highest species number to the benthic macroinverte- Results of this study contributed the interest-
brates community (Pham et al. 2012). Through out ing information on benthic macroinvertebrates
5 years of sampling in Tien Giang coastal, 28 spe- structure, their correlation with environmental
cies of benthic macroinvertebrates reported in which parameters and ecological characteristics, which
polychaetes was also dominant in species number was quite limited in Southern Vietnam. Besides,
(Pham et al. 2014). For the whole year of monitoring the results confirmed the advantage of using ben-
in this area, polychaetes contributed highest number thic macroinvertebrates and their indices as useful
of species. This should be related to the water char- tools for environmental monitoring and ecological
acteristics of the Dongnai Estuaries, strongly influ- health assessment.
enced by sea water from the East Sea.
In general, species number and densities during
the monitoring were effected by water quality in ACKNOWLEDGEMENT
Dongnai Estuaries. The environmental conditions
were favorable for benthic macroinvertebrates We would like to thank Dr. Dang Quoc Dung for
development as mentioned above. helping with the sampling map.
The bio-diversity index values were character-
ized for low mesotrophic condition in the rainy
season and high mesotrophic condition in the dry REFERENCES
season of the aquatic environment. Generally, the
biodiversity index values were similar between dry APHA-AWWA-WEF. 1998. Standard Methods for
season (April) and the rainy season of the year Examination of Water and Wastewater (20th Ed.).
American Public Health Association, Washington,
(September, Table 4). Besides, the values seemed to D.C..
be higher at the sites in Can Gio mangrove. Those Carmen, T. Agouridis, Evan, T. Wesley, & Tyler, M.
should be related to the better selpurification of Sanderson, Blake L. Newton (2015). Aquatic Macroin-
mangrove area. vertebrates: Biological Indicators of Stream Health.
University of Kentucky College of Agriculture, Food
and Environment, Lexington.
5 CONCLUSION EcoSpark. 2013. Water Quality Monitoring with Benthic
Macroinvertebrates (5th Ed). EcoSpark, CA.
During the two monitoring times in 2015 in Dong- MRC. 2010. Biomonitoring Methods for the Lower Mekong
Basin. Mekong River Commission, Vientiane.
nai Estuaries, the nutrients including NH4+ and Pham, A.D. 2004. Study on Benthic Macroinvertebrates
PO43− concentrations were characterized for low for Water Quality in River Systems of Can Gio Dis-
mesotrophic condition in the rainy season and high trict, Ho Chi Minh City. Master Thesis, Institute of
mesotrophic condition in the dry season. Besides, Environment and Resources—Vietnam National Uni-
pH were favorable for development of benthic versity, HCMC.
macroinvertebrates. There were 51 species of ben- Pham, A.D., Nguyen, T.M.L. & Pham, V.M. 2012. The
thic macroinvertebrates belonging to 5 groups of Water Environment and Ecological Monitoring in the
polychaetes, gastropods, bivalves, ophiuroids, and Dongnai River System. Institute of Meteorology,
crustaceans, in the studied areas of which crus- Hydrology and Environment, Tp. HCM.
Pham, A.D., Le, P.Q. & Le, P.N. 2015. Linking Benthic
taceans was dominant in species number. Gener- Macroinvertebrates and Physicochemical Variables
ally, species number and abundance of benthic for Water Quality Assessment in Lower Dongnai
macroinvertbrates during the monitoring charac- River System, Vietnam. International Journal of Envi-
terized in usual conditions. The values of benthic ronmental Science and Development, 6 (2), 88–92.
macroinvertebrates biodiversity index reflected for Pham, V.M., Pham, A.D. & Nguyen. T.M.L. 2014. The
light pollution (oligotrophic to mesotrophic) to Water Environment and Ecological Monitoring in the
low moderate pollution (mesotrophic) conditions. Tien Giang Coastal. Institute of Environmental Sci-
The species number of benthic macroinverbra- ence and Development, HCMC.
tes strongly correlated with almost environmental Rosenberg, D.M. & Resh, V.H. 1993. Freshwater biomoni-
toring and benthic macroinvertebrates. Chapman &
variables of pH, DO, BOD5, NH4+, PO43−, and Hall, New York.
coliform in water. While, density of benthic mac- Stiling, P. 2002. Ecology: Theories and Applications, 4th
roinvertebrates positively correlated with only Ed. Prentice-Hall of India Private Ltd, New Delhi.
pH and coliform; and negatively correlated with UNWP.—GEMS/Water. 1992. Operational Guide
DO, BOD5, NH4+, and PO43− concentrations in (3rd Ed.). UN Environment Programme, Burlington.

208
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Flow simulation in Sai Gon-Dong Nai river system using TELEMAC 2D

Q.D. Dang & T.D. Nguyen


Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: Application of hydraulic model has play an important role in simulating flow, flood, or
pollutants transport in the rivers or seas. TELEMAC MASCARET system consists of many modules
based on the powerful algorithms and utilizes both finite element and finite volume methods. In this
study, we have used TELEMAC 2D module to simulate the flow in Sai Gon—Dong Nai river system in
2014. The reasonability in calibrated model is the good foundation for computing the pollutants transport
and dispersion in near future.

Keywords: Flow simulation, Sai Gon-Dong Nai river system, TELEMAC 2D

1 INTRODUCTION 2004). The Saint—Venant equation can be used


to simulate a diversity of flow types in different
Sai Gon—Dong Nai river system is largely within natural settings, such as marine currents, coastal
the administrative boundaries of the cities of Tay currents, estuaries, lake and river flows, or used
Ninh, Thu Dau Mot, Tan An as well as a part of in conjunction with different modules to calculate
Ba Ria—Vung Tau, with the geographical location water quality, sediment transport and wave propa-
extending from 10°30'N 11°30'N and 107°13'E gation (Hyng and Vu 2015; Denis et al. 2014). The
105°60'E. This region is not only the most densely TELEMAC 2D code solves the following four
populated area in Vietnam, but is also the eco- hydrodynamic equations simultaneously (Telemac
nomic and commercial center of the country. This version 7.0):
river system not just consists of major rivers such
as the Sai Gon River (256 km) and Dong Nai River  
∂h
(470 km) but a variety smaller rivers like Vam Co
Dong (218 km) and Vam Co Tay (140 km) (Dang

⎪ ∂t
()
+ u grad ( ) + hdiv = Sh
⎪ ∂h    ∂Z
and Pham 2014).
Scientific flow study of Sai Gon—Dong Nai
⎪ + u grad ( ) = − g
⎪ ∂t ∂x
1
h
(
+ Sx + div hvt grad u )
⎨ ∂v    ∂Z
river system is a meaningful and practical issue.
Basing on the results, we can clearly see the influ-
⎪ + u grad (v ) = − g
⎪ ∂t ∂y
1
+ Sy + div
h
( )
∂T     
ence of flow on the downstream; while when coop-
erating with other modules, we can also evaluate the

⎪⎩ ∂t
1
(
+ u grad ( ) = ST + div hvvt grad T
h
)
distribution of pollutants in the basin or forecast
the possibility of flooding. This acts as the basis
in which:
for setting up projects to control the water quality
h (m): depth of water
and effectively manage basin, which helps improve
u,v (m/s): velocity components
clean water sources for people in the region.
T (g/l or °C): passive (non-buoyant) tracer
G (m/s2): gravity acceleration
2 BIDIRECTIONAL EQUATION IN FLOW Vt, vT (m2/s): momentum and tracer diffusion
SIMULATON coefficients
Z (m): free surface elevation
Bidirectional equation of Saint—Venant is derived t (s): time
from Navier—Stokes equation. It applied for x,y (m): horizontal space coordinates
incompressible fluids and under the assumptions Sh (m/s): source or sink of fluid
that the pressure is hydrostatic; the speed con- Sx,Sy (m/s2): source or sink terms in dynamic
forms vertically; the bottom is impermeable and equations
the surface retains the free flow (Lee and Lam ST (g/l/s): source or sink of tracer

209
3 TELEMAC 2D MODEL FOR FLOW
SIMULATION IN SAI GON—DONG
NAI RIVER SYSTEM

3.1 Computational domain


The computational domain is limited to the whole
river system of Sai Gon—Dong Nai river, includ-
ing the 05 discharge boundary and 01 water level
boundary (Figure 1). Water level boundary is data
extrapolated from two monitoring stations of Vam
Kenh and Vung Tau for 03 days (from 10/12/2014
to 12/12/2014).

3.2 Computational grid


The combined mesh for the whole Sai Gon—Dong
Nai river system is formed from 256893 notes and
507806 triangular elements (Figure 2).

Figure 2. Combined mesh in network.


3.3 Boundary conditions
The boundary condition of discharges from
10/12/2014 to 12/12/2014 are respectively shown in
Figures 3–7.

3.4 Model calibration


Calibration parameters of model are expressed in
Table 1.
Velocity field and water depth are shown in
Figures 8–9. Velocity field is in accordance with the
observed results of the HCMC Environmental Pro- Figure 3. Inflow at Tri An lake.
tection Agency (HEPA) in 2014 [Range: 0,004 m/s

Figure 4. Inflow at Phuoc Hoa.

Figure 1. Computational domain. Figure 5. Inflow at Dau Tieng lake.

210
Figure 6. Inflow at Go Dau Ha.

Figure 9. Water depth in SG—DN river system at 72h.

(Phu Cuong station) – 0,143 m/s (Phu An station)).


Figure 7. Inflow at Moc Hoa.
(HEPA 2014).

Table 1. Calibration parameters. 4 CONCLUSION


Issues Tough The result showed that two-dimensional hydrody-
namic model (TELEMAC-2D) can simulate the
Children Face Tough flow in SG—DN river system with high reliabil-
ity. Flow simulation is conducted in a short time
Children Face Issues (03 days) in rainy season; therefore, change in flow
velocities are not reflected fully. However, reason-
Children Face Tough Issues ability in calibrated model is the good foundation
for computing the pollutants transport and disper-
Children Face Tough Issues sion in near future.

REFERENCES

Dang, Q.D., & Pham, A.D. 2014. Application of gis in


estimating seasonal water quality in lower Dong Nai
river system. 1–6.
Denis, C., Moulinec, C., Barber, RW., Emerson, DR.,
HEPA. 2014. The observation results of the environmen-
tal protection agency in Ho Chi Minh City in 2104.
Ho Chi Minh City Environmental Protection Agency
(HEPA) in 2014.
Huynh, T.S., & Vu, C.C. 2015. Study on the vertical
velocity distribution in the Ganh Hao river (Bac Lieu
province). 455–458.
Lee, J.H.W., & Lam, K.M. 2004. Environmental hydrau-
lics and sustainable water management. 540–545.
Razafindrakoto, E., & Hervouet, J-M. 2011. Accurate
simulation of large-scale hydrodynamic events using
TELEMAC-2D. 2–5.
Telemac version 7.0. Release notes. TELEMAC-2D and
BIEF. [Link]
Figure 8. Velocity field in SG—DN river system at 72h. atid=355&subcatid=0&newsid=607&langid=0

211
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Toxicity of cyanobacterial extract from Cylindrospermopsis raciborskii


and potential solutions for mitigation the cyanobacterial mass
development in Xuan Huong Lake, Da Lat City, Vietnam

T.S. Dao & T.P.L. Nguyen


Faculty of Environment and Resources, Ho Chi Minh City University of Technology,
Vietnam National University, Ho Chi Minh City, Vietnam

T.K.T. Vo
Institute of Tropical Biology, Ho Chi Minh City, Vietnam

ABSTRACT: Cyanobacterial blooms have been increasing both frequency and intensity in water bodies
worldwide. Negative effects of cyanobacterial mass development on aquatic environment and ecosystems
attracted various attention and investigations. This study aimed to evaluate the detrimental impacts of
cyanobacterial extract of the cyanobacterium Cylindrospermopsis raciborskii isolated from Xuan Huong
Lake on the survival and reproduction of a micro-crustacean, Daphnia magna, through a chronic incuba-
tion. The results showed the cyanobacterial crude extract at the concentrations of 1 and 5 mg/L stimu-
lated the reproduction and slightly affect on survival of D. magna. However, the concentrations of 25 and
100 mg/L resulted in a high mortality proportion and reduced the total accumulated offspring of the
animals. Potential solutions for mitigation the cyanobacterial blooms in Xuan Huong Lake are suggested
to protect the ecological health of the local aquatic ecosystem.

Keywords: cyanobacterial extract, Daphnia magna, survival, reproduction, cyanobacterial mitigation.

1 INTRODUCTION other animals of the higher trophic levels (e.g.


small fish). Cyanobacteria are not only low nutri-
Cyanobacteria (cyanoprokaryota, cyanophyta, ent food for but also potent toxic to zooplankton
blue-green algae) are among the organisms firstly (Lampert, 1977; Dao et al., 2010a). Considerable
appearing on earth and existing for billions of numbers of laboratorial studies investigated and
years (Graham and Wilcox, 2000). They are showed the acute and chronic effects of cyanoto-
found in many different habitats. However, they xins on zooplankton in general and daphnids in
mainly occur in water bodies especially diverse particular concerning survival, food filtering, mol-
in freshwater lakes and reservoirs (Vincent, 2000; ting, enzyme activities and life history traits of the
Wynn-Williams, 2000; Barsanti et al., 2008). Being animals (e.g. Dao, 2010).
primary producers in water bodies, cyanobacteria In Vietnam, toxic cyanobacteria and their toxin
possess an important function in aquatic ecosys- production have been investigated and reported
tem. Together with algae, they offer primary pro- for over 15 years (Hummert et al., 2001; Nguyen
duction for organisms of higher trophic levels, et al., 2007; Dao et al., 2010b; Pham et al., 2015).
herbivorous animals, liberate a large amount of Besides, several investigations reported the toxicity
oxygen during their photosynthesis (Araoz et al., of cyanobacteria from Vietnam to fish (Dao et al.,
2010) and involve in the bio-geo-chemical cycle of 2013), plant (Dao et al., 2014a) and Daphnia (Dao
many basic elements (e.g. carbon, nitrogen, phos- et al., 2014b, c; Vo et al., 2015). In the mentioned
phorus). However, mass development or blooms publications, the cyanobacterial species Micro-
of cyanobacteria cause detrimental effects on cystis spp were used as the material for the tests.
aquatic organisms (e.g. zooplankton) and are of Another commonly found and potential toxic
serious concern for public health due to their vari- cyanobacterium Cylindrospermopsis raciborskii has
ous potent toxins. been increasing on its distribution and abundance
Zooplankton (e.g. Daphnia) have an intermedi- in tropical countries including Vietnam. However,
ate position in aquatic ecosystem. They feed on toxicity of C. raciborskii to Daphnia is not widely
micro algae and cyanobacteria, and are food for known and fully understood.

213
Xuan Huong Lake, the heart of Da Lat City, is
one of the best well known seight seeing for tourists.
This is a recreational water with around 32 ha
surface square. The lake has been human strongly
polluted by anthropogenic pollutants from activi-
ties such as farming and domestic waste (Dao et al.,
2014c). Mass development of cyanobacteria in the
lake has been occurred and intensively increased so
far (Fig. 1). The potential toxic cyanobacteria in the
lake were recorded such as Microcystis, Anabaena,
Cylindrospermopsis and Planktothrix with high
abundance (Dao et al., 2014c). In this study we
tested the toxicity of cyanobacterial extract of
C. raciborskii isolated from Xuan Huong Lake to Figure 2. Test organisms, Daphnia magna (left) and
Daphnia magna and recommended the potential Cylindrospermopsis raciborskii (right).
solutions on mitigation the cyanobacterial blooms
in the lake. cycle, samples were centrifuged at 4500 rpm, 4°C
for 15 min. Supernatant was collected and kept at
−70°C prior to experiments with D. magna.
2 MATERIALS AND METHODS Daphnia magna (obtained from Micro-Biotest
InC., Belgium) has well grown in the laboratory of
The cyanobacteriaum, C. raciborskii, was isolated the Institute of Tropical Biology for several years.
from Xuan Huong Lake (Dao et al., 2014c) and Prior to the experiments, fifteen female D. magna
cultivated in the laboratory conditions for biomass were incubated in a 500 mL beaker containing
collection. The dried biomass of C. raciborskii was COMBO medium (Kilham, 1998) and fed with
then used for cyanobacterial extract preparation Chlorella sp. for 2–3 weeks. Offspring from the
according to Pietsch et al. (2001) prior to the toxic- second clutch of these D. magna were used for
ity test with D. magna (Fig. 2). Briefly, the dried experiments. Daphnia was exposed to extract of C.
biomass of C. raciborskii on GF/C filters was raciborskii at the concentrations of 0 (control), 1,
homogenized, suspended into reversed osmosis 5, 25 and 100 mg DW/L. In each treatment, fif-
water, sonicated, frozen at −70°C over night and teen neonates less than 24 h old were randomly
thawed at room temperature. The freeze/thaw cycle selected and individually transferred into 50 mL
was repeated five times. After the last thawing glass beakers containing 20 mL of medium. The
animals were fed with Chlorella sp. at the concen-
tration of 2 mg C/L per day. The medium were
totally renewed 3 times every week. The tests were
run in the laboratory conditions of 20 ± 1ºC, light
intensity of around 1000 Lux, 12h light: 12h dark
cycle, and lasted for a period of 21 days (Dao et al.,
2010a). During incubations, animals were observed
daily for their survival, maturity and reproduc-
tion. Besides, pH and dissolved oxygen in the test
medium were measured on the date of starting and
medium renewal to confirm the favorable condi-
tions for the growth of D. magna.

3 RESULTS AND DISCUSSION

3.1 Effects of cyanobacterial extract on survival


of Daphnia magna
During the experiment, the pH of the test medium
ranged from 6.8–7.0 whereas the dissolved oxygen
concentrations valued 6.5–7.1 mg/L. These favo-
rable parameters excluded the negative effects of
Figure 1. Cyanobacterial mass development in (a, b) pH and oxygen availability to the test organism, D.
and a map of Xuan Huong Lake (c). magna, according to APHA (2005).

214
Table 1. Total Accumulated Offspring (TAO) of
Daphnia magna during the exposures.

Control 1 mg/L 5 mg/L 25 mg/L 100 mg/L

TAO 354 395 379 293 206

The cyanobacterial extract could induce the


increasing or decreasing the reproduction of
D. magna, depending on the cyanobacterial species
and exposed concentrations. For example, Dao
et al. (2010a) observed the 10%-decrease of total
Figure 3. Survival proportion of Daphnia magna dur-
offspring when D. magna exposed to extract of
ing the 21-day experiment. Microcystis aeruginosa. However, Tran et al. (2014)
reported that the number of offspring in exposure
to 10 and 50 mg/L of Planktothrix extraction were
The results from the chronic tests showed that 1.5–2 fold of the control. Therefore, further inves-
survival of D. magna in control and exposures to tigations for deeper understanding on the mecha-
low cyanobacterial extract concentrations (1 and nisms on stimulation and inhibition of Daphnia
5 mg DW/L) was not significantly different, from reproduction by cyanobacterial crude extract are
93%–100% (APHA, 2005). However, exposures suggested.
to higher extract concentrations, 25 and 100 mg
DW/L, the survival was 73% and 40% (Fig. 3).
Therefore, the negative effect of cyanobacterial 4 THE POTENTIAL SOLUTIONS FOR
extract on Daphnia survivorship was concentration MITIGATION THE CYANOBACTERIAL
dependence. This record was in line with a previ- BLOOMS IN XUAN HUONG LAKE
ous investigation from Vietnam (Dao et al., 2016).
The authors reported that D. magna exposed to Due to the negative effects of cyanobacteria on
10 and 50 mg DW/L of Planktothrix rubescens aquatic ecosystem and human beings, the control
crude extract slightly reduced its survival. How- and mitigation on cyanobacterial mass develop-
ever, exposure to 100 mg DW/L of P. rubescens ment have been implemented in the world. One
crude extract resulted in the mortality of 57% of of the first and important steps for control and
D. magna. Besides, Dao et al. mitigation is to limit and prevent the nutrients
(2014c) noted that all D. magna fed with around discharging into water bodies. Xuan Huong Lake
2 mg/L of live C. raciborskii died within 8 days of in Da Lat City has received untreated wastewater
incubation. Hence, live cells are more potent toxic from domestic and agricultural activities which
to D. magna than crude extract of C. raciborskii. enhanced the nutrient (e.g. dissolved nitrogen and
The explanation was that beside the potential toxic phosphorus) concentrations (Dao et al., 2014) con-
compounds, live cells of cyanobacteria in general sequently cyanobacterial bloom formation. Besides,
and C. raciborskii in particular were mal-nutrient the nutrients also settle at the bottom of Xuan
to D. magna. Huong Lake, a shallow water bodies, then could be
released back into the water through the geo-bio-
3.2 Effects of cyanobacterial extract on chemical cycle. Therefore, the potential solutions
reproduction of Daphnia magna (Chorus & Bartram, 1999; Falconer, 2005) for the
cyanobacterial bloom control and mitigation in
The total accumulated offspring in the control was
Xuan Huong Lake could be as below:
354. The number of total offspring in the expo-
sures to 1 and 5 mg/L were 395 and 379, respec- − Stop discharging the untreated wastewater into
tively, around 10% higher than that in the control the lake.
(Table 1). However, in the incubations of 25 and − Reduce the phosphorus concentration by means
100 mg/L, the total offspring were 293 and 206, of chemical (e.g. Fe2+), constructed wetlands.
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the D. magna. − Increase the water flow in and out of the lake.

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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Zooplankton from Thi Vai River in Southern Vietnam

T.T.H. Nguyen, T.M.L. Nguyen & A.D. Pham


Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

D.H. Vuong
College of Construction No 2, Ministry of Construction, Ho Chi Minh City, Vietnam

V. Lapčík
Faculty of Mining and Geology, VSB—Technical University of Ostrava, Ostrava, Czech Republic

ABSTRACT: In this study, the variables of zooplankton and water quality were investigated in Thi Vai
River, Southern Vietnam. Zooplankton were monitored in April and September 2015 at 5 sampling sites
in the river. Some basic environmental parameters were also tested including pH, Total Suspended Solid
(TSS), Dissolved Oxygen (DO), Biological Oxygen Demand (BOD5), inorganic nitrogen (NH4+), dissolved
phosphorus (PO43), and coliform. The biodiversity index of zooplankton were applied for water quality
evaluation. The results showed that pH ranged from 6.8–7.5 during the monitoring. The TSS concentra-
tions were in between 47–70 mg/L. The DO and BOD5 concentrations ranked from 1.8–6.1 mg/L and 4.2–
17.7 mg/L, respectively. The NH4+ and PO43– were from 0.87–1.94 and 0.22–0.53 mg/L, respectively. The
coliform number ranked between 2.3 × 103 – 1.1 × 104 MPN/100 mL. The zooplankton analyses showed
that there were 43 species of cladocerans, copepods, coelenterates, mysidacea, prochordates, protozoans,
and 5 larval types. Of which, species of copepods were dominant in species number. Zooplankton density
ranged from 16,900–81,800 individuals/m3 with the main dominant species of Acartia clausi (Copepoda)
and nauplius copepods. The values of biodiversity index during the monitoring were from 1.16–2.49 char-
acterized for oligotrophic to mesotrophic conditions of the aquatic environment. Besides, species richness
and density of zooplankton strongly correlated with DO, BOD5, NH4+ and PO43– while species richness
and densities did not correlation with TSS and pH, respectively. The results confirmed the advantage of
using zooplankton and their indices for water quality monitoring.

Keywords: Thi Vai River, zooplankton, water quality, biological index

1 INTRODUCTION Zooplankton is one of the most common organ-


isms on the earth, they mostly present and well
Zooplankton that consists of tiny animals, such as develop in aquatic habitats including lakes, ponds,
rotifers, copepods, and krill, and of microorgan- reservoirs, rivers, streams and oceans (Richardson
isms once classified as animals, such as dinoflag- et al. 2009). Many environmental factors inter-
ellates and other protozoans (Ferdous, Muktadir act to regulate spatial and seasonal growth and
2009). Like phytoplankton, Zooplankton are usu- succession of zooplankton (Ferdous, Muktadir
ally weak swimmers and usually just drift along 2009). The environmental variables DO and nutri-
with the currents (Ferdous, Muktadir 2009). ents are important for present and distribution of
Zooplankton are the key components of aquatic zooplankton for example the DO below 1.0 mg/L
ecosystems and the animal constituent of the would limit the development of zooplankton.
plankton, some are herbivores, feeding upon phy- Nutrients including NH4+ and PO43– are impor-
toplankton, while others are carnivorous, feed- tant for growth of zooplankton. Besides, pH and
ing upon other members of the zooplankton. TSS are essential for distribution of zooplankton
Some members of the zooplankton community, (Ferdous, Muktadir 2009; Orsi, Mecum 1986).
particularly copepods (small crustacea), are of Zooplankton could be used as bio-indicators for
importance to higher trophic levels as food for water quality and ecosystem health (MRC. 2010).
fish larvae. Zooplankton are critical links in riv- Besides, indices based on zooplankton such as bio-
erine food webs between phytoplankton and fish diversity, similarity, among others are useful for
(Thorp, Mantovani 2005). water quality and ecological health evaluation.

219
high, sometimes it was highly varied over 400 cm
with fast flows (Pham 2004; Pham and Le 2004). In
the dry season, the salinity of Thi Vai River fluctu-
ated from 24 to 32% in the dry season and from
14 to 28% in the rainy season (Pham 2004; Pham
and Le 2004). Therefore, the aquatic ecosystem of
Issues
Issues Thi Vai River belonged to the marine ecosystem.
Issues In Thi Vai River, samples of qualitative and
quantitative zooplankton at 5 sites were collected
and fixed with formaldehyde solution in April and
September 2015 (Figure. 1; Table 1) (MRC. 2010).
Issues The samples for water quality analysis in the
field were collected according to the Operational
Guide (3rd Ed.), UN Environment Programme
(1992) (UNWP.—GEMS/Water 1992). The sam-
ples were taken in April and September of 2015.
Issues Sample locations at each site were taken in the
Issues right and left parts of the river with depth layer of
surface water from 30–40 cm. The water samples
were collected in 2 liter plastic bottles and kept at
Figure 1. Thi Vai River with 5 sampling sites (TV1–TV5).
2°C temperature (UNWP.—GEMS/Water 1992).
Samples were taken at least 1 m from potential
contaminants such as debris and aquatic plants,
and at least 2 m from vertical banks. Samples are
In Vietnam, a variety of investigations have been
collected in the middle flow of rivers. At sites where
conducted focusing on morphological biodiversity
the water current is too fast to sample exactly in
of zooplankton (Nguyen 2007). However, publi-
the mid-stream, samples could taken in near the
cations on interaction between zooplankton and
right or left banks, but not too close to the banks
environmental parameters based on zooplankton
(MRC. 2010).
from rivers in Vietnam are limited. Nguyen et al.
Before sampling zooplankton at each site, the
(2007) found the variation of zooplankton abun-
equipment is washed to remove any organisms and
dance between dry and rainy seasons (Nguyen
other matter left from the previous site. 10 L of
2007). In this study we investigated the variation
river water at a depth of 0–0.5 m is collected in a
of zooplankton as well as the water quality based
bucket. The 10 L of river water are filtered slowly
on zooplankton in Thi Vai River in Southern
through a plankton net (with a mesh size of 20
Vietnam.
μm) to avoid any overflow from the net. Water is
splashed on the outside of the net to wash down
any zooplankton adhering to the inner parts of the
2 MATERIALS AND METHODS
net (MRC. 2010).
When the water volume remaining in the net is
2.1 Study area and sample collection
only about 150 mL, the water (which contains the
The Thi Vai River is a tributary of the Dong Nai zooplankton sample) is transferred to a 250 mL
River System. It flows for 76 km through the two plastic jar. The sample is immediately fixed in the
southern provinces of Dong Nai, Ba Ria—Vung field by adding ∼ 75mL of 10% formaldehyde to
Tau, and apart of Ho Chi Minh City with 400–600 achieve a final concentration of 4–5% formaldehyde.
m width and 12–20 m depth (the deepest site ∼ 60 The sample jars are labelled with the site name, the
m). The amplitude of tides at this river was very site code, the sampling position, and the sampling

Table 1. Coordinates and locations of the sampling sites.

Sampling sites Local names Longitude (N) Latitude (S)

TV1 Upstream 5 Km of Go 10°39’22.06”N 107°01’01.69”E


Dau Port
TV2 Go Dau Port 10°40’55.88”N 106°59’02.76”E
TV3 Phu My Port 10°34’36.76”N 107°01’22.28”E
TV4 Cai Mep River Mouth 10°31’01.67”N 107°00’36.74”E
TV5 Ganh Rai Bay 10°29’23.19”N 106°59’52.84”E

220
date. These information were also noted in the field cators of human impact by regressing values for
notebook, as is any information about the site that two seasons of 2015 (10 sampling events for 5 sites)
could be influencing the presence or abundance of against the water quality variables (pH, TSS, DO,
different types of zooplankton (MRC. 2010). BOD5, NH4+, PO43–, and coliform). For each metric
examined against these variables, p values and r2
values were calculated from regression analyses.
2.2 Physical, chemical and zooplankton analysis
The aquatic environmental parameters (pH, TSS,
DO, BOD5, NH4+, PO43–, and coliform) were ana- 3 RESULTS
lyzed according to standard methods (APHA-
AWWA-WEF 1998). All individuals collected The pH values of surface water during the moni-
were identified and counted under a compound toring times ranged from 6.8–7.5, neutral indicator
microscope (with magnifications of 40–1200x) or among the sampling sites and through out the year
a dissecting microscope (16–56x). The results were (Table 2). The TSS fluctuated from 47–70 mg/L.
recorded on data sheets and specimens are kept at In rainy season, the TSS concentration in Thi Vai
the Ton Duc Thang University, Ho Chi Minh City, River in was much higher than this in dry season.
Vietnam (MRC 2010). The DO and BOD5 values in were from 1.8–6.1
mg/L and 4.2–17.7 mg/L, respectively. The NH4+
and PO43– concentrations in Thi Vai River were
2.3 Data analysis
from 0.87–1.94 mg/L and 0.22–0.53 mg/L, respec-
For all sites sampled in April and September 2015 tively. And, the coliform values was from 2.3 × 103–
the following metrics were calculated (i) taxonomic 1.1 × 104 MPN/100 mL in Thi Vai River (Table 2).
richness (i.e. number of taxa); (ii) abundance (i.e. During the two monitoring times, there were 43
numbers of individuals per site); (iii) the Shannon- species and 5 larval types of zooplankton belong-
Wiener Diversity Index (Stiling 2002). The Pearson ing to 7 groups of zooplankton in the studied
test (SPSS, version 16.0) was used for calculation area. Among the zooplankton groups, copepods
on the correlation between zooplankton species were dominant in species number with 28 species
number, abundance and biodiversity index) and in total, gaining over 58.3% of total (Table 3). In
environmental parameters in Thi Vai River. The each monitoring, species number of zooplankton
three metrics were tested for their potential as indi- ranged from 36 (in April) to 39 (in September).

Table 2. Physical, chemical and microbial parameters from Thi Vai River during 2015. Data were presented as minima
to maxima values.

TSS DO BOD5 NH4+ PO43– Coliform


Sites pH mg/L mg/L mg/L mg/L mg/L MPN/100mL

TV1 6.8 47–65 2.6–3.7 8.8–14.0 1.33–1.55 0.37–0.43 9.3 × 103


TV2 6.9–7.0 48–66 1.8–2.9 10.1–17.7 1.46–1.94 0.46–0.53 1.1 × 104
TV3 7.1–7.2 54–70 2.4–3.5 10.9–15.9 1.38–1.69 0.40–0.48 9.3 × 103–
1.1 × 104
TV4 7.3 49–60 4.3–5.2 5.4–7.6 1.05–1.26 0.27–0.30 4.3 × 103
TV5 7.4–7.5 49–61 5.4–6.1 4.2–5.3 0.87–1.03 0.22–0.25 2.3 × 103

Table 3. Structure of zooplankton communities from Thi Vai River during 2015. Numbers in the table indicated the
species number of each zooplankton group.

Zooplankton groups April September Total %

Cladocera 1 0 1 2.1
Copepoda 23 23 28 58.3
Coelenterata 1 1 1 2.1
Mysidacea 1 1 1 2.1
Pronchordata 1 2 2 4.2
Protozoa 4 8 10 20.8
Larva 5 4 5 10.4
Total species number 36 39 48 100

221
Almost zooplankton species and genera Table 4. Biodiversity index values (H’) of zooplankton
recorded in the river were originated from the estu- from Thi Vai River during 2015.
ary or coastal region such as Paracalanus parvus,
Pseudodiaptomus incisus, Acartia clausi, Acartia H’ TV1 TV2 TV3 TV4 TV5
erythraea, Corycaeus erythraeus, Microsetella nor- 04-2015 1.58 1.16 1.41 1.70 2.11
vegica, Othona similis, Obelia sp., larva of shrimp 09-2015 2.06 1.82 1.86 2.21 2.49
and crabs… Therefore, the aquatic environment in
the studied area was affected by sea water via the
tide.
Zooplankton density ranged from 16,900– in Can Gio area (Pham 2014). In the rainy season,
81,800 individuals/m3, lowest at the sampling site the TSS concentrations were high than these in the
5 (Ganh Rai Bay) and highest at the site 1 (Go dry season because of strong flows.
Dau Port, Figure 2). The dominant species in the The NH4+ and PO43– concentrations in the Thi
monitored area were Paracalanus parvus, Acartia Vai River were lower than these inorganic nitrogen
clausi, Acartia pacifca, nauplius copepods. Among and dissolved phosphorus concentrations from
the dominant species, Acartia clausi and nauplius inside canals of Ho Chi Minh City, ranging from
copepods were dominant at most of the sampling 3.2–4.0 mg/L and 1.20 –1.34 mg/L (Pham 2014).
sites. Therefore, the Thi Vai River should be character-
The values of zooplankton biodiversity index ized for mesotrophic condition in both the dry
during the monitoring in 2015 ranged from 1.16– season and the rainy season, in term of NH4+ and
2.49 (Table 4). In Thi Vai River, the values of biodi- PO43– during the monitoring in 2015.
versity index at the site TV5 were higher than these Pham et al. (2012) recorded 94 species of zoo-
in the sites of TV1, TV2 and TV3. The values of plankton during 6 year monitoring in Can Gio
biodiversity index in the rainy season were higher area in which copepods contributed highest spe-
than these in the dry season (Table 4). cies number to the zooplankton community (Pham
The statistical data treatment showed that spe- et al. 2012). Through out 5 years of sampling in
cies number of zooplankton strongly correlated Tien Giang coastal, 58 zooplankton species were
with all environmental variables of pH, DO, NH4+, reported in which copepods was also dominant in
and PO43– in water (r = 0.4197–0.5188; Figure 3). species number (Pham 2014). For the whole year
While, density of zooplankton strongly correlated of monitoring in this area, copepods contributed
with DO, BOD5, NH4+, and PO43– (r = 0.5785 highest number of species. This should be related
–0.7746; Figure 4); and negatively correlated only to the water characteristics of the Thi Vai River,
with TSS concentrations in water (r = 0.0618). strongly influenced by sea water from the East Sea.
Besides, the biodiversity of zooplankton highly Most of species were estuary and coastal species,
correlated with almost environmental variables of and well developed in rich nutrient conditions.
DO, BOD5, NH4+, PO43–, and coliform in water This resulted from the small freshwater sources,
(r = 0.5282–0.9053). so the Thi Vai had the characteristics of salt-water
bay (Pham 2004; Pham and Le 2004).
In general, zooplankton communities during the
4 DISCUSSION monitoring in 2015 were higher than these com-
parison with zooplankton communities in inside
As a running water body, Thi Vai River had the pH canals of Ho Chi Minh City. They could be related
of neutral water (Table 2) and was similar the pH

Figure 3. Species richness of zooplankton strongly cor-


Figure 2. Zooplankton density from Thi Vai during related with environmental variables of pH, DO, NH4+,
2015. and PO43–.

222
Those should be related to the water current from
the sea which helped for self-purification.

5 CONCLUSION

During the two monitoring times in 2015 in Thi


Vai River, the nutrients including NH4+ and PO43–
concentrations were characterized for mesotrophic
condition in both the dry and rainy seasons.
Besides, pH values were favorable for development
of zooplankton. There were 43 species and 5 lar-
val types of zooplankton belonging to 7 groups of
cladocerans, copepods, coelenterates, mysidacea,
prochordates, protozoans, and larva, in the studied
areas of which copepoda was dominant in species
number.
In general, zooplankton communities during
the monitoring in 2015 was higher than this com-
parison with zooplankton communities in inside
canals of Ho Chi Minh City. They could be related
to the improvement of water quality in Thi Vai
River in recent years. This needs further investiga-
tion especially the monitoring on the water quality
to confirm. The values of zooplankton biodiver-
sity index were rather low in dry season (April) and
higher in the rainy season of the year (September).
Besides, the values seemed to be higher at the sites
in near river mouth and the Ganh Rai Bay.
The species number of zooplankton strongly
correlated with environmental variables of pH,
DO, NH4+, and PO43– in water. While, density of
zooplankton highly correlated with DO, BOD5,
NH4+, and PO43–; and negatively correlated with
only TSS concentrations in water. Besides, the bio-
diversity of zooplankton strongly correlated with
almost environmental variables of DO, BOD5,
NH4+, PO43–, and coliform in water.
Results of this study contributed the interest-
ing information on zooplankton composition
and abundance, their correlation with water qual-
ity parameters and environmental characteristics,
which was quite limited in Southern Vietnam.
Figure 4. Density of zooplankton strongly correlated
Besides, the results confirmed the advantage of
with environmental variables of DO, BOD5, NH4+, and
PO43–. using zooplankton and their indices as useful tools
for water quality monitoring.

to the improvement of water quality in Thi Vai


River in recent years. This needs further investiga- ACKNOWLEDGEMENT
tion especially the monitoring on the water quality
to confirm. We would like to thank Ms. Vo Thi My Chi for
The biodiversity index values were character- helping with the sampling map.
ized for mesotrophic condition in both the dry and
rainy seasons. Generally, the biodiversity index
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National University, HCMC.

224
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Spatial distribution of macroinvertebrate assemblages in inland waters


of Quang Ngai Province, Vietnam

V.M. Pham & T.T. Nguyen


Southern Institute of Ecology, Vietnam Academy of Science and Technology, Ho Chi Minh City, Vietnam

A.D. Pham
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: Conserving and enhancing freshwater biodiversity are global issues to ensure ecosystem
integrity and sustainability. To meet this, it is critical to understand how the biological assemblages are
determined in different spatial scales. This paper aimed to understand spatial distribution patterns of
macroinvertebrates in river systems across Quang Ngai Province. A total of 51 taxa, belonging to 19 fami-
lies in 3 classes of 2 phyla, were identified. Thus, Quang Ngai Province have not got too high biodiversity
of species composition of macroinvertebrates. Quang Ngai region was divided into two main landscapes
such as (1) the high mountains; and (2) the coastal plain. Generally, the diversity of macroinvertebrates
in the coastal plain area was higher than this in the mountains. In general, the types of lotic waters had
a higher biodiversity compared to lentic waters. The results provided basic information for establishing
the conservation and restoration strategies of macroinvertebrate biodiversity against anthropogenic dis-
turbances and developing more confident bioassessment tools for diagnosing stream ecosystem integrity.

Keywords: macroinvertebrate assemblages, biodiversity, spatial distribution, aquatic ecosystem

1 INTRODUCTION great impacts to the environment and biodiversity


in this province (Nguyen T.T. 2013).
Quang Ngai is a province in the South Central There are four major rivers of Tra Bong, Tra
Coast region of Vietnam. The topography of Khuc, Ve, and Tra Cau in Quang Ngai Province.
Quang Ngai is dominated by a large plain along These rivers have common characteristics that are
the coast and in the center of the province and by oriented parallel or subparallel flow routing, dis-
mountains and hills in the West, and along it bor- tributed fairly evenly over the plains of Quang Ngai
ders with Quang Nam and Binh Dinh provinces. (Quang Ngai People’s Committee, 2016). They are
It has a wide variety of ecosystems with different mostly derived from sources of high mountain
characteristics of natural environmental factors, ranges to the West of this province. Previously,
creating high biodiversity (Nguyen T.T. 2013). there have been some studies on aquatic fauna in
Quang Ngai forests are mainly poor forests some of the river, however, focused research on fish
and plantations or regenerations. Only some pri- resources. There were 41 species of freshwater fish
mary forests and secondary jungle less affected by occurring in Quang Ngai Province, many species of
human activities are distributed in the high moun- high economic value (WAR 2011). While the mac-
tains, steep slopes. Forests are also distributed in roinvertebrate data of inland waters in Quang Ngai
the Western mountains of the province. There is a Province have been undocumented. This group
distribution of the mangrove forests in the coastal plays a key role in the ecosystem, contributing to
zone. The area of Quang Ngai’s natural forest is environmental indicators of water in streams and
not many, while ensuring the diversity of forest rivers (Wallace and Webster 1996). Therefore, it
types and the abundance of plant species. Cur- was necessary to perform the survey to collect data
rently, there is no complete statistics on the cur- on the biodiversity of macroinverterates to create
rent state of biodiversity in this province, but the the database platform for further research on the
decline of forests, environmental pollution and effects of environmental changes to ecosystems of
over exploitation of natural resources are causing Quang Nai as well as in a geographic area.

225
2 MATERIALS AND METHODS Nghia Lam, Minh Long, Nui Ngang Reservoir
(Ba Lien—Ba To District); and, (3) high moun-
2.1 Study area and sample collection tains route such as Tra Xuan, Di Lang, Son Tay,
Ky Son (Son Ha).
Data from over 5,500 Km2 of river basin area
The specimens were photographed, then freezed
was used as a representative example for rivers in
before being preserved in alcohol 90% or formalin
Quang Ngai Province. Samples were collected at
5%–10%. In addition, the field and sampling site
study sites according representing each water body
characteristics such as time, date, kinds of sam-
in different habitats, such as rivers, streams, lakes,
ples, coordinates, water current, bottom bed, river
ponds, marshes, fields, caves... of the rivers Tra
width, water color, weather were taken notes. These
Bong, Tra Khuc, Ve, and Tra Cau at two time April
were very useful information for result explanation
and May of 2016. The sampling sites were selected
(MRC 2010; Pham et al. 2012).
according to their accessibility. Specimens of
Crustacea—Decapoda, Gastropoda, and Bivalvia
were collected by hand, hand net, traps in both the 2.2 Benthic macrorinvertebrate analysis
day and night (Pham et al. 2012).
All individuals were identified and counted under
The survey and sampling sites were arranged
a compound microscope (with a magnification of
in terrain lines from low to high, included: (1) Tra
40–1200x) or a dissecting microscope (16–56x),
Bong River from the regional town of Chau O
lamme, lammelle, pipette, petri dishes. Gastropoda,
to 7 km upstream Tra Xuan Town; (2) Tra Khuc
Bivalvia, and Crustacea are generally identified to
River from Quang Ngai City area to Di Lang
species level (MRC 2010; Pham et al. 2012).
Town, Son Ky, and Dak Drinh Dam; (3) Ve River
The identification of benthic macroinverte-
at Minh Long, Hanh Thien, Song Ve Bridge, and
brates was based on morphology and taxonomic
Giang Tien Reservoir; and, (4) Nui Ngang Reser-
books such as Crustacea (Bouvier 1925; Holthuis
voir at Ba To District, upstream of Ba Lien river,
1950; Tiwari 1963; Dang et al. 1980; Hayward
ponds and streams flowing into the sea gates of
and Ryland 1990; Thorp and Covich 2001; Sang-
Sa Huynh.
pradub and Boonsoong 2006); Thai 2007); Dang,
Additionally, the survey and sampling sites were
Ho 2012); Gastropoda (Brandt 1974; Dang et al.
followed in topographical landscape ecoregions,
1980; Thorp and Covich 2001; Dillon 2004; Sang-
included: (1) coastal plain region along Binh Son,
pradub and Boonsoong 2006; Thai 2007; Bivalvia:
Son Tinh, Quang Ngai City, Mo Duc, Duc Pho (Sa
Brandt (1974); Dang et al. (1980); Thorp and
Huynh); (2) low mountain route at Binh Chuong,
Covich (2001); Dillon (2004); Sangpradub and
Boonsoong (2006); Thai (2007). The results were
recorded on data sheets and specimens are kept at
the Southern Institute of Ecology, Vietnam.

2.3 Data analysis


For all sites sampled in April and May 2016 the
following metrics were calculated (i) taxonomic
richness (i.e. number of taxa); (ii) abundance
(i.e. numbers of individuals per site). In order to
determine the biodiversity of inland water bodies
of Quang Ngai province, three macroinvertebrate
classes of Crustacea, Gastropoda, and Bivalvia
which was focused survey for evaluating the distri-
butions characterized by areas of landscape ecol-
ogy, the natural geographical area, and by type of
water body.

3 RESULTS

During the two monitoring times, there were


51 species of macroinvertebrates belonging to
3 groups of crustaceans, gastropods, and bivalves
Figure 1. Map of Quang Ngai Province (Nguyen D. in the studied area. Among the macroinvertebrates
2013). groups, crustaceans were dominant in species

226
number with 27 species in total, gaining around 3.1.3 Bivalvia
52.9% of total (Table 1). Bivalvia recorded in the water bodies of Quang
Ngai Province was also quite rich with 11 species
belonging to 4 families. Among the species belong-
3.1 Species richness
ing to this class, the mussels and clams species were
3.1.1 Crustacea—Decapoda the richest abundance and most recognized in all
In Crustacea—Decapoda, discovered two species inland waters across the province. Among 11 spe-
of Brachyura including a freshwater crab species cies of bivalves, Limnoperna simensis (Mytilidae)
of Sayamia triangularis (Dang and Hai, 2005) that was originated from marine species that could
belonged to a species of Parathelphusidae, and adapted well with the freshwater environment
brackish water was Varuna litterata (Fabricius, entirely from ancient times, so this species must be
1798) that belonged to Grapsidae. Check all the considered a relictus species.
sampling locations from the plains to the moun- The river clams of Sinanodonta jourdyi, Sinano-
tains in Quang Ngai just discovered this species. donta elliptica, Nodularia douglasiae were recorded
Meanwhile, there were 11 species of Macrura to have distribution from South China to Quang
including 4 genuses of Palaemonetes, Macrobra- Ngai in South Central, Vietnam. However, two
chium, Palaemon, and Caridina. Two genuses of species of Sinanodonta jourdyi and Sinanodonta
Caridina, Macrobrachium have got 3 or more spe- elliptica also found in the types of water bodies
cies. Of which, there were 8 species belonging to the in Dongnai River basin such as La Nga River,
family of Palaemonidae and 3 species of Atyidae. Dong Nai River, Buong River, … with high densi-
This indicated that two orders of Decapoda— ties. For example, Pham et al. (2001) noted farmers
Brachyura and Decapoda—Macrua as well hav- at Cau Dap Moi Reservoir (Long Thanh—Dong
ing two families were recognized. But considering Nai) could be collected about 100 Kg per day. This
at levels of species and genus, the Decapoda— might be due to larvae and adults have sticked in
Macrura in Quang Ngai was somewhat higher the species of Cyprinidae moving from North to
than this of Decapoda—Brachyura. South of Vietnam due to the introduced species or
the aquaculture development.
3.1.2 Gastropoda
The results of sample analysis collected in the
3.2 Species diversity of natural geographical
inland waters of Quang Ngai province have identi-
regions
fied 27 species of Gastropoda. Species of Gastrop-
oda lived in freshwater environments including the 3.2.1 Crustacea—Decapoda
families of Viviparidae, Thiaridae, Pachychilidae, In the three species of Atyidae, Caridina nilotica
Ampullariidae, and Lymnaea viridis, Indolomantis and Caridina acuticaudata had widely spread from
exustus. North to South Vietnam, so Caridina tonkinensis
Meanwhile, Gastropoda species lived in low distributed from North to Central Highlands and
brackish to moderate brackish waters, including South Central, Vietmam. Palaemonetes tonkinensis
Sermyla riqueti, Neoradina prosongi (new spe- (Palaemonidae) had a similar distribution of Car-
cies discovered in Vietnam recently), Cyclotropis idina tonkinensis. The discovery of the two species
carinata, and species of marine origin migrated of Palaemonetes tonkinensis and Caridina tonkin-
into inland (Potamididae, Muricidae, Ellobiidae, ensis at Quang Ngai in this survey (2016) and in
Neritidae, Succineidae, and Littorinidae). These the Central Highlands (Pham et al. 2001) was to
groups were very abundant with 52% of all species expand our distribution area of these species from
of snails (14/27 species) which were recorded in this North to South Central and South of Vietnam.
survey, and they only distributed deeply inland of Of the six species of Palaemonidae, Macrobra-
rivers of Tra Bong, Tra Khuc, Ve, and river mouths chium javanicum, Macrobrachium equidens, Macro-
of some small rivers of Duc Pho District. brachium lanchesteri, and Exopalaemon vietnamicus
had the distribution from the South of Indochina
Peninsula and Southeast Asia to South Central of
Table 1. Structure of macroinvertebrates communities Vietnam (provinces of Quang Nam and Quang
from Tra Khuc and Tra Bong Rivers during 2016.
Ngai). Particularly, Macrobrachium lanchesteri
Classes No. Species % have distributed only to North Central (Thua
Thien Hue Province); Macrobrachium latidatylus
Crustacea 13 25.5 have so far been discovered in Quang Nam, Nha
Gastropoda 27 52.9 Trang (Pham and Le 2004; Nguyen 2010). Mac-
Bivalvia 11 21.6 robrachium nipponense have distributed in China,
Total 51 100% Japan, Taiwan to South Vietnam (Dang and Ho
2012). These species have also found in Quang

227
Ngai with high densities. Therefore, samples of distributed in the coastal plains. Only Paracrotoma
Macrobrachium nipponense samples collected in solemiana, Corbicula lamarckiana, species of
Dong Thap Province, Mekong Delta should be Amblemidae have distributed mainly in rivers in
reconsidered, because it could be Macrobrachium Quang Ngai mountains. However, due to the short
mekongense (Dang, 1998). If true, Macrobrachium river, slope of terrain, and large gravel substrates,
nipponense only distributed to South Central, these species were collected in the areas of Chau
Vietnam, along with the distribution of Macrobra- O Bridge, Tra Khuc Bridge, Ve River Bridge, but
chium hainanense on the territory of Vietnam. the number of individuals was very little in each
site. Therefore, the biodiversity of Gastropoda
3.2.2 Gastropoda and bivalvia and Bivalvia in coastal plains of Quang Ngai were
Species of Paracrostoma solemiana, so far has been much higher than these in the mountains.
found in Bung River (Quang Nam) and Dak Drink
(Quang Ngai) in the early years of the 21st cen-
3.4 Species diversity of inland waters
tury only. While snail species of Pila polita, Thiara
scabra, Melanoides tuberculatus, Tarebia granifera, There were two types of water bodies in Quang
Sermyla riqueti, Lymnaea viridis, clam species of Ngai: (1) type of lentic waters including ponds
Corbiculidae, and all marine species above have and lakes such as ponds, Gieng Tran reservoir, Nui
distributed widely in the subtropics and tropical Ngang reservoir, Thach Nham dam, Dak Drink
Asia. hydropower reservoir; and (2) type of lotic waters
Snail species of Angulyagra polyzonata and such as rivers and streams which played a key role
Cipangopaludina lecythoides, and clam species of in this type of Quang Ngai. The species diversity
Sinanodonta jourdyi, Sinanodonta elliptica, Nodu- was described in three classes of Crustacea, Gas-
laria douglasiae have distributed from South China tropoda, and Bivalvia.
to Quang Ngai (South Central of Vietnam). Par- For crustaceans, in lentic water such as ponds,
ticularly, two species Sinanodonta jourdyi and Sina- there were only species of Palaemonetes tonkinensis,
nodonta elliptica, have been recorded in various Macrobrachium lanchesteri, Macrobrachium nippo-
types of water bodies belonging to Dongnai River nense, and Caridina. While in rivers, in addition
basin such as La Nga River, Dong Nai river, Buong to the above species, also having Macrobrachium
River, … with large quantities recently (Pham et al. javanicum, Macrobrachium hainanense, Macro-
2001). Snail species of Filopaludina sumatrensis, brachium latidactylus, Macrobrachium equidens,
Idiopoma dissimilis, Pila ampullacea, and clam Exopalaemon vietnamicus. Therefore, the diversity
species of Physunio inornatus, Trapezoideus exoles- of crustaceans in the lotic waters was higher than
cens, Indonaia humilis have distributed in tropical these in lentic waters.
region of Southeast Asia (South Vietnam, Thai- For gastropods and bivalves, all the species col-
land, Laos, Cambodia) (Pham et al. 2001). lected in the lotic waters, this indicated that the lotic
waters played a key role in Quang Ngai. Whereas,
only species of Viviparidae, Ampullaridae, two
3.3 Species diversity of natural landscape regions
species of Lymnaea viridis and Indoplanorbis exus-
In terms the regional distribution of Quang Ngai tus were distributed in the lakes and rivers in the
landscape, could be divided into two areas of the coastal plain.
coastal plains and the mountains. For the regional
diversity of landscape of crustacean species, Saya-
mia triangularis, Palaemonetes tonkinensis, and 4 DISCUSSION
Macrobrachium nipponense had the wide distribu-
tion both in the plains and mountains. The remain- Establishing geographical areas for crustaceans and
ing species such as Macrobrachium javanicum, molluscs which played a key role in the research
Macrobrachium hainanense, Macrobrachium lati- and management of biodiversity resources of
dactylus, Macrobrachium equidens, Exopalaemon Quang Ngai. The species of macroinvertebrates
vietnamicus and Varuna litterata only distributed in were divided by two zones of natural geography
the delta. Therefore, in the plains of Quang Ngai and biodiversity protection.
had biodiversity of macroinvertebartes higher than
these in the mountains.
4.1 Zoning of natural geography
Considering the regional diversity of landscape,
the snails and bivalves such as species of Viviparidae, Quang Ngai Province belonging to the zone
Ampullaridae, Sermyla riqueti, Neoradina prosongi of Kontum—South—Ngai (its means Kon-
(Thiaridae), Cyclotropis carinata (Assimineidae), tum Province—South Vietnam—Quang Ngai
Littorinopsis scabra, Littorinopsis melanostoma Province), the natural geographic region of South
(Littorinidae), Unionidae, Corbiculidae have Central and Southern Vietnam, in terms of

228
geographical distribution of Crustacea—Decapoda lanchesteri, Exoplaemon vietnamicus. Some spe-
in the inland waters at Quang Ngai as mentioned cies characterized in South Central, needed to be
above, could identify three groups of species: (1) protected due to being over-exploited for food as
species widespreading in the subtropics—tropical Macrobrachium lactidactylus; Paracrostoma solem-
region consisted of Varuna litterata, Tarebia grani- iana, Neoradina prosongi. In addition, biodiversity
fera, Thiara scabra, Melanoides tuberculatus, Pila of the two regions with the landscape characteris-
polita; (2) species coccuring from the South China tics included: (1) the mountainous landscape was
to South Central of Vietnam included Angulyagra typical with distribution of Paracrostoma solemi-
polyzonata, Cipangopaludina lecythoides, Lymnaea ana; and (2) the plain landscape characterized by
viridis, Caridina tonkinensis, Palaemonetes tonkin- coastal biodiversity and high economic value were
ensis, Macrobrachium hainanense, Macrobrachium being overexploited for food with typical species
nipponense; and (3) species distributing in tropical such as Macrobrachium lactidactylus and Neo-
Southern Asia to Southern Central Quang Ngai radina prosongi.
comprised Sayamia triangularis, Macrobrachium
javanicum, Macrobrachium lanchesteri, Macro-
brachium lavidactydes, Macrobrachium equidens, 5 CONCLUSION
Exopalaemon vietnamicus; Filopaludina (F.)
sumatrensis, Idioma dissimilis, Neoradina prosongi, The survey results of macroinvertebrates in Quang
Paracrotoma solemiana, Cydotropis carinata, Pila Ngai Province have recorded 51 species, including
ampullacea, Indoplanoclis exustus; Physunio inor- Crustacea with 13 species belonging to 4 families,
natus, Trapezoideus exolescens, Indonaia humilis. Gastropoda with 27 species of 10 families, and
The freshwater snails and clams in Quang Ngai Bivalvia with 11 species of 4 families. Thus, Quang
were an intermediary for the North Vietnam and Ngai Province have not got too high biodiversity
South Vietnam, probably fauna from the Ngang of species composition of macroinvertebrates.
Pass to the Ca Pass. Starobogotov (1970) based Quang Ngai region was divided into two land-
on species composition and distribution of snails scapes such as (1) The high mountains; and (2)
and clams, established the Mekong animal region The coastal plain. Generally, the diversity of mac-
including Lao Zone, Zoo of East Truong Son, roinvertebrates in the coastal plain area was higher
and, Zone of South Vietnam—Cambodia. Thus, than this in the mountains. Additionally, the water
snails and clams in the aquatic waters of Quang bodies in this survey was divided into 2 categories:
Ngai Province have belonged to East Dong Truong (1) lentic waters; and, (2) lotic waters. In general,
Son, Mekong animal region (Dang et al. 2002; the macroinvertebrate assemblages at the types of
Pham and Le 2004). lotic waters had a higher biodiversity compared to
lentic waters.
4.2 Zoning of protecting biodiversity
Based on the analysis of biodiversity following ACKNOWLEDGEMENT
the distribution under the natural geographical
regions of Vietnam, Mekong animal region, the This study was performed under the project of
landscape of mountains and coastal plains of “Survey and Assessment of Biodiversity of Quang
Quang Ngai, types water bodies of Crustacea, Ngai Province” in Vietnam, and was supported
Gastropoda and Bivalvia, … the biodiversity of by the Southern Institute of Ecology, Vietnam.
inland waters in Quang Ngai could be determined. The authors also thanks a lot the survey members
The biodiversity of natural geographical areas of involved in the project.
Kontum—South—Ngai have mixed characteris-
tics of the 3 groups of species: (1) group of spe-
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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Life cycle assessment of different constructed wetland systems


in new Taipei City

V.M.T. Nguyen
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

T.M. Lee
Department of Geography, School of Science, Chinese Culture University, Taipei, Taiwan

ABSTRACT: The study applied Life Cycle Assessment (LCA) to evaluate the environmental impacts
of construction, operation, transportation of materials and wastes among the gravel contact oxidation
system in Yingge, constructed wetland in Chenglin and Xinhai 3, Taiwan. The goal of Life Cycle Assess-
ment was to assess the environment benefits of wetlands were used as a wastewater treatment plant and
the usefulness of converting waste land into biological treatment plant. Construction, operation phase,
sludge treatment and transportation of materials were taken into consideration by using Impact 2002+
method, reflected upon four categories human health, ecosystem quality, climate change and resources.
The results are elucidated that dominance of waste scenario at all categories in regard to either of projects
(Chenglin, Yingge, Xinhai 3). In consequences, a difference of impacts on environment between three
systems with different treatment way will contribute to the making-decision of the treatment process or
method. And so, it is a premise for studies in the future in comparison with other wastewater treatment
plant or using other methods to find the similarities and differences between them.

Keywords: constructed wetland, Life Cycle Assessment (LCA), municipal wastewater, subsurface flow,
Dahan River

1 INTRODUCTION often much lower than for competing technologies.


They require no chemical. Cost categories include
Wetland is a class of natural landscapes with physical maintenance, flow and quality monitoring
many types. Through conventional management and biological surveillance (Robert 2009).
of wetland, the landscape quality and biodiversity Life Cycle Assessment (LCA) in this study is
of wetland may be maintained. However, urbani- carried out based on “cradle to grave” concept
zation and industrialization have tremendous (Friedrich et al. 2007, Foley et al. 2010a, Lassaux
impacts on wetland around the world. To maintain and Renzoni 2007). The first goal of this study was
the natural quality of landscape and to bring resi- to compare the environmental impact of construc-
dents of urban-industrial area a more environmen- tion, operation and transportation of materials
tal friendly neighborhood, the constructed wetland between those systems. The second goal is assess
is proposed recently. This artificial wetland works the main contributors in each system. It contained
like a wetland, being able to mitigate and prevent all the processes, including the construction, oper-
pollutants from sewage and drainage wastewater. ation, and transportation stage and sludge treat-
It also can be a valuable part of urban design in ment. The drainage system without treatment
contributing for human activities, harmonizing discharge to receiving water body directly was not
building areas and educating for people. taken into account in this study. This study was not
Most CWs have been used for secondary, terti- taken account of demolition stage, recycling stage
ary or advanced treatment process (Wieder 1989). due to lack of data. They were assumed that these
Moreover, CWs can be used for pretreatment and factors are negligible. All of systems were not use
post-treatment too, because their ability to adapt chemical substances in operating, for this reason,
to fluctuation of water level and various organic related chemical issues were not consider in this
and inorganic pollutants conversion during meta- study. Sima Pro 7.0 software is applied to evalu-
bolic and other processes (Brix 1999). Neverthe- ate and compare the environmental impacts of dif-
less, operating costs for treatment wetlands are ferent type of wastewater treatment method and

231
environmental benefits between the gravel contact sewage is pumped into the aeration oxidation tank
oxidation system and two constructed wetland; through gravel filter attached as a biofilm. The fine
find out which process contributes the most effect particulate matter will be absorbed and interacted
in each projects. with microorganism on the surface of gravel. After
purification process, water is discharged to the
artificial valley of Sanying Reclamation Area. It
2 MATERIALS AND METHODS further flows through the water arena before going
into Dahan Stream.
2.1 Study area Xinhai pumping station pumps daily wastewater
from municipal sewage drainage system to wetland.
Chenglin constructed wetland is located within
The wastewater flow to preliminary sedimentation
the levee’s beach water zone at the east bank of
pond where it is placed in a lower level than pumping
Da-Han River. Constructed wetland is located at
station, creating a favorable condition to discharge
the east bank of the same river around 7 to 8 km
wastewater to the pond in an attempt to enhance
downstream (Figure 1). Chenglin constructed wet-
the efficiency of settling by gravity feed. Thereupon,
land is a subsurface flow wetland. The wastewater
water move to grassy marsh I where water plants
flow is led to the system via trenches or underdrain
grow densely, create an aerobic and anaerobic envi-
networks. The wastewater is kept below the perme-
ronments for denitrifying process. Then, the flow
able materials such as gravels or soil beds planted
keeps on moving to grassy marsh II where emergent
with vegetation. The water is not exposed to the
aquatic plants with a short stems take part in as a
atmosphere, as a result, minimize the risk of path-
main components to hold water during retaining on
ogen exposure and odor.
stage. At last, the flow comes to aquatic economic
Yingge District is located in the most peripheral
crops zone before discharging into Dahan stream.
part of New Taipei City. A gravel contact oxidation
The information of treatment efficiency of three
system is located on the west bank of Da-Han River
projects are summarized in Table 1.
in Yingge (Figure 1), was installed in the reclama-
tion area which can treat 40,000 CMD of sewage
daily in Yingge Creek. In the primary sedimenta- 2.2 Data collection and analysis
tion section, the settlement tank receives 300 m3/
Life Cycle Assessment (LCA) is a tool to quantify
m2/day for settling sand and rough sediments. Then
the environmental impacts of products, services
or processes on their whole life cycle, from the
production of raw material to the final disposal
of itself, is called “from cradle to grave” (Roux
2010). The functional unit can be understood as
a yardstick or comparison basis for different sys-
tems or processes. In this case, the functional unit
was defined as “1 m3 nominal volume of treated
wastewater at the end of each process”. The cho-
sen functional unit was not manifest the quality of
wastewater after treatment process or the scale of
system, in other words it represented the amount
Figure 1. Study areas. of wastewater goes through each unit treatment.
Table 1. Information of treatment efficiency.

Sites Description Influent design Effluent design Efficiency

Chenglin Completed in 2010 BOD < 60 mg/l BOD < 20 mg/l BOD > 65%
Site area: 26.5 ha SS < 200 mg/l SS < 40 mg/l SS > 85%
Water area:19.26 ha NH3-N < 10 mg/l NH3-N < 5 mg/l NH3-N > 50%
Retention time: 5 days
Yingge Completed in 2011 BOD: 20 mg/l BOD < 20 mg/l BOD: 50% –70%
Site area: 1 hecta SS: 300 mg/l SS < 30 mg/l
10 m depth NH3-N: 8.5 mg/l NH3-N < 8.5 mg/l
Xinhai 3 Completed in 2009 BOD < 55 mg/l BOD < 20 mg/l BOD > 60%
Site area: 6.5 ha SS < 30 mg/l SS < 15 mg/l SS > 55%
Water area: 4.13 ha NH3-N < 25 mg/l NH3-N < 15 mg/l NH3-N > 50%
Retention time: 3.16 days

232
In order to correspond with the goal and the scope 3 RESULTS AND DISCUSSIONS
of this study, the system boundaries were shown
in Figure 2 presents the boundary of wastewater 3.1 Life cycle assessment
treatment systems (includes two constructed wet-
In figure 4, the characterization result specifies
lands and one biological treatment) for the whole
the whole process of Yingge in red and the waste
system as well as the processes have been ignored.
scenario of materials in green. The vertical axis
Data were supported by “The construction
expresses the percentage is occupied by Yingge and
project of water quality purification treatment of
Waste Scenario. It shows that the end of life (waste
Dahan creek ecological corridor in Taipei County”
scenario) is dominating in almost impact catego-
for all the planning of construction and materials
ries, while the highest percentage that Yingge sys-
associated with costs. Electricity was calculated by
tem occupies only about 58%. The waste scenario
estimating the consumption of energy to produce
demonstrates it strongly influence on terresestrial
1 kWh. The consumption of electricity for pump-
ecotoxicity and ozone layer depletion that are
ing, mechanics and other processes were referenced
grouped in ecosystem quality under damage cat-
from manual documents. Data of cement, metal
egory. Yingge system impact on resources by min-
pipes, PVC pipes, gravel, rock and other materi-
eral extraction process, because extracted materials
als were provided by the project and were based
were supplied for construction stage. The result
on experience from engineers. The landfill was not
presents waste scenario dominates on land occupa-
taken account in this study.
tion than Yingge system. It may be explained that
This study applied Impact 2002+ method
the land used for wastewater treatment purpose is
(Figure 3) to assess the environmental impact from
installed into the reclamation area, while Shulin
two systems. This figure below describes the over-
Incinerator occupied a large scale in the city.
all features of method.
In Figure 5, the characterization result speci-
fies the process of ChenglinCW in red and the
waste scenario of materials in green. It shows
that the end of life (waste scenario) is dominat-
ing in almost impact categories, while the highest
percentage that Chenglin system occupies only

Figure 2. Flow chart of wastewater treatment system.

Figure 4. Characterization category in Yingge by


Impact 2002.

Figure 3. Overall scheme of the Impact 2002+ frame- Figure 5. Characterization category in Chenglin by
work. Base on Jolliet et al. (2003). Impact 2002.

233
about 38%. The waste scenario demonstrates it aquatic eutrophication and aquatic acidification
strongly influences on terresestrial ecotoxicity and are not affected by any projects. Noticeably,
ozone layer depletion that are grouped in ecosys- Chenglin gets about 28 kPt on terrestrial ecotox-
tem quality under damage category. Also, there are icity indicator, while Yingge only has 17 kPt and
some influences on human health through ionizing Xinhai 3 is about 14 kPt. It means, Chenglin
radiation and ozone player depletion (midpoint strongly impacts to terrestrial ecosystem and
categories). Chenglin system impacts on resources releases disadvantaged substances that for environ-
by mineral extraction activity in order to supply ment in construction stage. This can be explained
raw materials for construction. The result presents that because all three projects are built on land, so
waste scenario dominates on land occupation than extraction, backfill processes influence on ecosys-
Chenglin system. It may be explained that the land tem on land. Along with terrestrial ecotoxicity, there
used for wastewater treatment purpose is utilized is an aquatic ecotoxicity also influenced by releas-
from the bank along Dahan River, while Shulin ing or discharching materials during construction
Incinerator occupied a large scale in the city. Both stage. Moreover, Chenglin contributes more effects
aquatic acidification and aquatic eutrophication to non-renewable energy than Yingge and Xinhai
are impacted by ChenglinCW maybe caused of 3. Because the amount of materials supplied to this
nutrients from water plant decomposition mingle site consumes much fossil fuel as well as mineral
into water, especially in depletion period. like explained in previous section. The carcinogen
Figure 6 indicates that the end of life (waste indicator reveals that these three systems have very
scenario) is dominating in all impact categories, low points, less than 1 kPt. The non-carcinogen in
while the highest percentage that Xinhai 3 system Chenglin contributes most impact, compare with
gets only about 12%. The waste scenario demon- others. Beside 14 categories are available in mid-
strates it strongly influences on terrestrial ecotox- point category, one more human toxicity si split up
icity, aquatic ecotoxicity, aquatic eutrophication, in “carcinogens” and “non-carcinogens” as above.
ozone layer depletion and land occupation that In summary, ChenglinCW has strongest impact
are grouped in ecosystem quality under dam- and Xinhai 3 has least impact at all indicators, in
age category. Likewise, there are some influences comparison within three projects. It guides to the
on human health through ionizing radiation and notion that, even they (Chenglin and Xinhai 3) are
ozone player depletion (midpoint categories). At similar in treatment method, they still have dif-
mineral extraction category (belong to “resources” ferent impact on environment. It also means that
endpoint), Xinhai 3 system does not have much there are many factors influence to final result,
impact on resources, because Xinhai 3 is the suc- such as the way do the construction, the materials
cessor of Xinhai 2 and Xinhai 1. It inherits benefits need be supplied, the production of materials, the
and conveniences from its precursor. The result in method used to treat wastes and so forth.
land occupation is also conformable with explana- In Figure 8, the vertical axis expresses the point
tion above. of each indicator is impacted by process or sys-
tem, unit as kPt. The horizontal axis represents
four endpoint categories. In this graph specifies
3.2 Comparison of life cycle assessment
four endpoint categories include human health,
In Figure 7, the horizontal axis expresses the point
of each indicator is impacted by system, unit as
kPt at logarithmic scale. The vertical axis repre-
sents processes or systems or projects. There are
two directions of those impact categories with 1kPt
as a benchmarking. In this graph displays three
projects and their impact on each category. The

Figure 6. Characterization category in Xinhai 3 by


Impact 2002. Figure 7. LCA midpoint by Impact 2002.

234
According to (Foley 2010b), IMPACT 2002+
method does not include a damage endpoint under
aquatic eutrophication and acidification catego-
ries. This is a significant gap in LCIA damage for
wastewater treatment plants and is being addressed
in current revisions to IMPACT 2002+, and other
methods. By this limitation, damage assessment
can only be applied to scenarios that have equiva-
lent effluent quality (i.e. eutrophication damage
impacts from compared scenarios are equivalent
and hence to do not influent the relative compari-
son). Therefore, varying the data or assumption
by a set arrange (±20%), any significant changes
in the results that may be influenced by the study
Figure 8. LCA endpoint by Impact 2002. uncertainties (Dreyer et al. 2003).
In order to improve the environmental per-
formance, it is important to highlight the main
ecosystem quality, climate change and resources. contributor to the environmental load. As results,
As result shown, Chenglin effects on human health the production of products consumed by the con-
about 2.5 times to Xinhai 3, while Yingge has 4.4 structed wetland or treatment system such as con-
kPt. For ecosystem category, Chenglin has 28.19 crete, steel, cement, production of electricity or other
kPt, Yingge has 17.07 kPt and Xinhai 3 only has types of energy, extraction of resources and so on,
14.04 kPt. At climate change category, Chenglin— have impact strongly. These results are consistent
Yingge—Xinhai 3 contributes about 2.47 kPt, 1.77 with Foley’s study (Foley et al. 2010c) where infra-
kPt, 0.92 kPt, respectively. For resource category, structure resource consumption is great. Certainly,
Chenglin contributes most while Yingge is in inter- they release pollutants into air, water and soil in the
mediate point and Xinhai 3 is least. The result at form of solid matter, suspended matter or volatile
endpoint is in accordance with result at midpoint, substance. There are certain volumes of heavy metals
first of all, the highest impact is on human health cumulate in the air or at the bottom of ponds, turned
in which represent by respiratory effects and ion- to be sludge afterward. In other words, through
izing radiation. Secondly, these impacts on ter- changing technologies used to produce materials or
restrial ecotoxicity direct to ecosystem category. move to environmentally methods would be safer
Thirdly, the global warming surely leads to climate and better. The impact of consumption of materi-
change. Finally, non-renewable energy guides to als and energy might be compensated by a reduction
resource category. At once, it demonstrates that of the expense for treating wastewater. The study
life cycle of Chenglin contributes most impact on has shown that the building of a friendly environ-
environment, Yingge gets intermediate position mentally treatment system in general or constructed
and Xinhai 3 is least. wetland in particular, still harms to environmental
load. But, their effects even so lay on acceptable
limitation. Nevertheless, in spite of constructing in
4 CONCLUSION the similar ways or using similar methods, they are
some difference in their effects to the environment. It
There are some conclusions on these four catego- might depend on the materials were supplied and the
ries are impacted by three projects: production processes were generated.
Human health: the majority of the impacts is due
to emission of particulates matter and identified
by carcinogens and non-carcinogens indicator. ACKNOWLEDGEMENT
Ecosystem quality: in Impact 2002, it presents
noticeably a dominance of terrestrial ecotoxicity The authors express the thankfulness to Professor
cover three projects. Furthermore, in comparison Chun-Han Ko and his staff from National Taiwan
with human health and resources, ecosystem qual- University in providing Sima Pro software and
ity hardly suffers from those impacts, almost dou- documentary project.
ble or tripble with the remains.
Climate change: the impacts on climate change REFERENCES
are not remarkably.
Resources: the results on mineral depletion and Brix, H. 1999. How Green are aquaculture, constructed
non-renewable indicate exhaustion of resource by wetlands and conventional wastewater treatment sys-
Impact 2002. tems? Water Science and Technology 40 (3), 45–50.

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EDIP97, CML2001 and Eco-Indicator 99. Interna- (editors), The Wetlands Handbook agricultural
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hensive life cycle inventories of alternative wastewater Roux, P., Boutin, C., Risch, E., Heduit, A. 2010. Life
treatment systems. Water Research 44, 1654–1666. Cycle Environmental Assessment (LCA) of sanita-
Foley, J., David, H., Hartley, K., Lant, P. 2010b. Life cycle tion systems including sewerage: Case of vertical flow
assessment of biological nutrient removal wastewater constructed wetlands versus activated sludge. 12th IWA
treatment plants. International Conference on Wetland systems for
Foley, J., David, H., Hartley, K., Lant, P. 2010c. Compre- water pollution control, Venice.
hensive life cycle inventories of alternative wastewater Wieder, R.K., Tchobanoglous, G., Tuttle, R.W. In
treatment systems. Water Research 44, 1654–1666. Hammer D.A. (editor). 1989. Constructed Wetlands
Friedrich, E., Pillay, S., Buckley, C. 2007. The use of for Wastewater Treatment: municipal, industrial and
LCA in the water industry and the case for an envi- agricultural (1st edition, pp. 297–306). Michigan,
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236
Public health and environment
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Comparison of purifying flue gas with selective catalytic and non-catalytic


reduction in waste-to-energy plants with Life Cycle Assessment (LCA)

E. Picková & V. Kočí


University of Chemistry and Technology, Prague, Czech Republic

ABSTRACT: The amount of Municipal Solid Waste is constantly increasing. Two technologies of NOx
removal from the flue gas of a waste-to-energy plant were compared from an environmental point of view.
The two technologies that were compared are Selective Catalytic Reduction (SCR) and Selective Non-
Catalytic Reduction used in flue gas cleaning in the Prague Waste-to-Energy incineration plant. The Life
Cycle Assessment study evaluated these impact categories: abiotic depletion, acidification, eutrophication
and global warming. In general, the SCR process has environmental impacts due to an increased amount
of energy and abiotic resource consumption. On the other hand, it has less impact in categories such as
acidification and eutrophication which are the ones related to NOx. Those are the impacts that are related
the air emissions, and with the SCR process the plant has less emissions of NOx. Normalization values
indicated that acidification is the most significant impact category for this case study.

1 INTRODUCTION (Caneghema et. al, 2015). This study investigated


environmental impacts of NOx reduction from
Currently, 16 t of material are used per person flue gas by SCR and SNCR used in Prague WtE
per year in Europe and 6 t of these become waste. plant by Life Cycle Assessment (LCA) method.
Each person in Europe is on average producing The results of this case study show that the net
0,5 t of Municipal Solid Waste (MSW) (Euro- environmental impact of the incinerator in the
pean Council, 2015). From the long-term point impact category of global warming increases when
of view the production of MSW in the Czech switching from SNCR to SCR in the hazard waste
republic has been around 0,31 t per capita which incinerator. Therefore, from an environmental
means 3,2 million t in total. More than 55% of the point of view, optimizing existing SNCR should
production is still landfilled, 18% is incinerated be preferred (Caneghema et. al, 2015). Both SCR
(Czech Statistical Office, 2015). Waste to Energy and SNCR are used in the operation the Prague
(WtE) currently represents an important strategy WtE plant. However, they are not used at the same
in the area of waste treatment. The aim of thermal time. The SCR process was introduced in the plant
treatment of the waste is to lower its volume and to operation later to optimize the plant and update it
utilize the chemically bounded energy in the waste. to the best available technologies in the case when
Thermal treatment of waste is possible when reus- ELV for NOx would be lower.
ing or recycling are not possible (Tabasová et. al,
2012). However, incineration processes and other
1.1 Schema of the waste to energy plant
combustion processes of fossil fuel are the main
cuases of air pollution. Nitrogen oxides (NOx) are The projected capacity of Prague WtE plant is
the key combustion generated air contaminants. 310 000 t MSW/year. The MSW are incinerated
(Tabasová & et. al, 2012; Xingxing et. al 2014; in the boiler. The first stage of the NOx removal
Skalska et. al 2010) NOx represent precursors of takes place inside the boiler (SNCR). Next step is
acid rain and photochemical smog. The European the Spray dryer. It consists of a centrifugal cyclone
emission limit value (ELV) for combustion plants for dust removal. Then the flue gas moves to the
is set to 200 mg/Nm3 NOx. Selective non-catalytic electrostatic precipitator. The temperature of flue
reduction (SNCR) is an efficient and cost-effective gas is 220 °C. After that the gas moves to the SCR
technology for removing NOx. The efficiency of system. The gases are cooled before the wet scrub-
the Selective Catalytic Reduction (SCR) in NOx ber system down to 75 °C. After all these steps the
removal efficiency reaches 90%. But this technol- flue gas goes into the chimney and is emitted into
ogy also consumes more energy and resources. the air.

239
1.2 Nitrogen oxides removing technologies Table 1. Significant data in life cycle inventory. Inputs
and outputs of the SCR and
In both techniques, NH3 and urea are injected
in aqueous solutions. In the SNCR process, the Inputs SCR SNCR
reducing agent is injected into furnace and reacts
with nitrogen oxides. 40% urea is injected in to Energy consumption 1435,35 MWh 256 MWh
the flue gas. Optimal temperature for SNCR is Urea – 91 t
850–1000°C. For the optimisation it is important to Natural gas 1 341 774 m3 –
effectively mix the flue gas and NOx reduction rea- Ammonia water 82,7 t –
gent. Sufficient gas residence time to allow the NOx Outputs
reduction reactions to occur is also important.
The optimal temperature for SCR technology is NOx 179 t 208 t
280°C. However, it´s installed downstream of the PCDF/F 5,0E-5 kg 1,20E-5 kg
spray drayer and electrofilter. The temperature of
the flue gas is low and therefore it requires addi-
represents using SNCR. The reference flow corre-
tion of heat (natural gas). As a result, this technol-
sponds to the functional unit. LCA study utilizes
ogy significantly increases energy consumption.
the characterization model CML 2001–April 2013
The flue gas with the reduction agent pass over an
and evaluates the impact category at the midpoint
installed catalyst TiO2/V2O5/WO3.
level with the following categories assessed: Abiotic
resource Depletion Potential (ADP), Acidification
Potential (AP), Eutrophication Potential (EP) and
2 METHODS
Global Warming Potential (GWP).
2.1 Goals and scope definition
2.2 Life cycle inventory
The goal of the case study is to compare two NOx
removing technologies (SCR and SNCR) in the The data for Life Cycle Inventory (LCI) were
Prague WtE plant. Two models represent the life provided by the Prague WtE plant (daily data of
cycle of the WtE plant and assess the environmen- emission, amount of additives, energy consump-
tal impacts of the operation. The purpose of the tion). The environmental impacts of the electric-
system is to incinerate the MSW and purify flue ity, generation of the heat, production of the urea
gas. The functional unit is the amount of MSW and ammonium were calculated from the GaBi
(122 520 t) incinerated in the Prague WtE in speci- Databases. The scheme of the product system was
fied period of time (140 days) in one year. Two sce- modelled in GaBi. Relevant energy and resources
narios are modelled to compare (Figure 1). First consumption of SCR and SNCR and the amount
scenario represents using SCR. Second scenario of the emissions are given in Table 1.

2.3 Normalization
Normalization transforms the results of an
impact category indicator into a non-dimensional
value. A non-dimensional number is produced by
diving the impact category indicator of a given
elemental flow by the impact category indicator
of the elemental flow for the whole system (e.g.
region) (Heijungs et al., 2007). The normaliza-
tion was performed by Normalization model
EU25+3, year 2000 CML, IPPC, ReCiPe (person
equivalents).

3 RESULTS AND DISCUSSION

Specific environmental problems emerge as a


consequence of releasing elementary flows from
individual phases of the product life cycle into the
environment (Kočí, 2009). Using GaBi, the results
from the inventory phase were allocated to individ-
Figure 1. Modelled scenarios. ual impact categories. It is important to note that

240
NOx are assigned to the acidification category and specifies the quantity of nitrogen and phosphorus
the eutrophication category. from the elementary flow emissions that may be
Significant values are shown in the graph. released from the process into environment. When
Figure 2 and Figure 3 show the influence of the WtE plant use SCR technology, it has less impact
SCR and SNCR technologies upon the devel- on both impact categories because this technology
opment of the resources impact category. The emits less NOx (Figure 5, Figure 6).
resources impact category represents the influence Normalization values indicated that acidifica-
of the technology on the decreasing availability tion is the most significant impact category for
of renewable and non-renewable resources. This both situations (when WtE uses SNCR or SCR).
is caused the by high consumption of electricity In impact category, the SNCR pollutes the envi-
and natural gas which is necessary for heating the ronment more. Second significant impact category
flue gases before the catalytic reduction. Figure 4 is fossil abiotic depletion, see Figure 7. The increase
also depicts the influence of the assessed technolo- of AP and GWP impact categories when WtE uses
gies on the intervention impact category of GWP. the SCR is almost the same significant. The SCR
GWP represents a gauge for potential contribu-
tions of elementary emissions to withhold energy
from being released into the atmosphere. Higher
contribution to GWP pertains WtE plant when
using SCR technology.
Acidification of the environment is caused by
increased concentrations of acidifying agents in
the environment. Acid deposition influences not
only the quality and functionality of the natural
ecosystem but also the quality of the anthropo-
genic landscape. Anthropogenic eutrophication is
caused by the increasing emission of bioavailable
nutrients into the aquatic environment. The EP
Figure 4. Characterization profile in assessed category
global warming potential (kg CO2-Equiv.).

Figure 2. Characterization profile in assessed category


Abiotic Depletion (kg Sb-Equiv.).
Figure 5. Acidification potential (kg SO2-Equiv.).

Figure 3. Characterization profile in assessed category


Abiotic Depletion (MJ). Figure 6. Eutrophication potential (kg Phosphate-Equiv.).

241
malization values indicated that acidification is the
most important impact category. This category is
more affected by SNCR. The second and third sig-
nificant impact categories, after normalization, are
fossil ADP and GWP. These categories are more
affected by SCR. The increase of the impact on
the AP and GWP categories when the SCR is used
by the WtE is almost the same. SCR significantly
increases environmental impact on GWP. On the
other hand, if ELV for NOx emissions was lower
than it is these days, WtE with SCR would be able
to stand this limit.
Figure 7. Normalization values.
This study does not show that tightening of the
emission limits is not an environmentally correct
way. Another tightening of NOx—ELV would
significantly increases environmental impact on mean that the above mentioned WtE using the
GWP. SCR technology, which is able to reach those limits,
would, from an environmental point of view, have
lower impact on certain impact categories such as
4 CONCLUSIONS the EP category. However, it would also impact
categories such us ADP, EP and GWP more sig-
The NOx removal techniques are used in the plant nificantly. Therefore, from an environmental point
on different days and present both advantages and of view, optimizing existing SNCR should be pre-
disadvantages from the environmental and eco- ferred (Caneghema et. al, 2015).
nomical points of view.
The LCA evaluated the impact categories at the
midpoint level. SCR and SNCR present different REFERENCES
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242
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

The effects of reduction conditions on synthesis of graphene


by modified hummers and eco-friendly methods

H.H. Nguyen
Key Laboratory of Chemical Engineering and Petroleum Processing, Ho Chi Minh City University
of Technology, Vietnam National University, Ho Chi Minh City, Vietnam
Faculty of Chemical Engineering, Ho Chi Minh City University of Technology, Vietnam National University,
Ho Chi Minh City, Vietnam

ABSTRACT: In this work, Graphene (Ge) was synthesized from graphene oxide by modified Hummers’
method and reduced directly from graphite by eco-friendly method. Accordingly, for the reduction of
graphene oxide to form reduced Graphene Oxide (rGO), the effects of amount of required hydrazine
hydrate reductant, ultrasound power, and reduction time were investigated. Subsequently, for the directly
reduction of graphite to obtain Ge, the reducing agents as hydrogen peroxide, ammonium peroxydisul-
phate, and microwave radiation were used. Characterizations of obtained rGO/Ge were performed by
Fourier transform-infrared spectroscopy, X-ray diffraction, Raman spectroscopy, thermal gravimetric
analysis, electrical conductivity, Atomic Force Microscopy (AFM), and Transmission Electron Micro-
scopy (TEM). The successful synthesis of rGO/Ge products was confirmed by Raman spectra with the
characteristic bands as D and G. The fine structure of rGO/Ge nanosheets was further confirmed by
TEM and AFM images. The eco-friendly method produced Ge almost the same to that synthesized by
modified Hummers’ method.

Keywords: reduction, conditions, synthesis, graphene, modified, Hummers, eco-friendly

1 INTRODUCTION

Graphite (Gi) is a carbon allotrope, is found in


layers of sp2 hybridized carbons in the form of
planar hexagonal rings. These single sheets are
held together by van der Waals forces which are
weak enough to separate to some degree by sim-
ple mechanical exfoliation (Khot et al, 2012;
Figure 1. The structure of Gi.
Mukhopadhyay & Gupta, 2013). These layers
are 3.35 Å apart and the carbon-carbon covalent
sigma-type bond length within the layer is 1.42 Å
(Wattanaprayoon & Chaiyaporn, 2014). Gi is a
three dimensional (3D) carbon based material
made up of millions of layers as shown in Figure 1
(Mukhopadhyay & Gupta, 2013).
Graphene Oxide (GO) which was prepared by
chemically oxidizing Gi to form graphite oxide Figure 2. The structure of single GO sheet.
with strong oxidants and ultrasonic cleavage. In
addition, because of the large amount of oxygen drug-delivery, bio-devices, etc (Panwar et al 2015).
contains epoxide and hydroxyl groups within the Brodie first demonstrated the synthesis of GO in
sheets; carboxyl and carbonyl groups at the sheet 1859 by adding a portion of potassium chlorate to
edges, as shown in Figure 2; GO shows excellent a slurry of graphite in fuming nitric acid (Sengupta
hydrophilicity and is relatively easily dispersed in et al, 2011). In 1898, Staudenmaier improved on
water and even in other solvents through further this protocol by using concentrated sulfuric acid as
modification (Dreyer et al, 2010; Shao et al, 2012). well as fuming nitric acid and adding the chlorate
Nowadays, GO has been widely used in diverse in multiple aliquots over the course of the reaction
applications like composites, optoelectronics, (Staudenmaier, 1893). This small change in the

243
procedure made the production of highly oxidized than commercial silicon) and resistivity only about
GO in a single reaction vessel significantly more 10−6 Ω.cm (for minimum resistivity material in the
practical. In 1958, Hummers reported the method world). The outstanding performance of the ther-
most commonly used today: the graphite is oxi- mal conductivity (3000 W/m−1K−1, is three times
dized by treatment with KMnO4 and NaNO3 in that of the diamond) and mechanical properties
concentrated H2SO4 (Humers & Offeman, 1958). (Young’s modulus of up 1.0 Tpa, is more than 100
The Hummers’ method is widely used even today times of steel). The speed of movement of the elec-
with some modifications, including the modified trons in the Ge exceeds the speed of movement in
Hummers’ method (Shahriary & Athawale, 2014) the other single metal or a semiconductor, it is pos-
and the improved Hummers’ method (Marcano et sible to achieve the speed of light to 1/300 (Singh
al, 2010). et al, 2011; Khot et al, 2012; Mukhopadhyay &
Graphene (Ge) is a single layer sheet of Gi. Its Gupta, 2013; Wattanaprayoon & Chaiyaporn,
structure is two dimensional (2D) with aromatic lat- 2014). Owing to Ge’s unique physical and chemical
tices of carbon atom, as shown in Figure 3 (Singh properties, Ge and its derivatives have attracted tre-
et al, 2011; Khot et al, 2012; Mukhopadhyay & mendous interest in many different fields in recent
Gupta, 2013; Wattanaprayoon & Chaiyaporn, years such as energy, electronics, sensor, catalysis,
2014). supercapacitor, composites, and ultrafiltration
Ge is a 2D structure, it is only one carbon-atom (Brownson et al, 2011; Pu et al, 2012; Liu, 2014;
thick. The discovery of Ge by Andre Geim and Liu et al, 2014; Lonkar & Abdala, 2014; Randviir
co-workers at the University of Manchester using et al, 2014; Tan et al, 2014).
the deceptively simple scotch tape method has cre- Recently, researchers have been trying to find
ated a revolution in condensed matter physics (Loh a way to produce Ge precisely and productively.
et al, 2012). Thereafter, Ge is heralded as the next- New methods have been introduced, several of
generation material for nanoelectronic devices. which are very promising are mentioned such as
Ge boasts a one-atom-thick, two-dimensional chemical vapor deposition-CVD (thermal CVD,
structure, making it the thinnest material in the plasma CVD, and thermal decomposition on SiC
known universe (Khot et al, 2012; Mukhopadhyay and other substrate), exfoliation and cleavage
& Gupta, 2013; Wattanaprayoon & Chaiyaporn, (mechanical exfoliation and mechanical exfolia-
2014). A single layer of Ge, which is so thin that tion in solutions), chemical exfoliation (synthesis
it would require three million sheets stacked on of GO and the reduction, and surface functionali-
top of one another to make a pile just one mil- zation of GO), eco-friendly method (supercritical
limeter high, allows stretching by up to 20% of its CO2 extraction, electrochemical exfoliation, and
equilibrium size without sustaining any damage ultrasound-microwave assisted preparation of Ge)
(Gladstone, 2012). More importantly, the unique (Park & Ruoff, 2009; Sridhar et al, 2010, Singh et
structure of the Ge has multiple excellent proper- al, 2011, Khot et al, 2012; Loh et al 2012; Wattana-
ties, such as the smaller the mass density (2.2 g/ prayoon & Chaiyaporn, 2014; Chang et al, 2015;
cm3), a great specific surface area (∼ 2630 m2/g), a Subramanya & Bhat, 2015).
high intrinsic mobility (>104 cm2/Vs 10 times more Currently, Hummers’ method is a popular and
potential method for large-scale production of
reduced Graphene Oxide (rGO) or Ge (Dreyer
et al, 2010; Ren et al, 2011; Song et al, 2014). How-
ever, it involves environmental duty. Therefore,
researchers have been trying to find a way to pro-
duce Ge precisely and productively. A new method
for synthesis of Ge directly from Gi through eco-
friendly method (Sridhar et al, 2010). This method
decreases the cost and environmental duty of Ge
production.
In this work, the effects of reduction conditions
in synthesis of Ge through modified Hummers’
and eco-friendly methods were studied. The char-
acterizations of obtained Ge products were stud-
ied by Fourier transform-infrared spectroscopy
(FTIR), X-Ray Diffraction (XRD), Raman spec-
troscopy, Thermal Gravimetric Analysis (TGA),
electrical conductivity, Atomic Force Microscopy
(AFM), and Transmission Electron Microscopy
Figure 3. The structure of single Ge sheet. (TEM).

244
2 EXPERIMENTAL (467 W) at 35°C for 30 minutes. Then, the mix-
ture was centrifuged and repeatedly washed with
2.1 Materials distilled water. The suspensions were collected.
Finally, the resulted Ge was filtered and dried
Graphite powder (<20 μm) was purchased from
at 90°C for 24 h. The sample was designated as
Sigma Aldrich, Germany. Sulfuric acid (98%),
Ge-10.
Phosphoric acid (85%), hydrogen peroxide (30%),
hydrazine hydrate (50%), ammonium peroxydi-
sulfate (98%), and sodium nitrate (>99%) were 2.4 Characterization
purchased from Xilong Chemical, China. Potas- FTIR spectra were obtained on a Bruker (Tensor
sium permanganate (>99%) was purchased from 27) between 4000 and 400 cm−1, using a KBr
ViNa Chemsol, Vietnam. All chemicals were ana- disk method. XRD patterns were recorded on
lytical grade and used as received without further D500 (SIEMENS), employing a scanning rate of
purification. 0.03 °/0.8 s from 5° to 80° with CuKα radiation
(k = 0.154 nm). Raman spectra were recorded using a
2.2 Effects of reduction conditions on synthesis micro-Raman spectroscopy (LABRAM-HORIBA
rGO by modified Hummers’ method JONINYVON, the excitation wavelength at 632.8
nm). TGA was performed on LabSys Evo TG-
2.2.1 Amount of hydrazine hydrate reductant DSC 1600, model: D1935 (SETARAM—France)
GO was prepared from Gi by modified Hummers’ from 30 to 1000°C under nitrogen atmosphere
method (Hieu et al, 2016). 0.1 g GO was dispersed (heating rate: 1°C/min). Electrical conductivity was
in 100 mL water and the mixture was immersed into performed on OLYMPUS, model: 302466 (Japan),
an ultrasonic bath (467 W) at 35°C for 1 h. After samples were made by Four Point Probe. AFM
that, 3 mL hydrazine hydrate was added gradually measurements were performed on AFM Nanotec
under stirring for 30 min. The mixture was placed Electronica (Spain), samples were made by casting
into an ultrasonic bath (467 W) at 35°C for 4 h. the powder dispersions onto freshly cleaved mica
Then, the mixture was centrifuged and repeatedly substrates and drying under ambient condition.
washed with distilled water. The resulted rGO was TEM images were taken by using a microscope of
dried at 90°C for 24 h. The sample was designated JEM-1010 (JEOL Ltd., Japan) operated at 80 kV,
as rGO-1. The process was similar to that as shown samples were prepared by drop casting the powder
above. The amount of hydrazine hydrate reductant dispersion onto a holey carbon-coated copper grid
was changed into 4 mL, 5 mL, 6 mL, and 8 mL; and subsequent drying under ambient condition.
and the samples were designated as rGO-2, rGO-3,
rGO-4, and rGO-5, respectively.
3 RESULTS AND DISCUSSION
2.2.2 Reduction time
The process was similar to that as shown above. 3.1 Effects of reduction conditions on synthesis
Selecting the optimum volume of reductant, the of rGO
reduction time was changed into 3 h and 5 h; and 3.1.1 Amount of hydrazine hydrate reductant
the samples were designated as rGO-6 and rGO-7, The entire oxidation of Gi and reduction of GO
respectively. can be observed through the FTIR spectra, as
shown in Figure 4. The spectrum of Gi showed the
2.2.3 Ultrasound power absorption bands at 3432 cm−1 that can be attrib-
The process was similar to that as presented. uted the O-H stretching vibration of hydroxyl
Selecting the optimum time, the ultrasound power groups (Stankovich et al, 2007; Park et al, 2011;
was changed into 233 W and 700 W; and the Ren et al, 2011; Loryuenyong et al, 2013).
samples were designated as rGO-8 and rGO-9, After the oxidation, the FTIR spectrum of
respectively. GO-6 apparently changed compared to that of Gi.
Apart from the hydroxyl (O-H) stretching vibra-
tions, six new representative peaks arising from
2.3 Synthesis of Ge by eco-friendly method
GO could be indexed at 2925/2857 cm−1, 1738
0.125 g ammonium peroxydisulfate powder and 2.5 cm−1, 1635 cm1, and 1400/1070 cm−1, which corre-
g Gi were dispersed in 1.15 mL hydrogen peroxide spond to the stretching of alkyl (CH, CH2), car-
and the mixture was immersed into an ultrasonic bonyl (C = O) and carboxylic (COOH), sp2 C = C
bath (467 W) at 35°C for 10 minutes. After that, bonds, and epoxide (C-O-C) groups, respectively
the mixture was placed into a microware (800 W) (Stankovich et al, 2007; Park et al, 2011; Ren et
for 2 minutes. Then, the mixture was dispersed in al, 2011; Loryuenyong et al, 2013). The polar
400 mL water and placed into an ultrasonic bath groups, especially the surface hydroxyl groups,

245
Issues Issues

Helping Children Face Tough IssuesHelping Children Face Tough Issues


Figure 5. FTIR spectra of Gi, GO, rGO-3, rGO-6, and
Figure 4. FTIR spectra of Gi, GO, rGO-1, rGO-2,
rGO-7.
rGO-3, rGO-4, and rGO-5.

result in the formation of hydrogen bonds between


Gi and water molecules; this further explains the
hydrophilic nature of GO (Oyer, 2013).
After the reduction of GO, the stretching
vibrations of oxygen functional groups were sig-
nificantly decreased. The influences on the degree
of reduction of rGO increased in the order of 2
mL < 3 mL < 5 mL or 6 mL or 8 mL according
Issues
to the stretching vibrations of oxygen functional
groups (Zhang et al, 2010; Jin et al, 2013). The
FTIR spectra of rGO-3, rGO-4, and rGO-5 are
nearly identical to Gi. Therefore, 5 mL of hydra-
zine hydrate (rGO-3) was appropriate to synthesize
rGO. Besides, the presence of peaks at 2925/2857
cm−1 in Ge implies the sp2 hybridized carbon can-
not be entirely restored by hydrazine hydrate (Ren Helping Children Face Tough Issues
et al, 2011).
Figure 6. FTIR spectra of Gi, GO, rGO-7, rGO-8, and
3.1.2 Reduction time rGO-9.
The FTIR spectra of rGO-3, rGO-6, and rGO-7
are shown in Figure 5. After the reduction, the 2010; Jin et al, 2013). After the reduction, the
stretching vibrations of oxygen functional groups stretching vibrations of oxygen functional groups
were significantly decreased. The influences on the of rGO-9 were totally decreased and the FTIR
degree of reduction of rGO increased in the order spectrum of rGO-9 was nearly identical to Gi than
of 3 h < 4 h < 5 h according to the stretching vibra- the others. Therefore, the ultrasound power of 700
tions of oxygen functional groups. Additionally, W (rGO-9) was appropriate to synthesize rGO.
the FTIR spectrum of rGO-7 was nearly identical As a result of the modified Hummers’ method to
to Gi than the others. This result shows that the synthesize rGO, the optimum reduction conditions
reduction time of 5 h (rGO-7) was appropriate to to obtain the maximum degree of reduction of GO
synthesize rGO. are the amount of hydrazine hydrate of 5 mL for 5
h under the ultrasound capacity of 700 W.
3.1.3 Ultrasound power
The FTIR spectra of rGO-7, rGO-8, and rGO-9
3.2 FTIR analysis of eco-friendly Ge
are shown in Figure 6. The influences on the degree
of reduction of Ge increased in the order of 233 W The FTIR spectra of Gi and Ge-10 are shown in
< 467 W < 700 W according to the stretching vibra- Figure 7. The FTIR spectrum of Ge-10 appar-
tions of oxygen functional groups (Zhang et al, ently changed compared to that of Gi. Only

246
representative peak arising from Ge could be (Park et al, 2011). In the XRD pattern of rGO-
indexed at 1580 cm−1, which corresponds to the 9, the major peak is observed at about 24–26°
stretching of sp2 C = C bonds. Besides, the pres- (Park et al, 2011). In the XRD pattern of Ge-10,
ence of peaks at 2925/2857 cm−1 in Ge implies the the major peak is observed at 26° (Sridhar et al,
sp2 hybridized carbon can be entirely restored. 2010). In addition, the major peak of Ge-10 is nar-
Through the FTIR spectra, the eco-friendly row and clearly than rGO-9, which implies the sp2
obtained Ge is better than obtain the rGO prod- hybridized carbon can be entirely restored.
ucts by modified Hummers’ method.
3.3.2 Raman spectra
The Raman spectra of Gi, rGO-9, and Ge-10 are
3.3 Characteristic comparison between Gi,
shown in Figure 9 and Figure 10. The peaks around
modified Hummers (rGO-9) and eco-friendly
1580 cm−1 (G-band) and 1370 cm−1 (D-band) were
(Ge-10) products
detected for the Gi and Ge. The G-band around
3.3.1 XRD patterns 1580 cm−1 was related to the vibration of sp2-bonded
The XRD patterns of Gi, rGO-9, and Ge-10 are carbon atoms in a two-dimensional hexagonal lat-
shown in Figure 8. tice. The D-band around 1370 cm−1 was associated
It can be seen that Gi has a strong and sharp with the vibration of disordered sp2-bonded car-
diffraction peak at 2θ = 26.5°, corresponding to the bon atoms (Stankovich et al, 2007; Loryuenyong
highly organized layer structure with an interlayer et al, 2013). These bands could be used to evaluate
distance of 0.34 Å (Loh et al, 2012). The diffrac- the extent of carbon-containing defects. The final
tion peak of Gi is replaced by a broad diffraction peak is known as the 2D peak, which is located
peak of rGO-9 and Ge-10. This demonstrates an at approximately 2700 cm−1 (Loryuenyong et al,
increased interlayer distance between layers of Ge 2013).

Helping Children Face Tough Issues


Helping Children Face Tough Issues
Figure 7. FTIR spectra of Gi, and Ge-10.
Figure 9. Raman spectrum of Gi.

Helping Children Face Tough Issues


Helping Children Face Tough Issues
Figure 8. XRD patterns of Gi, rGO-9, and Ge-10. Figure 10. Raman spectra of rGO-9 and Ge-10.

247
The intensity of D-band was known to increase 3.3.4 Electrical conductivity
when Ge were formed. It could be observed from Ge is reported to have a high electrical conductiv-
Figure 10 that the intensity of D-band increased ity. The electrical conductivity of rGO-9 and Ge-10
while that of the G-band decreased for the Ge. are 200 S/m and 500 S/m, respectively, as shown in
These results reveal that rGO/Ge was success- Table 1. These results reveal that rGO/Ge product
fully synthesized and similar to previous works was similar to previous work (Pei & Cheng, 2012).
(Stankovich et al, 2007; Sridhar et al, 2010; Zhang Therefore, the eco-friendly obtained Ge is better
et al, 2010; Loryuenyong et al, 2013). The influ- than modified Hummers’ rGO.
ences on the defect of Ge increased in the order
of Ge-10 < rGO-9 according to the value ID/IG 3.3.5 AFM images
(rGO-9:1.35, Ge-10:1.02). Therefore, eco-friendly From the AFM image and height profile, the rGO-9
method was appropriate to synthesize Ge. layers was found to be about 0.953 nm, as shown in
Figure 13, and about 0.921 nm for Ge-10 layers, as
3.3.3 TGA analysis shown in Figure 14. The AFM images reveal that
Thermal stability of Gi, rGO-9, and Ge-10 was rGO/Ge was successfully synthesized and similar
examined by TGA analysis as shown in Figure 11. to previous works (≈1 nm) (Stankovich et al, 2007;
It is evident that Gi exhibited one clear step of Sridhar et al, 2010; Zhang et al, 2010).
weight loss. The first weight loss at 50–440oC
relates to the loss of water molecules and oxygen- 3.3.6 TEM images
containing groups (Loryuenyong et al, 2013). The The TEM images of rGO-9 and Ge-10 as shown in
Ge-10 shows similar characteristic but with lower Figure 15. After the reduction, rGO sheets become
amount of weight loss, compared to that of rGO- smaller and transparent. The sheet is so thin that
9. This could be explained that the amount of oxy- electron beam can be passed through sample. The
gen-containing functional groups in Ge-10 is lower images reveal thin transparent sheets folded at the
than that of rGO-9.
Table 1. Sheet resistance and electrical conductivity of
rGO and Ge.

Electrical
Thickness, Sheet resistance, conductivity,
Samples d (mm) Rs (Ω/ ) ζ (S/m)

rGO-9 1 5 200
Ge-10 1 2 500

where ζ = 1/(Rsd) (S/m), d (m): sample thickness, Rs (Ω/ ):


sheet resistance.

Helping Children Face Tough Issues


Figure 11. TGA curves of Gi, rGO-9, and Ge-10.

Figure 13. AFM image and height profile of rGO-9.

Figure 12. A tablet of Ge. Figure 14. AFM image and height profile of Ge-10.

248
Liu, J. 2014. Charging graphene for energy. J. Nat.
Nanotechnol. 9: 739–741.
Liu, M. et al 2014. Graphene-Supported Nanoelectrocat-
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Loh, K.P. et al 2012. The chemistry of graphene. J. Mater.
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Lonkar, S.P. & Abdala, A.A. 2014. Applications of
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Water-Based Exfoliation and Reduction Methods.
edges which is a featured structure of rGO/Ge J. Advances in Materials Science and Engineering
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successfully synthesized and similar to previous ene Oxide. J. ACS nano 4: 4806–4814.
works (Zhang et al, 2010; Zhang & Feng, 2010; Jin Mukhopadhyay, P. & Gupta, R.K. 2013. Graphite, GE
et al, 2013; Loryuenyong et al, 2013). and their polymer nanocomposite. New York: Taylor
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4 CONCLUSIONS mapping curvature at the nanoscale, Nano Letters 12:
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Oyer, A.J. 2013. Exfoliation and Chemical Modifications
In this study, rGO and Ge were synthesized by of Natural Flake Graphite. Doctoral Dissertations.
the modified Hummers’ and eco-friendly meth- Connecticut University (2013).
ods, respectively. The reduction conditions for the Panwar, V. et al 2015. A new facile route for synthesizing
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peroxydisulphate, and microwave radiation could Park, S. & Ruoff, R.S. 2009. Chemical methods for pro-
duction of graphenes. J. Nature Nanotech. 4.
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than that of rGO. Additionally, the Raman spec- oxide. Carbon 50: 3210–3228.
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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Assessment of body burden of Czech population to polycyclic aromatic


hydrocarbons

J. Pulkrabova, D. Lankova, K. Urbancova, A. Svarcova, M. Stupak & J. Hajslova


Department of Food Analysis and Nutrition, University of Chemistry and Technology, Prague, Czech Republic

ABSTRACT: Polycyclic Aromatic Hydrocarbons (PAHs), produced by incomplete combustion of


organic materials, are ubiquitous contaminants present in the environment. We assessed the concentrations
of PAHs in samples of (i) air, (ii) one week diet of pregnant women, (iii) human breast milk and (iv) OH-
PAHs in urine of both mothers and their newborns living in two region of the Czech Republic differing
in atmospheric contamination by PAHs, specifically the industrial city Karvina and the less industrialized
Ceske Budejovice. Samples were collected during two periods August-October 2013 and January-April
2014. Based on the obtained results, we evaluated the extent of mothers and newborns exposure to major
PAHs via different routes. For example for pyrene, the major part of exposure (80–95%) in „summer“ is
via diet while in „winter“ more than 70% is via inhalation, especially in Karvina region. The more results,
including the carcinogenic PAHs, will be showed in detail during presentation.

1 INTRODUCTION PAHs can undergo at least three major metabolic


pathways which form highly reactive electrophilic
Polycyclic Aromatic Hydrocarbons (PAHs) are intermediates capable of binding to cellular mac-
ubiquitous organic chemicals, typical products romolecules, in particular proteins and nucleic
of pyrolysis or petrogenic origin that enter into acids. Following absorption rapid biotransforma-
the environment from numerous sources, mainly tion process starts with the phase I metabolism in
though atmospheric deposition, road run-off, which these compounds are oxidized by the hepatic
industrial discharges and oil spills. PAHs never cytochrome P450 (CYP 450) monooxygenases to
occur individually but in mixtures. US Environ- form reactive epoxide intermediates followed by
mental Protection Agency (US EPA) defined the their reduction or hydrolysis yielding hydroxylated
key PAHs most frequently polluting the envi- derivatives (OH-PAHs). In the phase II metabo-
ronment commonly known as the “16 US EPA lism, the OH-PAHs are conjugated to glucuronic
PAHs”. Eight of them are known carcinogens and/ acid or sulphate to increase the water solubility.
or mutagens and give rise to a serious health con- OH-PAH conjugates with 2–3 benzene rings (low-
cern (IARC, 2010). In 2002, the European Com- molecular-weight OH-PAHs) are mostly excreted
mission’s Scientific Committee on Food (SCF) via urine and those with 4 or more benzene rings
assessed 33 PAHs potentially occurring in food, are mainly excreted via bile and faeces (high-mo-
confirmed the subset of eight PAHs from the US lecular-weight OH-PAHs) (Campo et al. 2008).
EPA list mentioned above, and identified eight Due to the above mentioned human health
additional PAHs as of major concern for consum- effects of PAHs, monitoring of an occurrence
ers’ health (EFSA 2008). of metabolites in biological matrices represents
The most common exposure pathway of a an important tool for the assessment of human
human body to PAHs is through a digestion of exposure. Currently the most common biomark-
contaminated foods which accounts for over 70% ers for the evaluation of PAHs overall exposure are
of the total PAH exposure for non-smokers. Other OH-PAHs.
important exposure route is the inhalation of air- The main aims of the presented study were to
borne PAHs, in case of smokers the tobacco smoke assess the exposure of human population to PAHs
is the major source (Moustafa et al. 2015). For the based on the analysis of (i) 24 PAHs in air sam-
occupationally exposed individuals transfer of pled by high volume samplers, in the total diet of
these substances through the skin may also play an women, in human breast milk samples, (ii) 11 OH-
important role (e.g. workers with asphalt or coal). PAHs in the set of urine samples obtained from the
The fate of PAHs in the exposed organism women and their newborn children living in Ceske
is fairly complex. Carcinogenic and mutagenic Budejovice and Karvina.

251
2 EXPERIMENTAL (3:1, v/v) in the Soxhlet apparatus, after concertation
the samples were purified on silica columns as
2.1 Samples already described above for previous matrices.
For analysis of urine samples a sample prepa-
The sampling was carried out in two rounds,
ration procedure based on Liquid-Liquid Extrac-
namely in August—September 2013 (summer
tion (LLE) with clean-up using dispersive solid
period) representing less air-polluted season by
phase extraction (d-SPE) is described in detail by
PAHs and in January—April 2014 (winter period)
Lankova et al. 2016. Briefly, deconjugation for
as more contaminated environment by these pol-
the release OH-PAHs was performed by enzyme
lutants due to more frequent use of heating in a
β-glucuronidase (overnight incubation), then the
winter season. The sampling was realized in two
analytes were extracted was extracted from thy
regions of the Czech Republic—Ceske Budejovice,
hydrolysate by ethyl acetate shaking. After cen-
the control locality with lower contaminated envi-
trifugation the upper organic layer was purified by
ronment by PAHs and Karvina, the locality with
Z-Sep and anhydrous MgSO4. A purified extract
high atmospheric pollution due to the heavy indus-
was evaporated and redisolved in methanol for the
try e.g. coke and steel production.
U-HPLC–MS/MS analysis on ultra-Performance
Duplicates of the total diet (without beverages)
LC system (Waters, USA). Analytes were separated
were collected from selected mothers approximately
on a PFP (pentafluorophenyl) Kinetex column,
one week before the delivery, in both regions and
Phenomenex, (USA) (100 mm × 2.1 mm × 1.7 μm)
the sampling periods. Filters from hi-vol samplers
To control background contamination by tar-
which were collected each third day of the sampling
get analytes the procedural blank (was prepared
period. Approximately 15–30 ml of human milk
together with each batch of 20 samples (per day).
and 15 ml urine from each mother (newborns) was
Concentration of contamination in the blank sam-
collected into the n-hexane-rinsed amber reagent
ple was subtracted from all samples prepared at the
bottles. The samples were stored in the freezer at
same day as the blank sample.
−20°C before analysis. More details on the number
of samples are summarized in Table 1.
3 RESULTS AND DISCUSSION
2.2 Analytical methods
Human milk and total diet samples were mixed Total diet samples were analyzed on levels of 24
with water and shaken with ethyl acetate in a PP PAHs within two sampling rounds. With exception
centrifuge tube. Subsequently, anhydrous magne- of DBahP, all target analytes were detected at least
sium sulphate and sodium chloride were added to in two samples. A quite high variability between
the mixture to induce the transfer of target ana- the samples from different mothers was observed
lytes into the organic phase. After centrifugation here but generally concentrations were very low,
an aliquot of the upper organic layer was concen- the maximum value for the sum of all targeted
trated and purified using a silica column. Analytes PAHs was below 20 μg/kg. When we compared the
were eluted with of mixture n-hexane: dichlo- results of PAH4 (BaP, CHR, BbFA and BaA), they
romethane (3:1, v/v). A collected eluate was care- were very similar in samples from all women, with
fully evaporated and redisolved in isooctane for the exception of four samples amount of PAH4 was
subsequent GC–MS/MS analysis using a gas chro- below 1 μg/kg. These four PAHs were selected for
matograph Agilent 7890A GC coupled to a triple illustration of results, since these compounds are
quadrupole mass spectrometer Agilent 7000B MS recommended for the monitoring in food by the
(Agilent Technologies), or the separation, capillary European Food Safety Authority (EFSA) and also
column Rxi®-PAH (40 m × 0.18 mm i.d. × 0.07 μm their levels are regulated in food. The major repre-
film thickness; Restek, USA) was used. More detail sentative of this group is CHR followed by BaP.
on the analytical procedure is described in our pre- The complex comparison of the data from both
vious study (Pulkrabova et al. 2016). localities and sampling periods is shown in the
Filters from the high volume samplers were Fig 1, but the contamination of all samples was
extracted using a mixture n-hexane:dichloromethane very similar and no trend was identified.

Table 1. Information on the analyzed samples.

Area Sampling period Urine (mothers/infants) Human diet Air Breast milk

České Budějovice 1st period: August–October 2013 98/91 68 23 96


2nd period: January–April 2014 100/80 70 26 95
Karviná 1st period: August–October 2013 65/65 71 36 66
2nd period: January–April 2014 64/54 69 46 67

252
Employing the newly developed, highly sensitive from mothers and their newborn children was
GC-MS/MS method 17 of 24 targeted PAHs were examined for the presence of eleven OH-PAHs.
detected at least in one of the human milk samples. To compensate for the differences in the hydration
PHE, FLA, PYE and FLN (i.e. non carcino- state of urine donors and thus enable comparison
genic species) were the most abundant PAHs repre- of biomarker levels creatinine concentrations were
sentatives found at average concentration of 13.81, also determined in all samples. Levels of target ana-
1.80, 0.86, 2.01 ng/g lipid weight, respectively. As lytes in urine were normalized using the ratio OH-
regards carcinogenic PAHs, BaP was detected only PAH/creatinine (creatinine concentrations ranged
in 19 of analyzed samples and made about 0.4% from 300 to 2,900 mg/kg, median was 920 mg/kg).
of the total PAHs amount. Comparing the data 2-OH-NAP was the most abundant of monitored
from two sampling periods (winter and summer), PAH exposure markers occurring in 100% of the
in both residential areas higher concentrations urine samples. At the same time it was the analyte
were measured in samples collected in the winter with the highest concentration (5,400 ng/g cre-
period. Also in the highly industrialized locality atinine for mothers and 3,100 ng/g creatinine for
with heavily contaminated air PAH amounts in infants, respectively). 6-OH-CHRY and 3-OH-
milk were higher than in the control locality but BaP, metabolites of carcinogenic PAHs were not
the PAHs profile were very similar. The contribu- detected in any of the measured samples. Regard-
tion of ingestion to the total intake is quite variable ing individual OH-PHEN isomers, the higher lev-
for individual compounds and in summer made els of 9-OH-PHEN were observed in urine samples
between 50 to 95% of the total intake, while in win- collected from both mothers and their newborn
ter in the heavily air contaminated industrialized children in the winter season.
locality the inhalation is unambiguously the domi- The median concentration of ΣOH-PAH in the
nant pathway. Obtained results are very important childrens´ urine were 1.6 times lower compared to
contribution for the complex assessment health their mothers. However, the correlation between
risks associated with to exposure to PAHs during all detected individual OH-PAHs in urine samples
breastfeeding period, but it is necessary to take into from mother and their newborn children was not
account also other sources such as inhalation. found.
Contamination of air samples was assessed While the content of ΣOH-PAH in mothers´
based on the analysis of filters from high volume urine collected in the summer period was com-
samplers. Samples from Karviná region was sig- parable in both localities, in the winter period
nificantly higher (5–7x) than from Ceske Budejo- the samples from the Karvina region showed 1.5
vice. In the winter period the levels of PAHs were times higher amounts of exposure markers. The
almost 10-times higher compared to the summer amounts of ΣOH-PAH in infants’ urine samples
season (e.g. BaP 4x; PYR 10x). from highly industrialized Karvina in the winter
The increase of the PAH levels started at the season were 1.5 times higher than in the summer
beginning of October with the start of a heating season collected in the same locality and 3.3 times
season. Similarly to diet samples, also for filters higher when compared with less polluted locality
profiles of individual compounds from PAH4 in of Ceske Budejovice.
samples from both localities were detected. This conclusions were probably due to the worst
Finally using the highly sensitive LC-MS/MS smog situation resulting from the heavy industry
method the set of 531 urine samples obtained and local heating.
Monohydroxylated metabolites of carcino-
genic CHRY and BaP, namely 6-OH-CHRY and

Figure 1. Comparison of various groups of PAHs in


total diet samples in both localities and sampling periods.
2 + 3-rings PAHs: NA, AC, ACL, FL, PHE, AN; 4-rings
PAHs: FA, PY, BaA, CHR, BcF, 5MC; 5 + 6-rings PAHs:
BbFA, BkFA, BjFA, BaP, DBahA, IP, BghiP, CPP, Figure 2. Comparison of various groups of PAHs in
DBalP, DBaeP, DBaiP, DBahP. human milk in both localities and sampling periods.

253
Figure 3. Comparison of various groups of PAHs in urine in both localities and sampling periods.

3-OH-BaP were not alike in similar studies REFERENCES


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ACKNOWLEDGEMENTS trometry. Rapid. Commun. Mass Sp. 18:2299–2308.
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clic Aromatic Hydrocarbons Residues in Human Milk,
of the Czech Republic P30113-13458S. The
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254
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Estimation of environmental economic for sustainable cultivation


of vines in Cu Chi District, Ho Chi Minh City, Vietnam

M.T. Dang
Faculty of Environment and Labor Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

Q.T. Dinh
Company HBP, Ho Chi Minh City, Vietnam

P.M. Dang
Faculty of Economics, Nong Lam University, Ho Chi Minh City, Vietnam

ABSTRACT: Global Good Agricultural Practices has been widely adopted in Asia from 1997. This
procedure was formally adopted in Vietnam on January 28th 2008, which is called Vietnamese Good
Agricultural Practices. This is considered a typical process contributing to actualize the goal of sustain-
able development of Vietnam agriculture. However, until now there is no scientific research to prove the
sustainability of VietGAP as a basis practice to convince communities to apply this process extensively
in Vietnam. Under this approach, the researchers performed environmental economics estimation, com-
putational experiments on vines, a group of plants has been applied VietGAP successfully in Ho Chi
Minh City—Vietnam. The evaluation was done based on regression methods, manipulated software R to
predict crop yields from the basis of resources, materials and other auxiliary sources served for cultivation
process. Calculation results will be contributed to confirm the sustainability and productivity of VietGAP
processes compared with conventional cultivation, creating a scientific and practical basis to accelerate
VietGAP applications in farming communities in Asia in general and Vietnam in particular.

Keywords: VietGAP, environmental economics, multivariate regression, R software

1 INTRODUCTION plays a very important implication for the overall


environmental quality of the Ho Chi Minh City,
Cu Chi is a suburban district, 45 km from Ho Chi Vietnam.
Minh City to the northwest. According to the pro- Based on the actualization of sustainable devel-
gram of agricultural restructuring in the direction opment goals, the application of sustainable agri-
of urban agriculture in the city in 2011–2015 phase cultural models in production is an urgent and
[10], Cu Chi will become the key development area lasting requirement in Cu Chi district as well as
of urban agriculture with 24 010 ha (in 2015 ), 20 other regions’ agricultural production in Vietnam.
620 ha (in 2020) and 18 960 ha (2025) (Depart- In addition, the question is how to convince the
ments of Statistics of Cu Chi District 2013). communities to accept and to apply the model. In
Accordingly, the area of land for agricultural pro- general, the current situation of rural areas, lead-
duction is declining; therefore, the requirements ing concern of farmers is to improve the family
of production efficiency, productivity, quality and economy. Therefore, in order to persuade people to
sustainability must be emphasized. Furthermore, agree to apply sustainable agricultural model into
in terms of geographic location, Cu Chi is located production, the first starting point to show them
in the upstream of the surface and groundwater. the benefits of economic and through process of
The lack of control in the exploitation of water applications, people will gradually recognize the
resources for agricultural production will detri- advantages of efficient use of natural resources,
ment to this important resource. In addition, waste protect the environment and human health when
and chemicals used in agriculture, if they are not practice sustainable production. Thus, the estima-
closely managed, can spread into the environment tion of environmental economics for sustainable
and downstream areas. Therefore, the prevention vines cultivation, a group of plants commonly
of pollution from agricultural activities of Cu Chi applied VietGAP in Cu Chi, as a basis to prove

255
the environmental economic value of agricultural resources, input materials for production (land,
models VietGAP is needed now. water, fertilizer, pesticides, seeds), and other infor-
The main objective of this study is to evaluate mation (scale farming, labor, years of experience,
the environmental economic of the agricultural professional qualifications); information about the
model VietGAP for planting vines in Cu Chi Dis- environmental awareness of farmers in the proc-
trict, Ho Chi Minh City, Vietnam. ess of producing vines; and, investigation method
selected households in Cu Chi district that have
cultivated vines to cater for the study. These steps
2 METHODOLOGY to be carried out as follows:
– Step 1: Field surveys, collect a list of farmer
2.1 Study area and sample collection households.
2.1.1 Study area – Step 2: Routing typical investigation in
Cu Chi is an agricultural district with steady pace commues.
towards increasing productivity, quality and effi- – Step 3: Trial questionnaire survey, then edit the
ciency, ensure long-term food security for Ho Chi appropriate questionnaire and determine inves-
Minh City, Vietnam; science degree in manufactur- tigation procedures.
ing industries, rural infrastructure is increasingly – Step 4: Perform extensive investigation by
enhanced, contributing to the development of pro- directly interviewing farmers with complete
duction. Therefore, Cu Chi has been focusing on questionnaires which were standardized.
investing to develop forms of urban agriculture in Program survey was conducted 02 times in May
the period 2011–2015. In recent 05 years, Cu Chi 12/2014 and 08/2015, the investigation results were
is one of the regions that has significant typical selected and matched with local reports and feed-
achievements of applying VietGAP on vines, like back with extension officers in village, commune,
squash, melon, cucumber. district, and experts in environmental organiza-
On this basis, the team’s site selection is Cu Chi tions under the Department of Resources and
district, namely 03 agricultural communes central- Environment in Cu Chi.
ized planning of agricultural production and rural
development in Cu Chi district to 2020 and vision
to 2025 including: Nhuan Duc, Trung Lap Ha and 2.3 Data analysis
Phuoc Thanh (Le et al. 2006). The research team Data statistic obtained from the collection of pri-
conducted 100 surveys in 03 communes, specific mary documents to field survey to choose the typi-
survey methods described in Section 2.2. cal data, consistent with the objectives and content
of research through the process with language of
2.1.2 Sample collection software R by means of multivariate regression.
Subject of research is the vines group which is Regression method is used to study the rela-
grown sustainably with VietGAP model in Cu Chi tionship between a dependent elements with one
district, specifically the 03 types of vines: squash, or more independent elements. Type of regression
bitter melon and cucumber. This group of plants is depends on many factors, including economic
successfully applied with VietGAP in Cu Chi. theory, rule of plant biology, the experience of the
study and the actual survey data are important
prop for building regression.
2.2 Methods of survey
The use of OLS to build regression on the rela-
Methods of sociological survey through interviews tionship between the dependent variable (Y) with
with questionnaires to be used to extract informa- the independent variable (X). The dependent varia-
tion from farmers in Cu Chi district. This will be ble can be crop productivity, independent variables
the data used to calculate the economic value of the can be: land, water, fertilizer, pesticides, seeds, farm
environment for planting vines in the study area. size, labor, years of experience, professional quali-
The content of the questionnaire is built on the fications. The regression variables were selected
basis of collecting the information needed to meet based on the cultivation process the vines in Cu Chi
the research objectives, including basic informa- include cucumber, melon, squash and the influence
tion groups as follows: information about surveyed of those variables on the dependent variable.
households (name, age, gender, address, number of Through the value of the regression coefficient (β)
household members, forms of agricultural produc- and statistical tests of the coefficient of this vari-
tion on sustainable or unsustainable development); able to reflect the level of impact of the independ-
information about raw materials, energy and sup- ent variables to the dependent variable. Callbacks
plies, labor,... farmers used to produce vines such crop yields and inputs are considered as conditions
as cucumber, melon and squash. The types of governing the production model (VietGAP or not

256
VietGAP) to perform maximize profitability through 3.2 Productivity of cultivating vines in Cu Chi
productivity gains and productivity here conditions District
tied to maximize the efficient use of resources.
Parallel with the investigative process about envi-
ronmental issues, research was conducted to survey
cultivation yield to assess the agricultural produc-
3 RESULTS AND DISCUSSION tion of farmers, as the basis for initial comparison
agricultural productivity between models of Viet-
3.1 Cultivation characteristics of Cu Chi District GAP and not follow VietGAP.
The average yield of the VietGAP form cul-
According to the survey results in Cu Chi dis-
tivation and not VietGAP are ranged values
trict, 98.84% domestic water has been arbitrarily
consistent with the agricultural survey of agricultural
extracted from boreholes; local aquatic water only
Manual—Department of Agriculture & Rural
account for 0.5% due to the local has no water
Development Ho Chi Minh City Publishing 2012
plant, only a few drilled wells under the manage-
(Do 2010).
ment of the districts DVCI Company. The concern
is the rainfall annual average in the area is between
1,300–1,770 mm, this is a good supply of water for
their daily needs but not yet harvested and used,
only 0.66% for 03 communes.
Similarly with domestic water, 75.67% of water
used in agricultural production were also arbitrar-
ily extracted from the wells. The cause of this situ-
ation is due to the infrastructures for agricultural
production have not been built synchronously and
promote all effects, inland waterway system has yet
to ensure adequate supply of water for irrigation
needs. Besides, the modernization of infrastruc-
ture for agricultural and rural development largely
depends on the budget and the natural conditions
of each commune.
The use of agricultural chemicals is not in
accordance with the manufacturer’s instructions
and extension officers, that is not only wasteful but
also the cause of many undesirable effects on crops
like insect resistant crops, trees develop abnormal,
disease-ridden prone, pests become resistant to the
medication... Besides, pesticide residues on produce
may affect the health of users. However, the propor-
tion of households using pesticides not under the
guidance of extension officer account for 57.43%.
Packaging, bottles of pesticides is type of haz-
ardous waste, but it is handled in ways such as
throwing and burning on the fields and canals with
high incidence, accounting for 45.63%. Meanwhile,
pesticide residue remaining in this kind objects
can emit into the atmosphere, follow water flow
from fields to canals... Then, people contact, use
this water source. The packaging, pesticide bottles
made from plastics or synthetic plastics, inability
to dissolve in the field or if spontaneous combus-
tion will generate toxic smoke.
Agricultural waste is a useful waste, can be uti-
lized for many different purposes, such as com-
post, feed for livestock.... The burn or dispose of
this waste has caused wasteful and polluting the
environment; however, this rate still accounted
38.94%. Details of the survey data is shown in
Figure 1. Figure 1. Cultivation characteristics of Cu Chi District.

257
Yield of VietGAP cultivation forms of all 03 Y = exp(bo)* exp(b1rt)/(b1t)/(b1tb)/(b1x)*
plants: squash, bitter melon, cucumber are higher (X2^b2)* (X3^b3)* (X4^b4)* (X5^b5)* exp(b6a)/
than forms of cultivation that not follow VietGAP, (b6b)* (X7^b7)* (X8^b8)*exp(b9b)* (X10^b10)
namely, such as squash (yield of VietGAP 4.85%
more than traditional form); cucumber (yield of The meaning of the variables are explained in
VietGAP 12.78% more than traditional form); Table 5.
and, bitter melon (yield of VietGAP 7.67% more
than traditional form). Table 2. Regression coefficients and statistical signifi-
cance of the independent variables.
3.3 The results of environmental economic Variable
assessment for sustainable vines cultivation symbol Variable name β Pr(>|t|)
Interpreting regression results: regression function
yields were estimated and used as a basis to ana- βo Intercept 9,679097 <2e-16***
lyze the influence of the independent variable (X) β1rt Very fertile soil 0 –
to the dependent variable yield (Y). In this section, β1t Fertile soil −0,059936 0,014199*
the identification of factors affecting cultivation β1tb Average soil −0,083501 0,000624***
yields in vines, made in growing conditions with β1x Infertile soil −0,084066 0,017091*
and without application of VietGAP. Regression β2 Water 0,026204 0,790351
coefficients and statistical significance of the inde- β3 Pesticides 0,030755 0,271099
pendent variables are shown in Table 2. The process β4 Fertilizers 0,028391 0,274794
of estimating the regression function performed by β5 Labor 0,089101 0,133895
the research team through the steps: β6a Type of cucumber 0 –
β6b Type of squash, −0,650528 9,68e-16***
– Step 1: Define the variables of the model. bitter melon
– Step 2: The hypothesis of the relationship β7 Occupational skills 0,007090 0,793441
between the independent variables and the β8 Number of years −0,005813 0,753281
dependent variable. of experience
– Step 3: Establishment of model mathematical β9a AseanGAP 0,114429 0,004656**
function of Cobb—Douglas, estimates the cor- Conditions
relation coefficients of the model with the help β9b Traditional 0 _
of R software. Conditions
The relevance of independent variables to the β10 Area −0,038699 0,065645
dependent variable is presented in Table 4.
Source: Analysis results from R software.
3.4 Estimated regression results of crop yields
Notes:
Regression of vines yield (squash, bitter melon, –Intercept: βo value of regression.
cucumber) in the study area after estimating have –β: Regression coefficients.
the following form: –Pr (>|t|): The statistical significance of the variables are
explained by symbols ***, **, * respectively with statisti-
cal significance at 1%, 5% and 10%.
–p-value: The probability of obtaining the data as a nega-
Table 1. The productivity of households apply and not tive hypothesis that is the independent variable (X) is not
apply VietGAP. related to the dependent variable (Y).
–Multiple R-squared (R2): The coefficient of determina-
Apply AseanGAP (ton/ha/harvest) tion, expressed “%” can explain the dependent variable
(Y) from prognostic variables (X).
Crop Trung Lap Ha Nhuan Duc Phuoc Thanh
Justified results:
Squash 32,67 33,75 32,17 –Variables value: b1rt (very fertile soil), b6a (type of
Cucumber 51,34 52,67 52,97 cucumber) and b9b (traditional conditions) (β = 0 because
Bitten Melon 27,31 28,11 27,13 these variables are used as the basis to compare with the
remaining variables have the same meaning).
Not apply AseanGAP (ton/ha/harvest) –The results showed that R2 = 91,47% (see appendix)
said the independent variable (X) can explain 91.47% for
Crop Trung Lap Ha Nhuan Duc Phuoc Thanh crop yield dependent variable (Y), on this basis can see
the variable (X) is significant to explain to (Y).
Squash 30,79 32,61 30,63 –F-statistic = 77.76, showed that the verified model is
Cucumber 45,73 46,98 46,48 logical.
Bitten Melon 23,49 27,07 26,12 –p-value <2.2e-16, hypothesize that independent variables
(X) are related to the dependent variable (Y) is very high.

258
Table 3. The average value of the independent variable.

Variables Symbol Unit Average value

Soil X1 Qualitative conversion 2.17


Water X2 m3/ha 641.73
Pesticides X3 Liter/ha 123.60
Fertilizers X4 Kg/ha 1479.40
Labors X5 1000 dong/ha 979.47
Type of plant X6 Qualitative equivalent 1.74
Occupational skills X7 The number of times of 4.04
agricultural training
Number of years of experience X8 Number of years of farming 10.61
Sustainable conditions X9 (D) hypothetical variable Qualitative conversion 1.20
AseanGAP: 1;
Non AseanGAP: 0
Cultivation area X10 ha 0.45

Source: Analysis results from R software.

Table 4. The relevance of independent variables to the dependent variable.

Variables symbol Variables interpretation Relevance (%) Range Standard error (se)

so Soil 2,0746561 3,00 0,10


wa Water 23,4205501 545,33 12,10
me Pesticides 19,9326699 224,00 5,85
fe Fertilizers 0,1518651 2311,34 53,95
la Labor 2,6233240 1665,00 30,82
se Seed 36,4171409 1,00 0,04
ed Occupational skills 1,5415210 10,00 0,28
yr Years of experince 0,3032317 38,00 0,69
d Sustainable Conditions 3,2014780 1,00 0,04
s Cultivation area 1,8049880 1,99 0,03

Source: Analysis results from R software.

Table 5. Explain the meaning of variables. agricultural products to compare economic ben-
efits per unit of currency between the models that
Variables Symbol Unit applied and not apply cultivation at VietGAP
(Table 7).
Soil X1 Qualitative conversion
Water X2 m3/ha
The yield of these crops in the prognostic
Pesticides X3 Liter/ha
model are mostly higher than the actual local
Fertilizers X4 Kg/ha survey research. This could be explained by: the
Labor X5 1.000 dong/ha objective element, the average yield value by self-
Seed X6 Qualitative equivalent calculated and providing inaccurate informations
Occupational skills X7 Number of agricultural and the correlation coefficient R2 = 91.47% said
training independent variables can explain 91.47% for the
Years of experience X8 Number of years of dependent variable; The remaining 8.53% due to
farming the external influence such as weather conditions,
Sustainable X9 Qualitative conversion production experience… However, the prognos-
conditions tic yield value is not much higher, which means
Cultivaion area X10 ha regression of yield of the research team has high
reliability.
Yield values are calculated into selling price to
Based on the yields regression from above, show the remarkable economic benefits of Viet-
estimated crop yield for each type of soil in the fol- GAP planting form, this benefit is doubled when
lowing results (Table 6). productivity of VietGAP produced forms is higher
The calculated price of agricultural products: than non VietGAP forms plus higher selling price
Conducting calculations for the selling price of of the price for VietGAP products.

259
Table 6. The yield of the crop applied and not applied VietGAP.

Not apply AseanGAP (ton/ha/harvest) Applied AseanGAP (ton/ha/harvest)

Soil type Cucumber Squash, Bitter melon Cucumber Squash, Bitter melon

Very fertile 51,26 26,74 57,47 29,98


Fertile 48,27 25,19 54,12 28,24
Average 47,15 24,60 52,87 27,58
Infertile 47,12 24,59 52,83 27,56

Table 7. The calculated price of agricultural products.

Economic value (Unit: Million VND)

Cucumber
Soil type VietGAP Non VietGAP Compared value (VG-NVG)

Very fertile 689.63 512.56 177.07


Fertile 649.51 482.74 166.77
Average 634.38 471.49 162.89
Infertile 634.03 471.22 162.81
Economic value (Unit: Million VND)
Squash, Bitter melon

Soil type AseanGAP Non AseanGAP Compared value (VG-PVG)

Very fertile 344.84 213.95 130.89


Fertile 324.78 201.50 123.28
Average 317.21 196.81 120.40
Infertile 317.03 196.70 120.33

3.5 Analysing the environmental resources amount of compost that was used to improve
meanings of independent variables the soil improve the soil, it does not have harm-
ful effects on the environment and human health
Environmental resources meaning analysis of
over the long term.
the independent variables to compare the eco-
– The amount of money spent on labor is 14,250
nomic value of the environment independent
VND/ha/harvest less, this showed that applying
variables that was used to predict the yield of
farm management under the criteria of Viet-
VietGAP and non VietGAP production form.
GAP is very economic for agricultural produc-
On that basis, assessing the efficient use of
tion of farmers.
resources, which is the basis to persuade the
– The times of extension training under VietGAP
communities to switch from non-VietGAP form
are 5.7 more times and years of farming experi-
to VietGAP form when the yield of VietGAP
ence of the VietGAP farmers is 7.68 more years.
form was proven in Table 6. The specific value
This suggests an encouraging sign that longtime
of the independent variable of the VietGAP and
farmer but boldly innovated and applied Viet-
non-VietGAP form:
GAP in farming due to these households had a
So, in the VietGAP form, farmers get the fol-
vision of yield change when switching to Viet-
lowing basic benefits:
GAP cultivation.
– The amount of saving water over about 35.99 – Besides the efficient use of resources, pro-
m3/ha/harvest. ductivity of VietGAP still guaranteed under
– The amount of saving pesticides are about 47.5 analysis in Table 6. So VietGAP cultivation was
liter/ha/harvest. proven to have efficient utilization of resources,
– The amount of fertilizer used approximately protecting the environment and ensuring
more than 319.7 kg/ha/harvest, but this is the productivity.

260
Face Tough
Face Tough

Face Tough Issues


Face
Face Tough
Tough Issues

Face Tough Face Tough

Face Tough Issues Face Tough Issues

Face Tough Face Tough

Face Tough Issues Face Tough Issues


Figure 2. Analysing the environmental resources meanings of independent variables.

261
4 CONCLUSION Le, T.H., Ngo, T.H., Nguyen, D.H. 2006. Evaluation of
the benefits of shrimp farming activities in Giao Thuy,
The research program has conducted environmen- Nam Dinh. Environmental Economics Program in
tal economic estimation for VietGAP and non- Southeast Asia.
HCMC DARD. 2012. Agricultural Handbook. Ho Chi
VietGAP agricultural model, case study on vines Minh City Department of Agriculture and Rural
(squash, bitter melon, and cucumber) in Cu Chi Development, HCMC.
District, Ho Chi Minh City, Vietnam. Measurable Do, N.T. 2010. Ministerial level Science and Technology
results have demonstrated the efficiency of used Subject “Developing the scientific basis and methodol-
resources, environmental protection, and increase ogy to quantify the economic value of national parks
productivity when producing under VietGAP. service for management and sustainable development”.
These are the scientific and practical results to con- Dinh, D.T. 2006. Economic Dissertation “Assessment of
clude that VietGAP production form is a perfect economic value service for resource management AGRI-
fit for the sustainable development of urban agri- CULTURE—applied at AGRICULTURAL area at
the Ba Lat river mouth, Nam Dinh Province”, Hanoi.
culture in Vietnam in particular and the countries Cu Chi District People’s Committee. 2008. Land use
in the ASEAN region in general. planning of Cu Chi district until 2010 and orientations
towards 2020. Cu Chi District People’s Committee.
Cu Chi District People’s Committee. 2010. Planning of
ACKNOWLEDGEMENT agriculture and rural development in Cu Chi district
to 2020 and vision to 2025. Cu Chi District People’s
The authors would like to thank Dr. Dang Minh Committee.
Phuong—Nong Lam University lecturer—for his HCMC People’s Committee. 2011. Decision No 13/201/
dedicatedly guidance and sincerely thanks to the Restructuring agriculture towards urban agriculture in
HCMC area period from 2011 to 2015. HCMC Peo-
People’s Committee of Cu Chi district have enthu- ple’s Committee.
siastically provided informations, datas service for Schreiner, M. 2002. Environmental Management—the
the research program. path to ecological economy, Building Publisher, Hanoi.
Bonters, P. 2008. Environmental Economics, Youth House
Publisher, Hanoi.
REFERENCES

Departments of Statistics of Cu Chi District. 2013.


Reporting on socioeconomic in Cu Chi district. Depart-
ments of Statistics of Cu Chi District.

262
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Working posture analysis and design using ergonomics methods


and simulation software in brick production process at Truong Viet
Company

P.L. Nguyen & D.K. Le


Faculty of Environment and Labor Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: Brick making workers with the manual works had the awkward postures repeating many
times capable of experiencing musculoskeletal disorders (MSDs). In particular, this study has conducted
a survey of the MSDs symptoms by Nordic questionnaire on 11 workers are working in 4 processes: mix-
ing the dry cement paste, transforming dry cement paste, pressing brick and lapping brick. Among them,
the shoulders and back pain problems should be noticeable. Working postures of workers are evaluated
on ergonomic aspects. The assessment of working postures will be performed by RULA, REBA, OWAS
methods. The data for assessment will be collected through the methods: direct observation, photography,
video recording. In addition, the application of virtual human simulation software from the data will be
applied to support the assessment by three methods. The evaluation results from three methods are re-
indicated and used as the basis to select out the group of priority posture improved. A total of 26 classic
postures from 4 processes have been selected. The results are analyzed and synthesized for the inference
with 3 postures—no need to change, 12 postures—need to give treatment to overcome in the near future
and 11 postures—need to change posture immediately. In this study presented 8 proposed measures to
resolve all 11 postures—need to change posture immediately.

Keywords: working posture, RULA, REBA, OWAS, virtual human simulation

1 INTRODUCTION on a variety of conditions. There are many obser-


vation techniques was introduced. For example as:
Although on a modern society with advanced RULA, REBA, LUBA, OCRA, OWAS (David
machinery but in many studies show that workers 2005, Takala et al 2010) and many other methods
in the brick making jobs recorded still suffer mus- such as: 3D & 2D QUEC, MAC, SPSS, PEO, PLI-
culoskeletal problems (Basra and Crawford 1995, BEL, JSI, … . In that, through researching the sci-
Cook et al 1996, Heuer et al 1996, And Lee 2000, entific articles and studies shows that in the current
Trevelyan and Haslani 2001). Despite advances in techniques, OWAS, RULA, REBA methods has
technology, many workers who do heavy manual been and is still being used in the widely, popular
works in the developed countries. Some studies in way and in many different areas from the service
developed countries have shown that the workers industry to the manufacturing, mining industry. In
must undergo a full spectrum of the disease because particular, there have been a series of comparisons
of the dangerous postures and lifting heavy related and conclusions about 3 methods OWAS, RULA,
to shoulder in India (Mukhopadhyay 2008, Sett REBA (Dohuyng Kee and Waldemar Karwowski,
and Sahu 2008, Sett and Sahu 2010). The author 2007). The study results showed that the posture
has concluded that the Musculoskeletal Disorders evaluation in the higher risk rate is considered
(MSDs) are the results from the regular bend, the more sensitive but this is not entirely accurate
twist; the repeated process with many bricks in a because of lack of data, measurement of biome-
short period of time. The burden of labor workers chanical researched and publicated. Therefore, a
is very big. Therefore, the assessment of working large proportion of works with the high posture
posture with a reasonably objective will be of great burden is not a sign for that method was better
helping in ensuring safety for workers. than the rest. That means there wasn’t be able to
There were a lot of observation techniques fit know which method would better reflect the fun-
in the ergonomic researches of working posture. damental risks with different jobs. Also, according
The techniques that’s been studied and improved to (Nopparat Manavakun 2004) gave the opinion
because of different reasons and are usually applied that no method would be ideal for any situation,

263
because it depends on the needs of the reviews and In the process of conducting assessment, the
objects, the observing way that reviewers would collection of data from the posture encountered
like to do. In the article (Douwes M MC, Mie- many difficulties in reality as likely to have had
dema, Dul J 1997) pointed out that on the basis of the hidden corners of observation and spend a lot
the maximum maintenance time for 19 postures, of time in recording each small data of a working
the classification of 3 posture group following posture under the traditional way. Instead of it, the
holding time (comfort, moderate and not comfort- researchers have gradually improved to the virtual
able) more relevant to the classification based on human simulation. As the study (Hou Honglun,
biomechanical data and measure anthropometry, Shouqian Sun, Pan Yunhe 2007) had mentioned
but their classification for study of 10 in 19 posture to the research of an ergonomic simulation sys-
is different with the classification by OWAS. This tem based on analysis and assess the ergonomic
demonstrates the ability to assess working posture factors. Therein, the working posture is a factor
following the time of OWAS does not guarantee in ergonomic. Thus, the application of simulation
reliability. Each method has strengths and weak- software in assessing working posture will be a
nesses. However, there is not possible yet to give practical application.
a conclusion about a specific method is the most Therefore, the simulation software application
guarantee or how to choose a method scientifically. and using the results from all three OWAS, RULA,
The assessment is mainly based on the observation REBA methods (except working posture assessment
technique. The observation requirements accord- direction according to the time of OWAS) to build
ing to REBA will be the most comprehensive. If we a basis for evaluating working postures at a manual
observe in this direction, we were able to have the brick production factory is suitable for the assess-
relatively sufficient information to assess by the 2 ment of working postures to be objective and easier.
remaining methods. So in working posture assess-
ment has been made, the authors have used one
method to assess working posture or if they use
2 METHODS
from 2 or more methods, their goal was to compare
and determine the sensitivity of the results of the
2..1 Non-experimental research
evaluation. Therefore, the application of evalua-
tion methods will be subjective by each method, Before going into the experimental research with
there is no uniformity in the use of evaluation the workers, the researcher need to conduct sur-
results. Therefore, we simultaneously used the vey by Nordic questionnaire on whole workers are
OWAS, RULA, REBA methods to build a base of working in the processes to determine the MSDs
more objective assessment from the results of each status of the workers. Thereby, determine the need
method. of doing experimental research.

Figure 1. Nordic questionnaire.

264
Because the purpose of the study is not deep, we Step 3. Collect information: the collection of
decided to only use a questionnaire sample for the information is accomplished through the weight
survey: “The questionnaire on the issue of advo- that worker need to wear, carry, manipulate;
cacy agencies” based on the Nordic questionnaire experimental manipulations with the equipment
sample were used in (Dickinson CE et al 1992) and instruments; the frequency; the duration.
(Figure 1). We use the scale, clock, laptop, force measuring
device equipments. The results should be obtained
2.2 Experimental research are the mass; the force—separated into 4 levels:
Description of experiment: the experiment will be not significant (respectively about ≤ 2 Kgf),
carried out on all the workers working in the proc- small (respectively about on 2 to under 5 Kgf),
esses. In each process, researcher will perform a average (respectively about 5 to 10 Kgf), large
series of analysis activities and data collection are (respectively about on 10 Kgf to 20 Kgf), extra
described from step 1 to step 6 as follows: large-strong (respectively about 20 Kgf); the fre-
quency (repeated or steady in a minute).
Step 1. Observe the work: be done through take the Step 4. Imitate/describe the posture: the posture
survey; directly monitor posture, tool, working, simulation based on information obtained from
actual job content; photographing the workers actual observation, clips, and pictures. Specifi-
when they are working; recording video of work- cally with a posture will have one representation
ing processes and working manipulations. We photo recorded. Then, the posture in the photo
can use camera (camcorder mode) equipment will be imitated by software. The simulation
on every time when the workers operate. The aims to clarify the worker's posture. Thereby,
results should be obtained are photos, clips of the arm/leg/back/neck angles also can be clearly
the working processes of workers at each proc- showed if the recorded photos can not meet. In
ess. At every stage the turns should achieved is particular, the cases with the hidden corners can
5 working cycles in 5 alternated separate shifts; only observe from fact. However, this measure
the overall content of the work, the working has a weak point is the accuracy of the simu-
process; the work is subdivided into steps and lation will be depended on the drawing ability
analysis into smaller operations; cyclicality of of the person and the software. The selected
the work, operation: time, frequency. The statis- simulation software is “Pose Studio”—Japan
tic data will be calculated and using the average because two advantages are easy to use; human
of the results obtained from the 5 cycles. body model to be studied has the basic move-
Step 2. Choose the posture to assess: each work of ments; limited rotation, bending that human
workers includes many small activities consti- can do like a normal person. Based on represen-
tuted. For each activity requires a series of steps tation photo, simulation image and the infor-
associated with the constantly changing pos- mation obtained from step 1 and 3 to describe
tures. This means that there will be up to hun- the needed information for scoring.
dreds of the postures for the best comprehensive Example with “Place the brick on drying frame”
assay. However, we can see that each job has the posture:
typical operations. Therefore, the requirements 1. According to OWAS:
to select the postures need to ensure (i) pos-
ture to perform working tasks (not redundant
postures); (ii) creating pressure on the body’s
musculoskeletal system; (iii) maintain stability
for long periods of the cycle or repeated many
times in a short time.

2. According to RULA and REBA: the left hand


uses a negligible force propped up the top of
brick to hold the balance for 10 kg brick are
lifted by the right hand. The manipulation
was performed for about 3s/a cycle; square
iron piece was used to hold is unacceptable
(not guaranteed) but can be used temporarily;
rapidly changing posture cause postural insta-
bility (bent over and turn up). We perform it
like Table 1.
Figure 2. The interface and simulation product from Step 5. Scoring: based on the form of each
Pose Studio software. method (appendix) and the information, the

265
Table 1. Detailed simulation images of “Place the brick on drying frame” posture.

description image to score follow instruction. Example with “Place the brick on drying frame”
With RULA and REBA, we can conduct dif- posture (Table 2).
ferentiate assessment according to the left/right Step 6. Determine the corresponding action level/
position (expressed through the arm). However, group: after comparing the action groups/levels
we need to determine which manipulation hand of the methods, we can see the compatibility
to assess. If it was both hands, we evaluate fol- between the groups/levels. Therefore, to be more
low each side or select the side which has higher simple and easier to grasp, the groups and the
score for general evaluation. In this study, for levels will be reflected by color (Table 4) with
more detailed, we chose separate assessment. the following re-indicated (Table 3).

266
Table 2. Scoring “Place the brick on drying frame” high risk. Therefore, the further investigation is
posture. certainly need to be done and must have the meas-
ures to change, overcome immediately with the
highest priority.

3 RESULTS

Based on the data collection has been done. Here


are the results of the MSDs symptom suffered situ-
ation of the workers currently working in 4 proc-
esses of the company.
The results from table 3 show the noticeable
problems with the worker. Firstly, that is a seriously
problem about shouder (both 2 sides). They have
suffered pain (45.5%—nearly 50% workers) and a

Table 4. The compatibility of the action groups/levels


of OWAS,RULA,REBA.
OWAS RULA REBA
1 nctlon group 1: the Action level1: Action level0: no 1
normal posture, do not the pose is significant risk,the
need anyspecial allowed; corrective actions
include
attention; no need to acceptable further investigationis not
change. posture. necessary; negligible risk.
I Group action 2:

posture should he
concemed abouthow
Action Level
2: need to
conduct further
1
Action level1: low risk,
Table 3. Re-indicated the groups/levels of OWAS, the testworked equally investigation
the edit action including
forthcoming, the and changeif
RULA, REBA to types. further investigationmay
remedv ,mav ,he necessary;
be needed; low risk,
further
Type 1: Risk is not significant, does not ~ ~ e ; " ~ e ~investigation,
~ ~ , " ~ e
change ifnecessav.
need to intervene. action in thenear change if
Type 2: Low risk, intervention by necessary.
Action Level2: medium
investigating more, change if necessary. risk, corrective actions
Type 3: High risk, interventions byfurther Action level3: including further
investigation, the changeshould soon make. required early investigation is necessary;
~ e ~ ~ ~ ~ ~ , the" , " ~investigation
e 3 : moderate risk, further
Type 4: The risk is very high, further interest in theshortest and soon made
investigation intervention and change time; corrective action the change;
should hetaken as further the corrective action
immediately. soon as possible. investigation, including further
change soon. investigation is needed
soon; high risk,investigate
Example with “Place the brick on drying frame”
posture (Table 1). Action group 4: the 4: required
From the action type were recorded from immediately to Action Level4: risk level
posture needed
investigate and lSve'y hi*' the corrective
3 methods with each posture, we build the solu- urgently concemed;
tions as follows: (a) which posture was evaluated
by the 3 methods is of type 1 and 2. With this two
types are recommended in the kind of posture is
corrective actionsto
improve to be
performed
immediately.
?&z?ate
implement

change
include
investigation is needed
and immediately; very high
risk, immediately change.

likely to cause injury to the human body with neg- 1 immediately.


ligible risk and low. Therefore, this posture may
allow maintained, no need to change; (b) which
posture was evaluated by the 3 methods with the Table 5. Re-indicated assessment result for “Place the
low consistency (posture that has been evaluated brick on drying frame” posture.
type 1,2 by a method but has been evaluated type OWAS RULA REBA
3,4 by other methods). This posture should be fur- Posture Level Level
Group
ther investigate but the measure isn’t priority; (c) Left Right Left Right
which posture was evaluated by the 3 methods is Place the
- - ~~ - - ~ 4 3 4 3 4
of type 3 and 4. With this two types are recom- brick on
mended in the kind of posture is likely to cause drying
injury to the human body with high and very frame

267
large percentage of workers has experienced shouder Table 7. OWAS,RULA,REBA results for 26 postures.
symptoms (up to 72.7% in the past 7 days and up to OWAS RULA REBA
90.0% in the past 1 year). Secondary, that must be Process Posture Posture
code Type Type Type
problem about back and especially with lower back L R L R
(more than 50% worker severed pain and more than
80% has experienced lower back symptoms in the (2) Rakingmaterial
past year). Finally, we should pay attention to the Bend lifting material
4 4 4 4 4
(3) tank
problem about hips/thighs and neck. Carrying the material
Through the results in table 7, it shows some Mixing (4) tank
conclusions as follows: (a) (6),(8),(21)—3 postures the dry Pour the ingredients
were evaluated by 3 methods is of type 1 and 2. cement (5) into thedry cement 1 3 33 3
Therefore, these postures may allow maintained, paste paste mixing machine
no need to change; (b) (4),(5),(7),(9),(10),(11),(12), (6) Holding emptytank 1 1 1
(14), (16),(17),(18),(19),(20),(24),(25),(26)—16 pos- (7) Lifting bag of cement 1
tures were evaluated by the 3 methods with the low Turn onloffdry
consistency. The discrepancies can export from the (8) cement paste 1 2 2
mixing machine
re-indicated with REBA’s level 2 (medium risk) into
type 3 (high risk)—appear in (14),(17),(18),(24), (9) Pull the bar to open 1 4 4 4 4 14
(25),(26) postures. This expresses the apprecia- Transfor (10) Standing torake 3 4 4 3 3
cement paste out
tion higher than the hurting risk of these pos- ming dry
cement Sitting to rake cement
tures. However, as the original purpose is to avoid
paste paste out
neglecting the risks by the identification of all three (12) Pourthe cementpaste
methods. Therefore, all of these postures should tank into trough
Y
be further investigate; (c) (1),(2),(3),(13),(15),(22), (13) Ladlethe surface 3 4 3 4 3
(23)—7 postures were evaluated by 3 methods is of mixture
type 3 and 4. Therefore, the further investigations Put the surfacemixture1
2 2 3 3
with these postures are certainly need to be done (I4) into themold
and must have the measures to change, overcome (15) Spreadingmixture 3 73
3 3
immediately with the highest priority. (16) Ladling dry cement
There are the analysis and prosed improvement paste
for 7 postures must have the measures to change, (17) Put dry cement paste 2 2 2 23
Pressing Into the mold
bricK
Table 6. Nordic questionnaire results on 11 workers. (18) Wippingout redunt
cement paste
Experiencing (19) Tacking brick 2 2 3 3 3
Experiencing Severe symptoms (20) Controlling thebutton 2 2 2 33
symptoms in pain in the in the past (21) Movingbrickoutthe
Part the past 1 year past 1 year 7 days tray
(22) Place thebrick on
Neck 5 (45.5%)
Shouders Left
0 3 (27.3%)
9 (81.8%) 5 (45.5%) 8 (72.7%) (23)
drying frame
Bending to take brick 3
-4 4 -4 4
Right 10 (90.9%) Put brick inlout the
Elbows Left 2 (18.2%) 0 1 (9.1%) Lapping (24) grindingframe
Right 2 (18.2%) brick (25) Operating grinding 2 2 2 3 3
Wrists/ Left 5 (45.5%) 0 1 (9.1%) machine
Hands (26) Bulking 1 2 2 3 3
Right 5 (45.5%)
Upper 6 (54.5%) 2 (18.2%) 4 (36.4%)
back overcome immediately with the highest priority
Lower 9 (81.8%) 6 (54.5%) 6 (54.5%) (Table 8).
back
Hips/ 4 (36.4%) 2 (18.2%) 3 (27.3%)
Thighs
4 CONCLUSION AND
Knees 2 (18.2%) 0 2 (18.2%)
RECOMMENDATION
Ankles/ 0 0 0
Feet
Nordic survey results create a basis for deter-
Through assessment of working posture by 3 meth- mining the MSDs status of workers. The serious
ods OWAS, RULA and REBA, we have the aggregated problems in shouder and back should be height
results: attention.

268
Table 8. Analysis and proposed improvement on 7 postures must to change immediately.
Face Tough Face Tough

Face Tough
Face Tough
Face Tough Face Tough

Face Tough
Face Tough
Face Tough
Face Tough

Face Tough
Face Tough
Face Tough
Face Tough

Face Tough
Face Tough

Face Tough Face Tough


Face Tough Face Tough

The evaluation is done quickly and efficiently highest priority and 16 (61.5%) postures should
through a clear implementation steps. In particu- be further investigate and change in near future.
lar, using simulation software support. Some simple solutions are recommendations based
Using both 3 methods (OWAS, RULA, REBA) on the results of research to resolve and prevent
in evaluating helps us to build a more objective the problem of MSDs in the company.
basis to determine priority measures. In this study, From the systematic description and scoring,
3 (11.5%) postures is no need to change, 7 (27%) futher investigate will be easier done by retrospec-
postures is need to change immediately with the tive method. Also, when proposing a solution, it

269
can be re-evaluated following the steps to initial Heuer, Klimmer, Kylian, Seeber, Schmidt, Hoffmann &
determine the solution effectiveness. Luttke-Nymphius. 1996. Musculoskeletal problems in
The study has detail steps and data aimed to the brick layers as a function of length of employment:
risk management related to working posture of the role of secondary selection by low-back pain.
Work and Stress, 10:322–335.
workers in a factory. Evaluation results have quan-
Hou, H., Sun, S. & Pan, Y. 2007. Research on virtual
titative values about dangerous levels of workers human in ergonomic simulation. Zhejiang University,
labor posture. Zhejiang, China.
The study can continuous developed in design- Kuorinka, I., Jonsson, B., Kilbom, A., Vinterberg, H.,
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a formula to take the best advantage from both 1987. Standardised Nordic questionnaires for the
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Manavakun, N. 2004. A comparison of OWAS and
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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

The methods for air pollution emission control from industrial boilers
in Ho Chi Minh City, Vietnam

T.L. Phu & Q.V. Nguyen


Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

V. Lapčík
Faculty of Mining and Geology, VSB—Technical University of Ostrava, Ostrava, Czech Republic

ABSTRACT: Ho Chi Minh City is a municipality can speed very fast industrialization thus leading to
serious environmental pollution, especially the air environment. Among the factors affecting the atmos-
phere, the use of the boilers with burning of fuel wood, coal, FO to serve the needs of industrial produc-
tion is very interesting. Currently, the production enterprises that use boilers has gradually implementing
measures to reduce pollution emissions arising. However, the method of reducing pollution from emis-
sions generated by the boiler is still not completely solved the problem crossbar air pollution. The boilers
use gas and DO as fuel for combustion that does not need to take measures to handle emissions; with
the boilers that use FO as fuel, the disposal of emission is completely controllable; with the boilers using
wood and coal as fuel, it can only control the concentration of dust, SO2, NOx in the emission stream,
while the concentration of CO is not able to effectively control. Since then, leading to the air environment
in the industrial parks, businesses have used the boiler still more pollution. Therefore, the proposal for an
optimal method for enterprise applications produced using boilers need to be calculated and studied in
more detail in the future.

Keywords: air pollution, boilers, emission, concentration

1 INTRODUCTION producers scattered outside the export processing


zones and industrial parks. Enterprises use boil-
Boiler is a very important device used to pro- ers mainly concentrated in the areas such as Binh
duce steam for the industrial manufacturing sec- Chanh District, Nha Be District, Binh Tan District,
tor. The industrial production sectors using the District 12.
boiler including: textile, footwear manufacturing, The fuel can be used to operate the boiler includ-
paper, woodworking, food production, … Accord- ing: wood, coal, fuel, diesel, gas. For DO and gas,
ing to Nguyen Xuan Quang, Vietnam now has the emissions arising from the combustion furnace
about 3,000 boiler with capacity from 1–100 tons will not have much impact on the environment but
of steam per hour, 65% of which is 1–10 tons per investment costs for stoves and fuel usage is very
hour; 20–30% is 20–40 tons per hour; about 0.1% high. For fuel, the emissions arising from the com-
of boiler capacity is 40 tons/hour. In the South bustion furnace will greatly affect the environment
Vietnam, most of the boiler is used in areas such but the handling emissions generated environmen-
as industrial development the Ho Chi Minh City tal pollution caused quite easily by the exhaust
(HCMC), Binh Duong, Dong Nai (General Direc- gas treatment system common. While using wood
torate of Energy 2016). and coal, the emissions arising from the combus-
In HCMC, the boiler is used mainly to cater to tion furnace will significantly impact on the envi-
the needs of industrial production of enterprises ronment but there is still no effective measures to
located in the export processing zones, industrial reduce emissions.
parks include: Linh Trung 1 Export Process- For small and medium businesses which cur-
ing Zones, Export Processing Zones Linh Trung rently make up the majority in HCMC, they occupy
2, Tan Thuan export processing Zone, Tan Binh the majority of businesses choosing wood to burn
Industrial Park, Le Minh Xuan Industrial Park, boilers. The investment for in boiler with wood fuel
Vinh Loc Industrial Park. In addition, the boiler has the advantage of low investment costs and low
is also widely used in enterprises and medium-scale fuel costs. Since it will also cause negative effects

271
on the air environment of the region. The main
components of the gases generated from the burn-
ing of wood boilers include: dust, SO2, NOx, CO.
Currently, in order to minimize the impact
of air pollution from the boilers using FO, coal,
firewood, … businesses primarily use methods
of absorption tower with 5% NaOH solvent. To
increase efficiency of absorption tower, the exhaust
gas will be processed preliminary by cyclone and
some other methods.
This paper discuss methods of air pollution Figure 1. Structure of individual cyclone and multi
treatment for wood burning boilers. These meth- cyclone.
ods are based on analysis of the advantages and
disadvantages of the treatment being applied.
the technology most commonly used today. The
principle of this method is to use gravity and cen-
2 METHODS trifugal force to separate dust from the waste gas
stream. The treatment efficiency of the methods
Study area was selected as the Ho Chi Minh City. are summarized in Table 1.
This is one of the cities with the fast development
• Treatment efficiency:
of the number of enterprises of small and medium
− Moderate treatment efficiency (50–70%) for
manufacturing. In addition, the use of boilers in
large dust particles;
service production in these enterprises has also
− Low treatment efficiency (0–10%) for fine
contributed to a significant negative impact on the
dust particles;
environmental pollution in this region.
− Low energy cost.
Data to assess collected from these sources by
• Advantages:
the HCMC Department of Natural Resources and
− Easy to use, operation, maintenance;
Environment announced; and documents from a
− Low investment cost;
number of businesses that use the boiler in HCMC
− Less area.
and related data.
• Disadvantages:
Data analysis is done by analyzing the advantages,
− Low treatment efficiency for fine dust
disadvantages and effectiveness of each treatment
particles;
methods to minimize the environmental impact
− Difficult to remove condensed matters;
caused by emissions of wood burning boilers.
− Low treatment efficiency for others SO2,
NOx, CO.
3 RESULTS AND DISCUSSION
3.2 Exhaust treatment by venturi scrubber
According to a survey on the air pollution emmi-
The device applies the principle of operation of the
sions from nearly 400 enterprises in the province of
Venturi, the airflow velocity changes abruptly after
Ho Chi Minh City, with 55% of businesses have not
the neck of the tube (from 80–200 m/s reduced
invest the air pollution treatment systems. In partic-
to 10–20 m/s). Water is sprayed into the cylinder
ular have got the largest gas emissions (35%); metal
tube in place before tightening the line segment to
product enterprises (18%); food processing and bev-
form larger drops of dust. The drops of this dust
erages enterprises (12%); the rest are pulp, chemi-
is collected thanks to the cyclone (Nguyen D.T.,
cals, agriculture, forestry (HCMC Department of
Nguyen T.H. 2009).
Natural Resources and Environment 2014).
So to find out the reason why businesses have • Treatment efficiency:
not invested the exhaust treatment systems from Treatment efficiency of the device can be sum-
boilers, or incinerators, this paper discuss the marized in the Table 2.
research issues on the specific measures to address • Advantages:
these air pollution emissions. − Easy to produce, low cost, high efficiency of
dust filter;
− Can filter size of dust < 0.1 μm;
3.1 Exhaust treatment by cyclone
− Can reduce a part of the exhaust stream tem-
The treatment methods of wood-burning boiler peratures from the boiler.
emissions generated by cyclones include: Individual − Can treat a part of pollutant emissions such
cyclone and multicyclone (Figure 1). They are as SO2, NOx.

272
Table 1. Effective treatment of the emissions of wood fired boilers by cyclones.

Methods Parameters Efficiency Assessment

Single PM10 50% – Low cost


cyclone PM2.5 5% – Effectless for fine particle treatment
– Can not remove SO2, NOx, CO
Combination PM10 75% – Low cost
cyclone PM2.5 10% – Effectless for fine particle treatment
– Can not remove SO2, NOx, CO

Source: Emission Control Technologies for Small Wood-Fired Boilers, Resource Systems Group, 2010.

Table 2. Treatment efficiency of wood burning boiler emissions of Venturi Scrubber.

Concentration (g/m3) Average


Size of particles efficiency
Sources (μm) Begin End (%)

Metallurgy technology
– Iron casting furnace 0.1–10 2.3–4.6 0.115–0.344 95,0
– Oxygen blowing furnace 0.5–2.0 18.4–23 0.115–0.184 98,5
– Electricity furnace 0.01–1.0 22.9–27.5 0.09–0.184 99,0
Fertilizer production
– Drunk 0.05–1.9 0.23–1.15 0.115 85.0
Other technologies
– Boiler 0.1–3.0 2.29–4.58 0.114–0.183 98.0

Source: (Tran 2004).

− Gas flow coming out of the treatment system


Children that corrodes the equipment materials due to
Children gases generated from boilers in the line with
Children SO2, NOx.
Children − Low treatment efficiency for SO2, NOx.
− Inability to treat CO.

3.3 Exhaust treatment by absorption tower


Children
Children Absorption tower by means of gas scrubbing is
usually gas washing towers. Exhaust stream enters
the device, then the absorbent is sprayed into small
Children particles moving against the direction of move-
Children ment of the exhaust flow or cross direction. The
particles absorb liquid tiny to be exposed to emis-
sions and absorb harmful gases in the exhaust gas.
Children In the absorption tower with cushioning material
Children Children layer in order to increase the contact area between
the two phases, thereby increasing treatment effi-
ciency (Nguyen D.T., Nguyen T.H. 2009).
Figure 2. Structure of Venturi scrubber.
• Treatment efficiency:
Treatment efficiency can be achieved depend-
• Disadvantages: ing on the type of toxic gas and liquid absorbed
− Dust collected in the form of sludge that may (Table 3).
complicate the waste water and sludge treat- • Advantages:
ment system; − Suitable for toxic gases that dissolved in the
− Gas flow coming out of the treatment system solution easy or easy response to absorbing
with high humidity; agent such as SO2, NOx.

273
Table 3. Treatment efficiency of some system absorption towers.

Pollutants Absorbents Efficiency

Nitrogen oxides in the exhaust gas according Ammonia alkaline solution 93% at 300,000 ft3/h
to molar ratio NO:NO2 = 1:1
Smoke of HCl and SiO2 Water at 3.8 gal/ min.ft2 99.9%
SO2 from exhaust of metal furnace Dilute alkali solution 99.0%
SO2 from exhaust of zinc steel furnace Ammonium sulfite solution 97.0%
SO2 from boiler Dilute alkali solution 99.0%

Source: (Lam 2007).

method at present to control hazardous emissions


Children arise from the wood fuel boiler. However, this
method is only effective for emissions of dust, SO2,
and NOx arising from the combustion of boiler
Children fuel; for the CO emissions generated have not got
the effective treatments recently.
In order to effectively control pollution levels
in emissions arising from wood burning boilers,
Children especially the removal of CO concentration, there
should be more specific research on more effective
solutions. In detail, the furnace technology need be
developed to minimize emissions of CO.

ACKNOWLEDGEMENT

Children We would like to thank Dr. Pham Anh Duc for


helping with the manuscript revision.

Figure 3. Structure of absorption tower.


REFERENCES

− High efficiency of NOx treatment, reaching Nguyen, D.T. & Nguyen, T.H. 2009. Control of Air
93%; Pollution. Publishers of National University in
− High efficiency of SO2 treatment, reaching HCMC. HCMC.
99%; Lam, M.T. 2007. Environmental Engineering. Publishers
of National University in HCMC. HCMC.
− Can use this method when large exhaust gas Tran, N.C. 2004. Air Pollution and Waste Gas Treatment.
flow and high toxic gas concentration; Publishers of Science and Engineering. Hanoi.
− Costs of investment, operation and maintance Biomass Energy Resource Center. 2011. Particulate
are suitable for the conditions of enterprises. Matter Emissions-Control Options for Wood Boiler
• Disadvantages: Systems. Biomass Energy Resource Center.
− Wastewater generated from absorbing tower DONRE. 2014. Alarms for inadequacies air emission
should be treated separately; treatment. HCMC Department of Natural Resources
− Inability to treat CO. and Environment. HCMC.
General Directorate of Energy. 2016. Project Promo-
tion of Energy Efficient Industrial Boiler Adoption and
Operating Practices in Viet Nam. General Directorate
4 CONCLUSION of Energy. Viet Nam.
NESCAUM. 2008. Controlling emissions from wood
Results showed that measures the boiler exhaust boilers. Northeast States for Coordinated Air Use
treatment device by absorbing tower is the optimal Management. USA.

274
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Application of the Analytical Hierarchy Process (AHP) for landslide


susceptibility mapping: A case study in Yen Bai province, Vietnam

T. Trinh, D.M. Wu & J.Z. Huang


College of Computer Science and Software Engineering Shenzhen, University, Shenzhen, China
Department of Remote Sensing and Geo-informatics, Vietnam Institute of Geosciences and Mineral Resources,
Hanoi, Vietnam

B.T. Luu, K.H. Nguyen & H.Q. Le


Department of Remote Sensing and Geo-informatics, Vietnam Institute of Geosciences and Mineral Resources,
Hanoi, Vietnam

ABSTRACT: Yen Bai province places in the north part of Vietnam, where the landslide phenomenon
occurs frequently and affects seriously local living conditions. Landslide susceptibility mapping is an
urgent task for the government for the mountainous regions. This case study focuses on the spatial analy-
sis of landslide susceptibility, and using the analytical hierarchy process approach and opinions of experts
is to establish landslide susceptibility map. The resulted map with five landslide susceptibility classes: very
low, low, moderate, high, and very high susceptibility for landslide, which are derived based on the corre-
spondence with landslide inventory. The map indicates that about 36% of the area is very high and highly
susceptible for landslide, which means that more than a third of the area should be considered prone to
landslide. The landslide susceptibility map can be useful for the decision-makers and planners in choosing
suitable locations for the long-term development.

Keywords: Analytical Hierarchy Process (AHP), landslide, susceptibility map

1 INTRODUCTION literature, which can be divided into direct and


indirect methods (VanWesten, Rengers, & Soeters
The northwest mountainous regions of Vietnam 2003). In which, direct methods, basing on expe-
with various strong dissections by tectonics, the rience and knowledge of experts is to determine
areas are heavily affected by landslide phenom- the degree of landslide susceptibility. The indirect
enon. Recently year, Vietnam is influenced by methods, using the landslide inventory is to assess
climate change and human activities such excava- or make the relationship between conditioning
tion of slopes for road cuts or such deforestation, factors. Landslide susceptibility mapping depends
which are one of the causes contributed to landslide on the existing landslide inventory, and the accu-
happening (Le 2014). Frequency and magnitude of racy and sufficiency of contributed factor maps,
landslides in the regions have been increased, not and the research scale and the analysis method in
only causing losses and damages to people, also each study area (Cascini 2008).
damaging enormous properties in terms of both Several studies on landslide susceptibility map-
direct and indirect costs (Bui, Pradhan, Lofman, ping have been conducted with the consideration
Revhaug, & Dick 2012a) (Duc 2013). of the complex interactions among controlling fac-
Landslide susceptibility mapping is an urgent tors. Most of them have been applied the spatial
task for the government for the mountainous analysis in different landslide modeling, such as
regions (Le 2014), including Yen Bai province, frequency ratio, weight of evidence, probabilistic
to find proper and effective strategies in land use approach and neural networks to evaluate the sus-
planning and management, also forecasting and ceptibility of landslides in relation to tectonic frac-
finding measures to mitigate subsequent losses ture, slope, aspect, curvature, soil, vegetation and
to future landslides (Bui, Pradhan, Lofman, land cover (Bui, Pradhan, Lofman, Revhaug, &
Revhaug, & Dick 2012b). Dick 2012a) (Bui, Pradhan, Lofman, Revhaug, &
May different type of landslide techniques Dick 2012b). Various approaches have been devel-
and methods have been developed in landslide oped for landslide susceptibility mapping, including

275
heuristic approaches based on expert experience. landslide susceptibility mapping (Van Westen
In this study, causative factors were analyzed by 1993). The land slide inventory can be done by
analytical hierarchy process is to assess the spatial many techniques, in this case the landslide inven-
susceptibility distribution in the area. This paper tory was carried out from 2012−2014 (Le 2014).
summarizes the outcome of landslide susceptibil- Which contains two landslide inventory types,
ity mapping study in Yenbai province. one is the field-check survey along roads which
identifying 1162 happened landslide locations.
And the other is delineated by air photo inter-
2 STUDY AREA AND DATASET pretation and 3 D relief analyses, identifying
1095 landslide-polygons, in which square size
Yen Bai province locates in the Northwest part of of average polygons and maximum are 0.13 and
Vietnam, and Figure 1 represents the study area, 1.98 km2 respectively. Using landslide inventory is
which is the mountainous area. It covers an area very important when assessing the contribution
of about 6888 km2, between the latitude 212440 N of each causative classes of each factor map in
and 221632 N and between longitude 1035626 E landslide happening, and that is also the key point
and 1050307 E, and the altitude of the area ranges assigning weights for each causative class of each
from 8 to 2970 m (Le 2014). The region happens factor map.
landslide phenomena, losing properties and dam- Using the natural break classification (Michael D.
aging constructions each year. Kennedy, Jack Dangermond 2013) classified each
Causative factors for landslide susceptibility map of 4 factor maps (slope, drainage, deep cleav-
mapping in a certain study area should be selected age and lineament density) into 5 classes. And the
carefully based on relevance, availability, and scale 4 remain maps using experience of experts and evi-
of mapping. (Cascini 2008) (Soeters & van Westen dences of previous work (Nguyen 2009) (Le 2014)
1996) Landslide susceptibility mapping is carried (Nguyen 2012) (Nguyen & De Smedt 2011) to
out at the medium scale, in this area is 1: 50000 classify.
scale. Basing on previous studies in the same area A Digital Elevation Model (DEM) for YenBai
of Nguyen (2009) and Nguyen (2012), from that area, with the resolution of 20 m, was generated
examining the correlation and contribution in from the Vietnam topographic maps in 1: 10000
happening landslide, also identifying the scale and scale having a contour interval of 10 m. Slope,
accuracy and sufficiency of maps, therefore the drainage and deep cleavage factor maps were
eight factor maps have been considered for heu- extracted from the Digital Elevation Model (DEM)
ristic landslide susceptibility mapping. Figure 2 with the resolution of 20 m.
describes causative factor maps which were The slope map (Figure 2 A) was grouped into
selected: slope, drainage, deep cleavage, weather- five different classes, 0°−9.38°, 9.38°−19.13°,
ing crust, water storage, shear strength, lineament 19.13°−27.6°, 27.6°−36.44°, > 36.44°. The drain-
density and land cover as input data. age map (Figure 2B) was categorized into also 5
Carrying out a landslide inventory is very classes with m/km2 unit. The deep cleavage map
crucial and used as a preliminary step toward (Figure 2C) was also classified into five different
classes with m/km2 unit.
The water storage map (Figure 2D) was gained
from the survey of (Le 2014) and classified into
4 classes: very low, low, moderate, high.
The shear strength map (Figure 2E) was stand-
ardized and adjusted from engineering geology
map (Le 2014) and divided into 4 classes: low,
moderate, high and very high.
The lineament density map (Figure 2F) was
established based on analyzing Landsat 7 EMT +
image, and resulted in the density of lineament dis-
tribution map that classified into 4 classes with
m/km2 unit: 164−3275.52, 3275.52−4325.67,
4325.67−5142.44, 5142.44−5998.11, > 5998.11.
The weathering crust map (Figure 2G) was estab-
lished and selected from (Le 2014) and it was classified
into 10 groups: Loss Sediment, Unpreserved weath-
ering curst, Carbonate, Sialite-Sialferrite, Ferroalite-
Ferrosiallite, Sialite-Ferrosialite, Sialferrite-Sialite,
Figure 1. The study area map, Yen Bai province. Sialferrite, Ferrosialie-Sialferrite, Ferrosialite.

276
Figure 2. The causative factor maps were selected: slope, drainage, deep cleavage, weathering crust, water storage,
shear strength, lineament and land cover.

The Landcover map (Figure 2H) was resulted AHP is a semi-quantitative method, is a decision-
from analysing and assessing vegetation changed aiding tool for address multi-criteria decisions,
in two periods, 1999−2002 and 2003−2005. The which has been incorporated into GIS-based
map was grouped into 7 classes: Bust and grass, suitability procedures (Marinoni 2004), and deci-
Mixed trees, Agricultural land, Residence and bare sions are taken using weights through pairwise
soil, Rock mountain, Major forest, Minor forest, relative comparisons without inconsistencies
and Landcover change. in the decision process. AHP is based on three
principles: decomposition, comparative judg-
ment, and synthesis of priorities (Malczewski
3 METHODOLOGY
1999). Concepts and techniques in AHP include:
hierarchical structuring of complexity, pair-wise
3.1 Analytical hierarchy process
comparisons, redundant judgments, eigenvector
The Analytic Hierarchy Process (AHP) was devel- calculation for deriving weights, and consistency
oped by Saaty (1980), Saaty and Vargas (2001). considerations.

277
Table 1. Scale of preference between two parameters in AHP.

Preference factor Degree of preference Explanation

1 Equally Two factors contribute equally to the objective


3 Moderately Experience and judgment slightly to moderately
favor one factor over another
5 Strongly Experience and judgment strongly or essentially
favor one factor over another
7 Very strongly A factor is strongly favored over another and its
dominance is showed in practice
9 Extremely The evidence of favoring one factor over
another is of the highest degree possible of
an affirmation
2,4,6,8 Intermediate Used to represent compromises between the
preferences in weights 1, 3, 5, 7 and 9
Reciprocals Opposites Used for inverse comparison

Table 2. Random Consistency Index (RI).

n 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

RI 0 0 0.58 0.90 1.12 1.24 1.32 1.41 1.45 1.49 1.51 1.53 1.56 1.57 1.59

The advantages of using AHP as an expert factor map (Nguyen & De Smedt 2011) (Yalcin
based method in landslide susceptibility analysis 2008) (Yalcin, Reis, Aydinoglu, & Yomralioglu
(Nguyen & De Smedt 2011) are: (i) all types of 2011). In this study, the AHP was used to assign
information related to landslides can be included to both factor maps and different classes of factor
in the discussion process; (ii) judgment is struc- maps.
tured so that all information is taken into account;
(iii) discussion rules are based on knowledge and
3.2 Weights for causative factors
experiences of experts; (iv) when a consensus
is reached, weights for each relevant factor are In the case study, the eight factor maps were
obtained automatically by eigenvector calculation selected is an initial input. The following steps as
of the comparison matrix; and (v) inconsisten- adapted from (Kayastha, Dhital, & De Smedt 2013)
cies in the decision process can be detected using are involved in the AHP method: (i) break down a
consistency index values in Table 2, corrected if decision problem into component factors; (ii) from
needed. The one of great advantages using AHP is the Table 1 making an order of component factors
that re-arranging the complexity of data set by the and assigning numeric value for each component
hierarchy with a pairwise comparison between two factor; (iii) comparing each pair-wise component
variables, and then allows reducing the inaccuracy factors, what factor is more important or less.
in weighting, also ensure that processing different (iv) set up of comparison matrix; (v) computation
data is coherent. Allowing to validate pair con- of the normalized principal eigenvector, which give
sistency is one advantage of AHP. However, this the weight of each factor (Saaty & Vargas 2001);
approach based on opinion of experts, judgment (vi) Checking the consistency of the comparison
and ranking of causative factor may differ from using the Consistency Index (CI) (Saaty & Vargas
one expert to another, therefore this is a minor 2001) in Equation (1), Random Index (RI) in
disadvantage. Table 2 was developed by Saaty (1980). And Con-
AHP method was used in many studies to estab- sistency Ratio (CR) is defined as the ratio of the
lish landslide susceptibility mapping in the world. Consistency Index (CI) and the random consist-
In which some studies only used AHP to assign ency index (RI), in which the CR must be lower
the weighting factors for landslide causative fac- than 0.1 to accept the computed weights, oth-
tors, and some work used AHP for both causative erwise, the pair comparison matrix needs to be
factor maps and different classes of the causative re-calculated.

278
λ max − n 4 RESULTS AND DISCUSSION
CI = (1)
n −1 Basing one expert knowledge and landslide inven-
tory is to assign weights for both each class of each
Where, λmax is the largest eigenvalue and n is the factor map and factor maps. Hence, Landslide
order of the comparison matrix in step (iv). Finally, Susceptibility Index (LSI) map was established
Landslide Susceptibility Index (LSI) is calculated via Equation 2. The resulting LSI map is shown in
by summation of weighted value of each factor Figure 3a, in which the LSI values vary from 0.024
map multiplied by the weighted value of each class to 0.321.
of factor map. Using natural break classification method, the
LSI map is classified into five zones: very low; low;
n moderate; high and very high. The resulting land-
LSI
S ∑W w
j
j ij (2) slide susceptibility zonation map is shown in Fig-
ure 3b. In such way, Table 4 described that 10.72%
of the study area has very high LSI values, 25.37%
Where Wj is the weight value of factor map j, wij of the study area has high LSI values, 35.39% has
is the weight value of class i of factor map j, and n moderate values, 25.06% of the study has low LSI
is the number of factor map. These weight values values, and only 3.47% of the study area has the
were taken from the normalized principal eigenvec- very low LSI values. The highest and high suscep-
tors of each matrix in step (v). tible zones cover 24.43% and 31.78% respectively
Table 3 shows the result of using AHP method, of the total observed landslide-polygon areas;
and CR for all causative factor maps, and CR for whereas moderate zone covers 30.35% of the
different classes of factor maps are lower than observed landslide-polygon areas, the remaining
0.1. Hence, the weights for all causative factor is of observed landslide-polygon areas in the low and
able to establish landslide susceptibility mapping very low susceptible zones are 13.44% and 0.00%.
effectively. Table 4 also shows that the two highest suscepti-
ble zones cover 383 landslide locations in the field
check, moderate and low susceptible zones cover
Table 3. N classes, largest eigen value λmax, consistency 478 and 300 landslide locations respectively. The
index CI, random consistency index RI, and consistency result portrays gathering certain landslide points in
ratio CR, for the landslide causative factors. the field check correctly because almost happened
landslide locations were gathered along roads and
Causative factors N λmax CI RI CR nearby living areas. Some happened landslides
were recorded in regions with various strong dis-
All factor maps 8 8.12 0.017 1.41 0.012
sections by tectonics, far away from roads and
Slope 5 5.12 0.031 1.12 0.027
communities.
Drainage 5 5.11 0.028 1.12 0.025
The landslide density was calculated by percent-
Deep cleavage 5 5.20 0.051 1.12 0.045
age of and slide ploygon area dividing percentage
Weathering crust 10 10.74 0.082 1.49 0.055
of susceptibility. The results for the density highest,
Water storage 4 4.12 0.039 0.90 0.043
Shear Strength 4 4.05 0.017 0.90 0.019
high, moderate, low and very low susceptible zones
Lineament density 5 5.09 0.023 1.12 0.021
are respectively 2.28, 1.25, 0.86, 0.54 and 0.00 in
Landcover 10 7.13 0.021 1.32 0.016 Table 4. These results show that there is a signifi-
cant decrease in landslide density from the very

Table 4. Landslide density in the different susceptibility zones of the landslide susceptibility map.

Landslide polygon Landslide


Susceptiblity area Landslide point area density
Susceptibility
zones Km2 % (a) Number % Km2 % (b) (b)/(a)

Very low 595643 3.47 1 0.09 0.00 0.00 0.00


Low 4304457 25.06 300 25.82 19.50 13.44 0.54
Moderate 6078968 35.39 478 41.14 44.04 30.35 0.86
High 4357414 25.37 313 26.94 46.11 31.78 1.25
Very High 1841639 10.72 70 6.02 35.45 24.43 2.28

(a) and (b) were used to calculate landslide density

279
Figure 3. The landslide susceptibility map; (a) is the landslide susceptibility index map; and (b) is the final landside
susceptibility map with 5 susceptible zones.

high to the low susceptible zone and there is also a Possibly, this map can be used by the concerned
considerable separation in landslide density values authorities in disaster management planning
between the different susceptible zones. Hence, it is to minimize or avoid the adverse impact of
can be concluded that the calculated and classified landslides.
susceptibility zones are found to be in good agree-
ment with occurrences of inventory landslides.
ACKNOWLEDGMENT

5 CONCLUSION The author would like to thank Doctor Le Quoc


Hung, the deputy of Vietnamese Institute of
In this study, the AHP technique was used for Geosciences and Mineral, is also the leader of the
landslide susceptibility mapping in Yen Bai prov- government project (Le 2014), who provided all
ince, Vietnam. The AHP technique possesses some dataset.
distinct advantages for analyzing complex deci-
sion problems and has proven to be applicable and
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assessed the landslide inventory, hence obtaining Hoa Binh province of Vietnam: A comparison of the
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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Measures of mitigating the negative impacts of the urbanization and


industrialization to the land resources and environment in Vietnam

T.L.C. Nguyen
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: Urbanization and industrialization are the inevitable tendency of a developed economy.
However, the urbanization and industrialization always accompany with the natural environmental change
in both positive and negative sides; as a result, the controls of the urbanization and industrialization
always challenge countries, especially the developing country like Vietnam so as to achieve the sustainable
development target.

Keywords: urbanization, industrialization, environmental change, sustainable development

1 KEY IMPACTS FROM THE − A large number of construction materials,


URBANIZATION AND resources and minerals shall be moved to the
INDUSTRIALIZATION TO THE urbans and industrial parks; the demand of con-
NATURAL RESOURCES AND suming energy and fuels is increasing.
ENVIRONMENT IN VIETNAM − The demand of exploiting the water resource
for daily activities, services and manufactur-
In Vietnam, the big urbans have been recently ing shall be increased; this degrades the water
expanding and modernizing. A significant feature resources.
is that most of the urbans are closely connected to − The fast increasing urban population causes the
the industrial manufacturing activities. Most of the overloading to the technical infrastructure of
industrial manufacturing plants have been locating the urbans (the systems of water supply, water
in residential areas and the industrial parks have drainage, water treatment, traffic, garbage col-
been planning in or adjacent to the urbans. This lection and treatment, etc.). The increasing
causes not only conflicts regarding the land use population in combination with the increasing
for living and the land use for trading and manu- living standards shall increase the waste from
facturing inside an urban, but also severe environ- daily activities and urban services, especially the
mental problems affecting to the life of the urban waste water and waste garbage and decrease the
residents such as: pollution caused by waste gas, environmental sanitary.
waste water, solid waste; reduction of the green- − The increasing industrial and home craft manu-
ery area, water surface. This causes to the popula- facturing shall arise a lot of waste that causes
tion and degradation of the land. It is possible to pollution to water, air, land and CTR, of which
consider some key impacts to the urbanization and the percentage of toxic wastes is more and more
industrialization to the resources and environment increasing.
as follows: − The urban development shall boom the mecha-
nized traffic means inside the urban, discharge
− The land resources will be completely exploited
lots of dust, toxic gases and noise. This causes
to build urbans and industrial parks. The per-
air pollution and serious noise pollution to the
centage of land for greenery and water surface
urban.
in the urbans has been decreasing and the land
− It is difficult to meet housing demands. This
surface for absorbing and draining water; the
makes some slums where the environmental con-
agricultural land and other land shall be used
ditions in these areas are very poor and it is dif-
for building houses and urban works. The local
ficult to handle this problem.
communities at this urbanized areas shall lose
their working means and their traditional live- These pressures may exceed the ‘loading’ capac-
lihood; the urban environmental pollution shall ity of the environment and the natural resources;
be strongly affected. exceed the ‘meeting’ capacity of the environmental

283
cause environmental pollutions and decline the
resources, especially the big cities and localities
where the urbanization and industrialization are
quick.

2 MEASURES OF MITIGATING
THE NEGATIVE IMPACTS OF
THE URBANIZATION AND
INDUSTRIALIZATION TO THE LAND
RESOURCES AND ENVIROMENT IN
VIETNAM

As analyzed above, negative impacts from the


urbanization and industrialization to the land and
Figure 1. The process of rapid urbanization, one of the enviromental resources will mainly change the land
causes of environmental pollution. use structure; this causes pollution and degrada-
tion to the land. The mitigations to these negative
impacts as stated above are mainly divided into
two groups: (1) planning solution and (ii) manage-
ment solution.

2.1 Planning solution


The planning solution includes:
− To restrict the development of big urbans and
giant urbans.
− To expand the urbans to suburbs to take advan-
tages of improving old quarters.
− To build satellite towns in addition to big and
Figure 2. Rapidly increasing personal transport, one of giant urbans; build a chain of towns in accord-
the causes of environmental pollution. ance with the national traffic system.
− To set up rural residential areas (in form of four
towns) to urbanize the rural areas.
− To set up centralized industrial parks outside the
urbans in consideration of the possibilities of
expanding the urbans.
− To strictly remove the manufacturing plants in
the urbans to the centralized industrial parks.

2.2 Management solution


The management solution includes:
− To strengthen the management effectiveness
of the government regarding following fields:
administrative management, planning manage-
Figure 3. Do not control the amount of solid waste
ment, construction management, investment
generated. management and management of land use and
exploitation.
− To set up preferential investment policies for
protection of the society and the government. remote areas.
This causes the urban environment to be more − To strengthen urban environmental manage-
and more polluted. The urban development is not ment policies to ensure sustainable development
sustainable. of the urbans while fostering the industrializa-
In general, the urbanization and industrializa- tion and modernization.
tion, without appropriate policies, measures and − To maintain and foster the socialization of the
mechanisms of environmental management, shall enviromental protection.

284
3 MANAGEMENT MEASUREMENTS • Special urban must meet following standards, as
OF THE URBANIZATION AND follows:
INDUSTRIALIZATION TO MEET ECO − The capital or an urban with its functions of this
FRIENDLY REQUIREMENTS type of urban as the political, economic, cul-
tural, scientific-technical, tourism, service center
The management measurements of the urbanization and a traffic clue for domestic and international
and industrialization consist of two big aspects: exchanges with its roles of promoting the social-
economic development of the whole country.
− Management of the urbanization in eco friendly
− The percentage of non-agricultural labourers over
orientation.
total labourers is from and above 90% tro?ˇ lên.
− Management of the industrial parks under the
eco friendly direction. − The built infrastructure is basically overall
and completed.
− Population size is from and above 1,5 million
3.1 Management of the urbanization in the eco people.
friendly orientation − The average population density is from and
above 15.000 people/km2.
Parallel with the investigative process about envi-
ronmental issues, research was conducted to survey • Level I urban must meet following criteria:
cultivation yield to assess the agricultural produc- − The functions of this type of urban are as the
tion of farmers, as the basis for initial comparison political, economic, cultural, scientific-technical,
agricultural productivity between models of Viet- tourism, service center and a traffic clue for
GAP and not follow VietGAP. domestic and international exchanges with its
The establishment and development of the roles of promoting the social-economic develop-
urbans require to reinforce the management roles ment of a joint-provincial territorial region or
of the government for the general benefits of the of the whole country.
local communities because in a modern urban, − The percentage of non-agricultural labourers
conflict between the socio-economic develop- over total labourers is from and above 85%.
ments and the enviromental protections is always − Many fields of the infrastructure is built over-
appeared. Building the eco friendly urban is also a ally and completedly.
good solution for this conflict. − Population size is from and above 500 thousand
To set up and manage an urban in the eco people.
friendly direction, it is necessary to know how − The average population density is from and
to: (i) classify an urban and (ii) which criteria are above 12,000 people/km2.
needed to meet for the eco friendly urban. • Level II urban must meet following criteria, such as:
− The functions of this type of urban are as the
political, economic, cultural, scientific-technical,
3.1.1 Classification of urbans
tourism, service center and a traffic clue for
Decree No. 72/2001/NĐ-CP dated 5/10/2001 of
domestic and international exchanges with its
the Vietnamese government regarding to the clas-
roles of promoting the social-economic develop-
sification of urbans and urban management level
ment of a joint provincial territorial region or
stipulates that an urban is residential areas con-
some fields of the whole country.
taining following basic factors:
− The percentage of non-agricultural labourers
− Its functions are as the general centre or special- over total labourers is from and above 80%;
ized center with its roles of fostering the socio- − The built infrastructure is pretty overall and
economic development of the whole country or completed;
a specific territorial area. − Population size is from and above 250 thou-
− The percentage of non-agricultural labourers sand people;
over total labourers is at least 65%. − The average population density is from and
− The infrastructure for the residents’ activities above 10,000 people/km2.
must meet 70% the standards and regulations
• Level III urban must meet following criteria, as
for each type of urban.
follows:
− Population size is at least 4,000 people (this
− The functions of this type of urban are as the
number may be lower for mountainous areas).
political, economic, cultural, scientific-technical,
− The population density must be appropriate
tourism, service center and a traffic clue for
with its size, features and characteristics of each
domestic and international exchanges with its
urban type.
roles of promoting the social-economic develop-
In according with this Degree, our country ment of a province and some fields of a joint
urbans are classified as follow: provincial region.

285
− The percentage of non-agricultural labourers − To make priority investment to build urban
over total labourers is from and above 75%; economic—technical facilities to create jobs
− Each field of the infrastructure is overal and for local communities.
completed;
− Population size is from and above 100 thou- • Urban traffic
sand people; − The network of urban traffic road accounts for
− The average population density is from and 20–30% the urban land area (inclusive of works
above 8,000 people/km2. in the sky, on the ground and underground).
− The public traffic accounts for 50% and is
• Level IV urban must meet following criteria, diversified: traffic on the ground, underground
such as: and waterway.
− The functions of this type of urban are as the − The traffic order management is highly effective.
political, economic, cultural, scientific-technical,
tourism, service center and a traffic clue for • Urban water supply
domestic and international exchanges with its Water supply at urbans: 100% urban popula-
roles of promoting the social-economic develop- tions are supplied clean water with standard
ment of a province or a joint provincial region. around 120–150 litters/person/day and night.
− The percentage of non-agricultural labourers over
total labourers is from and above 70% tro?ˇ lên. • Water drainage, collection and treatment of waste
− Each field of the infrastructure has been water and environmental sanitary
building overally and completedly. − The urbans must have their waste water drain-
− Population size is from and above 50 thou- age system different from the rainy water drain-
sand people. age system; centralized waste water treatment
− The average population density is from and stations to treat all urban waste water that
above 6,000 people/km2. meets required standards before being dis-
charged to the receiving source. The percentage
• Level V Urban must meet following standards, of collecting and treating waste water must be
as follows: over 80%.
− The functions of this type of urban are as the − There are no box latrines. Public toilets are
political, economic, cultural, scientific-technical, enough at residential areas.
tourism, service center and a traffic clue for − The percentage of garbage and solid waste
domestic and international exchanges with its collected and treated by appropriate technol-
roles of promoting the social-economic develop- ogy is over 90%. Measure of reusing the waste
ment of a district and a group of communes; must be available.
− The percentage of non-agricultural labourers − The funeral house or cemetery must be avail-
over total labours is from and above 65%; able and appropriately planned.
− The infrastructure has been building without − The hospitals must have their separate waste
being overal and completed; water treatment systems; the solid garbage
− The population size is from and above 4,000 must be separately collected and treated.
people; − Land for the urban greenery achieves the cri-
− The average population density is from and teria of 7–10 m2/person with a system of lakes
above 2,000 people/km2. and natural protection areas to balance the
In Vietnam, during recent years, the development urban ecosystem, especially big urbans.
of urbans has been strong and mainly in densely
populated deltas such as Northern Delta, Central • Social infrastructure
Region Delta and Southern Delta. Until 2012 − The housing criteria must achieve 10–12 m2
the whole country has had 633 urbans, of which floor/person.
there are two special urbans, two level I urbans, 82 − The public works meet material and spiritual
level II to level IV urbans (provincial urbans) and demands of the local communities. The per-
547 Level V Urbans (district level urban). centage of the land for building public works
must achieve 4–5 m2/person.
3.1.2 Necessary criteria for an eco friendly urban
• Awareness of the local communities
The eco friendly urban should meet following criteria:
− The high awareness of the local communities
• Population size and manufacturing infrastructure regarding urban enviromental protection is
− Population size and the social-economic shown via movements of green-clean—nice
development of the urban are kept in an enviromental protection.
appropriate size with the appropriate size of − 100% households are aware of classifying gar-
the loading capacity of the enviroment. bages in their houses.

286
• Urban management system − If the manufacturing technology causes the
− The advanced management system ensures to enviromental pollution, the companies must
be able to monitor the enviromental change. have positive measures to mitigate the pollution.
− Laws and policies regarding enviromental
• A set of criteria regarding measures of the enviro-
protection are well executed.
mental protection
− The companies apply Cleaner Production
3.2 The results of environmental economic solutions in their manufacturing processes.
assessment for sustainable vines cultivation − The pollution treatment technology at the end of
the pipes achieve the enviromental standards.
“The eco friendly industrial park is the old typi- − Solutions of exchanging and reusing waste
cal industrial park that has been gradually changed among the companies in the industrial park
its manufacturing and organizational system with or the companies outside the industrial park
its strategies of each company size and the whole are available.
industrial park size into the eco friendly industrial − The greenery system achieves the enviromental
park or the new built eco industrial park to meet standards.
eco friendly increasing criteria in the direction of − The working environment in each factory
sustainable industrial ecology. The advanced envi- must be ensured.
romental management system is available to ensure
the effectiveness implementation of the laws and • A set of criteria regarding infrastructure
policies of the government. There is development Completed infrastructure consists of: traffic
planning closely connected with the enviromental system; lightning and electricity supply system;
protection under the sustainable ecological prin- communication and telecommunication system;
ciples with technological and scientific level high water supply and drainage system; medical and
enough to be able to control and mitigate the pol- health care system for labourers.
lution, degradation, enviromental problems and
implement industrial and enviromental ecological
principles to ensure the enviromental and eco- 4 CONCLUSION
nomic benefits, balance the ecology and integrate
the international economy and care the local com- In Vietnam, since the policies of opening doors of
munities’ health” (Phung 2004). the government has been available, the urbaniza-
From the concept of the eco friendly industrial tion and industrialization has been strong and out
park as stated above, it is possible to propose cri- of control of the various local authorities. The
teria to assess the eco friendly industrial park as the urban increasing population is not based on
follows: actual demands of labour but the very big differ-
ence regarding the living standards between the
• A set of criteria regarding management system and urbans and rurals. The overloading population
policy mechanism makes the socio-economic factors of the urbans
− The industrial park management staff is more and more complicated. The socio and tech-
highly aware of the enviornmental protection nical infrastructure system is quickly degraded,
via strict implementation of the law of envi- especially the housing and environmental sanitary.
ronmental protection, regulations regarding The mass development of industrial and home
enviromental management, criteria regarding craft manufacturing makes the urban environment
industrial enviromental protection and other more serious. The main reason making the cour
legal regulations regarding the enviromental country urbans degraded is the land use without
protection. planning and effective enviromental protection
− Modern enviromental management and mon- measures and the poor management system that is
itoring system is available to be able to con- not met the development requirements of modern
trol the enviromental change in the industrial urbans. As the result, in addition to connecting the
park. planning with the enviromental management and
− Encouraging and preferential policies for urban management, to enable the urbans to be able
companies that strictly follow the law of envi- to have sustainable development under the urbani-
romental protection must be available. zation and industrialization process, it is necessary
to implement overall planning and management
• A set of criteria regarding manufacturing technology solutions to mitigate the negative impacts of the
− Most of the factories in the industrial park urbanization and industrialization to the resources
apply advanced and modern manufactur- and enviroment and in the future, it is necessary
ing technology that causes less enviromental to manage the urbanization and industrialization
pollution. process to meet eco friendly requirements.

287
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of the Poliburo regarding Enviromental protection in
Hoang, K.H. 2007. Report of the topic “Researching to the period of strengthening the industrialization and
set up the enviromental planning process for districts in modernization of the country.
Ho Chi Minh city, pilot implementation for District 2”. Workshop material. 2005. Urbanization and urban life in
Ho Chi Minh city. the future in Vietnam—discussion of public space in the
Ministry of Construction. 2002. Classification of urbans urbans.
and urban management decentralization. Construction Workshop material. 2006. Orientation of sustainable
Publishing House, Ha Noi. development strategies in Vietnam and the link with
Nguyen, T.B. 2004. Construction Planning of Urban enviromental planning.
Development. Construction Publishing House. Ha Noi. Workshop material. 2006. Setting up enviromental plan-
Nguyen, T.T. 2004. Enviromental planning for sustainable ning process for districts.
development. Scientific and Technical Publishing
House, Ha Noi.
Pham, N.D. 2000. Management of urban and industrial park
enviroment. Construction Publishing House, Ha Noi.
Phung, C.S. 2004. Discussions about some necessary
policies to foster to widely apply the model of eco
friendly industrial parks under the transitional industri-
alization and modernization in our country. The report
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288
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Identifying hazards at latex workshop of Ben Suc Rubber Factory,


Vietnam

T.N.S. Tran
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

A. Bernatík
Faculty of Safety Engineering, VSB—Technical University of Ostrava, Ostrava, Czech Republic

ABSTRACT: In Vietnam, the rubber processing industry entails safety risks for workers. At the latex
workshop of Ben Suc Rubber Factory, workers always have to work in wet environments, and the risk of
electrocution, roll and clamp or slip can easily occur. Identifying hazards and risk assessment in the work-
shop is an important basis to determine the measures for prevention of occupational accidents. Measures
to improve the working environment can be made simple but it can bring rapid effectiveness and safe for
workers.

Keywords: Latex workshop, hazards and risk assessment, workers, prevention of occupational accidents

1 INTRODUCTION Identifying hazards and risk assessment in the


workshop is an important basis to determine the
Natural rubber as raw materials have an important measures for prevention of occupational accidents
role with more than 50,000 uses that is extremely and to improve the safety working environment for
widespread applications in industries as well as in workers as well.
daily life. In Vietnam There are over 500 rubber
latex processing enterprises.
This is enterprises which are responsible for 2 METHODOLOGY
planting, and processing of rubber with many dif-
ferent sizes, and attracting large number of workers 2.1 Determining the estimated criteria
in each locality. At the rubber processing factory,
Criteria for estimating the consequences of injury
use of chemicals for the manufacturing process
is presented in Table 1.
have affected on the health and safety of workers.
Criteria for estimating the probability of risks is
At the latex workshop of Ben Suc Rubber Factory,
presented in Table 2.
workers must perform the production stages to
Criteria for ability to identify risks is presented
cause unsafety risks such as hardened latex, trans-
in Table 3.
port of hardened latex, foam cleaning for latex,
uses of rolling and cutting machines, drying ovens
Levels of risks = Probability of risks *
or pressing machines. These caused many potential
Consequences of injury * Ability of identification
risks of unsafe with at least three accidents occur-
ring each year at factories. The process of rubber
latex manufacturing is presented in Figure 1.
Table 1. Rates for consequences of injury.

Levels Description Score


Children
Children Children
Children Minimal No injury or disease, can return 1
to work normally
Minor Minor injuries, minor illness, 2
resignation from 1–3 days
Children Children Children Major Injury, serious illness, leave for 3
3 days, no loss of working capacity
Severe Death or loss of working capacity 4
Figure 1. Process of rubber latex manufacturing.

289
Table 2. Rates for probability of risks. 3 RESULTS AND DISCUSSION
Probability of risks Score 3.1 Identification of hazards by each area
Not occur or occur very rarely (≤1 times/year) 1 3.1.1 The risks in area receiving water latex
Occasionally it occurs (1 times/week, 1 times/ 2 material
month, 1 time/quarter) Table 6 presented the risks in area receiving water
Frequently occurring (whenever conducted or 3 latex material.
1 times/day)
3.1.2 The risks in area freezing latex material
The risks in area freezing latex material is pre-
Table 3. Rates for ability to identify hazards.
sented in Table 7.
Probability of risks Score
3.1.3 The risks in area molding and washing latex
Existing hazards certainly know 1 material
Potential hazards hardly recognizable, 2 Table 8 is presented the risks in area molding and
identifiable only by using the measuring washing latex materials.
device
3.1.4 The risks in area of drunking latex material
The risks in area of drunking latex material is pre-
Table 4. Risk assessment matrix.
sented in Table 9.
Ability to
identify risks 3.1.5 The risks in area of molding and packaging
Table 10 is presented the risks in area of molding
1 2 and packaging.
Consequences of injury * 1 1 2 3.1.6 The risks in warehouse area
Probability of risks 2 2 4 Table 11 is presented the risks in warehouse area.
3 3 6
4 4 8
6 6 12 3.2 Risk assessment for control approaches
8 8 16 The risk assessment is presented in Table 12.
9 9 18
12 12 24
3.3 Approaches for risk control

Table 5. Regulation of risk levels. There are some approaches for risk control sug-
gested bellows:
Risk levels Requirements for control − Use non-slip coating on the floor, into ditch
1
(Figure 1).
(1÷4)
Perhaps accepting − Use non-slip flooring panels (Figure 2);
(6÷12) 2 − Design barriers for hardened ditches (Figure 3);
Medium
(16÷24) 3
Truly remarkable 4 CONCLUSION

An incident or accident derived from unsafe condi-


Table 4 presented the matrix assessing the levels tions or unsafe behavior, which led to the injury to
of risks. workers, disrupt production lines and cause prop-
The regulations of risk levels is presented in erty damage to plants, companies and enterprises.
Table 5. Identifying safety at workplace is contributing to
discover the source of the problem, find out the
hazards to workers. From that the hazards are con-
2.2 Methods of risk identification
trolled to ensure the safety of workers.
Using fishbone chart with the factors determining At the latex workshops of Ben Suc Rubber Fac-
the risk derived from man, machinery, material, tory that exists the danger can lead to occupational
management, measurement and method (6M), accidents. Therefore, identify hazards and risk
combined with questions 5 Why to identify risks assessment at the workshops, and take measures
that can lead to occupational accidents. to improve the working environment is essential.

290
Table 6. Risks in area receiving water latex material.

Activities Risks Causes Consequences

Discharge latex from Fall down Unfocused, careless; Minor scratches, bruises,
tankersw There is no place for swelling, chipped or
standing broken bones
Direct contact with latex Workers do not use the Irritation, allergic reactions,
containing antifreeze means of personal corrosion
chemicals protection
Rubber shot in the eye Workers mounted exhaust Eyesore
pipes improperly;
Workers do not use
personal protective
means
Workers stand on a Fall down Workers stand on a Skin abrasions, swelling,
conduit stir in sifted stainless steel rod pipes bruises, chipped or
latex combines broken bones
strategy with Hand injury Manipulating the spray Discomfort hands, fingers
stainless steel spray nozzle with great do not move
bar pressure
Direct contact with latex Workers do not use Irritation, allergic reactions,
containing antifreeze personal protective corrosion
chemicals means
Using high-pressure Hand injury Manipulating the spray Discomfort hands, fingers
water tap to wash nozzle with great do not move
trays and pipes pressure
Sieve was hit in the leg or Heavy grate Skin abrasions, swelling,
body Unfocused, his grasp; bruises, chipped or
Workers do not use broken bones
the means of personal
protection
Fall down Wet and slippery Skin abrasions, swelling,
background bruises, chipped or
broken bones
Bumping into the pipe The pipes and wires to not Skin abrasions, swelling,
and sieve tidy, with no way to travel; bruises, chipped or
The area of the narrow broken bones
working area.
Direct contact with latex Workers do not use the Irritation, allergic reactions,
containing antifreeze means of personal corrosion
chemicals protection
Make of chemicals Shockwave Electrical control box stirrer Numbness, loss of feeling,
into the mixture rust, peeling insulation fainting
reservoir, stage by Make falls into mixture Mixture reservoir close Injury
stirrer and froth reservoir walkways, small paths;
surface spray Workers joking when
working.
Falls into the chemical drums Chemical drums uncovered, Injury
uncovered;
Slippery floor;
Workers joking when
working.
Pouring chemicals on people, Workers should get too full Irritation, allergic reactions,
on the floor of chemicals spilled when corrosion
moving on the floor, Chemical leakage
poured on people;
The workers collide due
to the narrow aisles, no
attention around;
Workers do not use the
means of personal
protection.

291
Table 7. Risks in area freezing latex material.

Activities Risks Causes Consequences

Acid phase and stirring Chemical and rubber Workers are not compliant Chemical and latex
the latex with two flow spill workflow, distraction, leakage;
working individually Corrosive, Explosive
Clean hardening channel Fall down Walls and ditches are small, Skin abrasions, swelling,
slippery, wet; bruising
Workers do not pay
attention, distraction.
Hand injury Manipulating the spray Discomfort hands, fingers
nozzle with great pressure. do not move
Water and PERUM Water, reflections PERUM Eyesore
latex splash in splashed in the eyes of the
the eye toilet drain bend;
Workers do not use the
means of personal
protection.
Direct contact Workers do not use personal Irritation, corrosion
with wastewater, protective means
PERUM latex
Going down along the Fall down Walls and ditches are small, Skin abrasions, swelling,
ditch water spray and slippery, wet; bruises, chipped or
spray foam on the Workers ease off balance broken bones;
surface antioxidant because using the medium Serious head injury and
latex pressure and moving; parts if fall down;
Workers lack focus, joke Chemical being invaded;
around while working; Chemical leakage,
Workers move back and damage to property
forth between the ditch if a fall while wearing
no grip, handrail; chemical spray.
Workers stand on a stainless
steel rod pipes

Table 8. Risks in area molding and washing latex materials.

Activities Risks Causes Consequences

Pull latex on the top Fall down Slipped into the gutter led latex; Skin abrasions, swelling,
of ditch by pus None frozen latex, hooks do bruising
clinch not hook slip causing loss of
balance
Pull the latex into Falls, banging his Loss of balance when standing Head trauma, skin
rollers head on the mill drops to 2 feet above the trench abrasions, swelling,
2; when pus sliding blocks fast bruising
forward when pulled into the
machine
Direct contact with Workers do not use the means of Corrosion, skin irritation
latex was freeze personal protection
Displacement pump Fall down Jump back and forth between Skin abrasions, swelling,
and discharge the ditch has a slippery, small bruising hands and feet;
between the ditch standing area Chemicals intrusion if
and iron sticks falling to perum ditch
moving along Direct contact with Workers do not use the means of Corrosion, skin irritation
ditches freeze perum latex personal protection
Mill operation Hands jammed into Wrong operation of safety rules; Serious injuries such as
the mill Negligence, distraction; a broken arm, broken
Exposure to actuators, motion. fingers
Shockwave Electrical box at mill location Shockwave
damaged, rust

(Continued )

292
Table 8. (Continued )

Activities Risks Causes Consequences

Fall down Tier stood slippery, broken; Skin abrasions, trauma


Button to adjust the reach
higher than workers
Exposure to rubber The noise emanating from the Headaches, tinnitus,
smell combined drying zone nausea
with noise Rubber smell in the air;
Workers do not use the means
of personal protection
Mill cleaning Hand injury Manipulating the spray nozzle Sore hands, the fingers
with great pressure can not move
Fall down Slippery and wet background Skin abrasions, swelling,
bruising limbs
Exposure to the Drying noise emitted; Headaches, tinnitus,
smell of rubber Rubber smell in the air; nausea
combined with the Workers do not use means of
noise personal protection
water and wastewater Workers do not use means of Eyesore
shot in the eye personal protection

Table 9. Risks in area of drunking latex material.

Activities Risks Causes Consequences

Scattered latex spread Water from rubber splash Workers crouched put into areas Eye pain, irritation
in drying bins into the skin, eyes close to the water shot out,
and floor vibration hand made
mouth water hook back into the
couch;
Workers do not use the means of
personal protection.
Direct contact with the Health and drying area noise Headaches, tinnitus,
smell of latex and high emitted; nausea
noise levels Rubber smell in the air;
Workers do not use the means of
personal protection.
Head injury Use your mouth to push through the Headache
discharge of latex cells drying bins
Direct contact with latex Latex dropped directly into the Hand blistering and
hands when using hand-crocheted cracking
in purulent tonsillitis and spread
evenly;
Workers do not use the means of
personal protection.
Push the crate to the Fall down Latex barrel slide rapidly on rails; Minor scratches,
dryer or the container Workers do not use the means of bruises
to the area of the personal protection
dryer inlet Direct contact with latex Smoking area emits noise; Headaches, tinnitus,
smell and high noise Rubber smell in the air; nausea
levels Workers do not use the means of
personal protection
Pull latex containers Fall down Latex barrel slide rapidly on rails Minor scratches,
from cooling areas bruises
after drying out Burned Hot latex container Burned in 1st level
Workers do not use the means of
personal protection.

293
Table 10. Risks in area of molding and packaging.

Activities Risks Causes Consequences

Use the hook to hook Fall sown Using the wrong hook Aches, swelling,
the rubber blocks was bruising
drying out and put on Body discomfort Waiter rubber blocks from the Body discomfort,
roller path drying barrel to rails, body dizziness
turned 180 degrees
Fan blowing directly Use industrial cooling fans Heat loss, dry eyes
on people with placed too close
high wind speeds
Weigh rubber blocks under Hand fatigue Waiter rubber blocks on Hand discomfort
the weight requirement scales
Cut into the hands Workers do not pay attention, To cut one’s finger
distraction
Putting the rubber blocks Hands jammed into Wrong operation of safety Hand Fractures
on presses and operation presses rules
Hands jammed Frame of presses move back Hand Fractures
and forth with non-shielded
Fan blowing on the Use industrial cooling fans Eye pain, dry eyes
face, body placed too close
Cut rubber sample after To cut one’s finger Workers do not pay attention, Broken fingers,
drying distraction hands
Rubber blocks coated by Burned Workers do not pay attention, Burned in 1st level
plastic, mouth stick and distraction while heating
labeled by heating the packages
Close pallets of finished Sore arms and back Waiter blocks of finished Hand and back
rubber rubber, bent body posture discomfort

Table 11. Risks in warehouse area.

Activities Risks Causes Consequences

Move the pallet into and Push the pallet into Workers are not observed Hurt;
out of warehouses the other workers when moving the forklift; Fallen goods
with forklifts or packages The corner has no observation
mirror, out of sight
Sort pallets in warehouse Fallen Workers lose focus Trauma, bleeding, skin
abrasions, bruises;
Damaged pallets

Table 12. Risk assessment.

Risks Levels

Direct contact with latex containing antifreeze 6


chemicals
Electrocuted while operating mill 6
Falls when cleaning hardened raceways; 6
Falls when the water spray foam or antioxidant
on latex surface;
Move pumps between the ditch
Exposure to hardened rubber smell combined 12
with the noise in the area of rolling mills
and smoking areas
Push the crate into drying inlet
Water from rubber splash on skin 8 Figure 1. Working floor in latek receiving area (a) and
latek freezing area (b).

294
Besides this paper also proposed measures to
control hazards.

REFERENCES

Ben Suc Rubber Factory. 2010. Work instructions of latex


production process. Ben Suc Rubber Factory, Binh
Duong.
Ben Suc Rubber Factory. 2015. Survey on manufacturing
and environmental issues arising in the latex produc-
tion process. Ben Suc Rubber Factory, Binh Duong.
Figure 2. FRP (a) and vinyl (b) plastic slab.
Ben Suc Rubber Factory. 2016. Labor protection plan in
2016. Ben Suc Rubber Factory, Binh Duong.
Hoang, V.B. 2010. Occupational health. Publishing House
of Science and Technology, Hanoi,
Nguyen, V.Q. 2002. Principles of labour protection.
Teaching materials, Ton Duc Thang University, Ho
Chi Minh City.
Tran, T.N.S. (2004. Risk assessment of working condi-
tions. Teaching materials, Ton Duc Thang University,
Ho chi Minh City.

Figure 3. Barriers for hardened ditches.

295
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Building forecast maps of dust dispersion in the Song Hau 1 Thermal


Power Plant, Vietnam

T.T.H. Nguyen & A.D. Pham


Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

T.V. Nguyen & T.K. Do


Power Engineering and Consulting Joint-Stock Company No.3, Ho Chi Minh City, Vietnam

ABSTRACT: This study aims to enhance the mapping of forecast for dust dispersion in the Song Hau
1 Thermal Power Plant project area, Hau Giang Province. The data from 115.2 ha of the Song Hau 1
Thermal Power Plant in the year 2012 was used for calculation and mapping, and the data from total 355
hecta of the Hau Giang Power Complex were applied for reference purposes. Breeze AERMOD GIS Pro
software was used to forecast dust dispersion. This software was compiled by Trinity Consultant based on
AERMOD model which was recommended by United State Environmental Protection Agency for calcu-
lating or forecasting dust dispersion. AERMOD model was more advanced than ISC3 (Industrial Source
Complex Model). The results showed that the Song Hau Power Complex in the phase 1 with operation
of the Song Hau 1 TPP, after installing the dust removal system (99%), exhausted dust of the plant met
the National Technical Regulations QCVN 22:2009/BTNMT in the stack mouth and QCVN 05:2009/
BTNMT on ambient air quality. Besides, the Song Hau Power Complex in the phase 2 with operation of
the Song Hau 1 and Song Hau 2 TPPs, after installing the dust removal system (99%), exhausted gas of the
plants gained the National Technical Regulations QCVN 22:2009/BTNMT in the stack mouth and QCVN
05:2009/BTNMT on ambient air quality. The dust concentrations in the ambient air affected by exhausted
gas of the Song Hau Power Complex with operation of all three plants of Song Hau TPP 1, 2 and 3.

Keywords: forecast maps, dust dispersion, thermal power plant, AERMOD model

1 INTRODUCTION Song Hau 1 TPP): 4.5 hecta (Electricité De France


and PECC4. 2008; PECC4. 2010).
The Song Hau 1 Thermal Power Plant (TPP) Normally, thermal power plant have got the
locates at Song Hau—Hau Giang Power Complex strong impacts on the environment and ecosystems
(PC) belonging to Phu Huu A Commune, Chau because of massive pollutant dispersion (Tran
Thanh District, Hau Giang Province. Geographi- 2000). Especially, dust emission was exhausted by
cal position of the Hau Giang PC is 09°56’22” fuel and coal combustion; coal reception, trans-
–09°57’49” North latitude and 105°50’20”– portation and storage; transportation of fly ash.
105°51’51” East longitude. The Song Hau—Hau So, building the forecast maps of dust dispersion
Giang Power Complex is located on right shore in the Song Hau 1 TPP needed be done to control
of the Hau River belonging to Phu Huu A Indus- the project impacts.
trial Group, far away Can Tho City about 1.3 Km
toward downstream of Hau River, An Dinh Estu-
2 MATERIALS AND METHODS
ary about 66 Km toward upstream and Ho Chi
Minh City about 180 Km (Electricité De France
2.1 Study area
and PECC4. 2008; PECC4. 2010).
The Song Hau 1 TPP required about 115.2 hecta The Song Hau 1 TPP locates in the Song Hau
in area, as follows: main plant area, auxiliary zone Power Complex, was built after the Infrastructures
of the Song Hau 1 TPP: 42 hecta; 220 kV substa- of Song Hau Power Complex project had been fin-
tion area: 2.5 hecta; area of cooling water dis- ished the stage 1 (finished clearing the ground and
charge canal: 20.5 hecta; executing site area: 12.5 building infrastructures of the Song Hau 1 TPP),
hecta; ash, slag disposal pond area: 33 hecta; area main work items include: main zone of the Song
of internal roads and other auxiliary area (in the Hau 1 TPP, 220 kV switchyard, coal storehouse,

297
ash dispose pond, importing coal port, and auxil- Table 2. Regulation on ambient air quality.
iary systems (Figure 1).
Song Hau 1 TPP was proposed to use coal QCVN 05:2009/BTNMT
Parameter
imported from Indonesia or Australia as main
(mg/Nm3) Average 1 hr Average 24 hrs
fuel. Fuel combustion process could cause air pol-
lutants, especially such as SO2, NOx and dust. The Dust 0.3 0.2
report considered main pollutants in the exhausted
gas such as dust (Electricité De France and PECC4.
2008; PECC. 2010).
The environmental regulations applied for Table 3. Parameters used for calculation of emission
exhausted dust gas and ambient air quality was rate (TSERM. 2011).
the National Technical Regulation on emission of Parameters Song Hau 1 TPP
thermal power industry: QCVN 22:2009/BTNMT
issued Circular No.25/2009/TT-BTNMT dated Capacity (MW) 2 × 600
Nov.11th 2009 of Ministry of Natural Resources Boiler type Pulverized-coal-fired
and Environment on the provisions of national boiler
technical regulations on environment (Table 1, 2). Steam parameters: 250bar 540–560°C
Pressure super critical
Temperature high
2.2 Calculation of emission rate of Song Hau 1 pressure/return baking gas
TPP Annual consumption coal 3,660,585
Emission rate of pollutants from stacks was cal- (tons/yr)
culated for the most unfavorable scenario that Average annual operation 6,500
time (hrs/yr)
the plant have been operated with full capacity
Total volume of emission 2 × 2,285,200
and coal as main fuel; so, emission rate of pollut- gas (kg/h)
ants reached maximum at that time (Hau Giang Gas temperature in the stack 82.05
DONRE. 1999). Coal used for calculation was mouth (°C)
steam coal (main fuel of the plant). Velocity of emission gas 21
(m/s)
Stack diameter (m) 2 × 6.2*
% Sulfur in coal (%) (adb) 0.86
Coal ash percentage (%) (adb) 12
Volatile (%) (adb) 42

Notes: *02 stack of the plant will be located side by side


with an inner diameter of 6.2 m for each.

To calculate emission rate and concentration


of pollutants in exhausted gas of the plant, the
project followed Steam Pro software (US EPA.
2004). This was designed based on the combus-
tion characteristics of the boiler. Steam Pro was a
program designed for power plants that use steam
following Rankine cycle (US EPA. 2004). The data
Figure 1. Study site. from 115.2 hecta of the Song Hau 1 Thermal Power
Plant in the 2012 was used for calculation and map-
ping, and the data from total 355 hecta of the Hau
Table 1. Regulation on emission of thermal power Giang Power Complex were applied for reference
industry. purposes. The input data of the program was as
follows: select the profile and thermodynamic data
QCVN 22:2009/BTNMT for the design (usually under nominal, full load);
Parameter (Cmax = Ctc*Kp*Kv) with input data on the natural conditions of project
(mg/Nm3) Kv = 1.2; Kp = 0.85 area, such as pressure, air temperature and humid-
Dust 204 ity, altitude, water temperature, temperature of
cooling water; and, input date on solid fuel used to
Notes: Kv = 1.2 (due to the project locates in rural region) burn in the boiler, for example with coal we need to
and Kp = 0.85 (the capacity is 1,200 MW). input data such as moisture, volatile components,

298
ash, heating value and composition of elements in AERMOD model which are recommended by U.S
coal such as carbon, hydrogen, nitrogen, chlorine, Environmental Protection Agency (EPA) for cal-
sulfur, oxygen (Hau Giang DONRE. 1999). culating or forecasting concentration and disper-
The program calculated heat balance and effi- sion of air pollutants. AERMOD model was more
ciency of the plant. Besides, based on the com- advanced than ISC3 (Industrial Source Complex
bustion of the fuel, the program calculated the Model) (US EPA. 2004). Meteorology input data
concentration of exhausted gas into the atmos- for modeling software was a set of hourly data col-
phere. In addition, the program can find the lected during one month which was represented
parameters of main equipment and devices. rainy and dry season. The highest 24-hr and 1-hr
average concentration values which were calculated
by the modeling software (background concentra-
2.3 Calculation scenarios and data analysis
tion included) have been compared with ambient
Breeze AERMOD GIS Pro software was used to air quality regulation ones.
forecast dust dispersion (US EPA. 2004). This soft- The Song Hau 1 TPP located in the Song Hau
ware was compiled by Trinity Consultant based on PC. Designed capacity of the power complex was
5,200 MW. Hence, in the calculation and forecast of
exhausted gas dispersion of the Song Hau 1 TPP, it
was necessary to consider and forecast exhausted gas
Children
Children Children dispersion in case of the Song Hau power complex
operates at full capacity (all plants Song Hau TPP 1,
2 and 3 have operated together) so as to meet QCVN
05:2009/BTNMT. In addition, the height of stacks
and efficiency of removal systems of each plant was
ccalculated so that it was effective and economical,
but also met permitted regulations. Therefore, the
calculated scenarios were as follows: Scenario 1—
the Song Hau PC in phase 1 with the operation of
the Song Hau 1 TPP; Scenario 2—the Song Hau PC
in phase 2 with the operation of the Song Hau 1 and
Song Hau 2 TPPs; and Scenario 3—the Song Hau
PC in phase 3 with the operation of the Song Hau 1,
Song Hau 2 and Song Hau 3 TPPs.
Input data for air dispersion modeling software
Of which: CTot is the total concentration (g/m3); CHoriz is the
n ng đ theo tr ng th i ph ng ngang c a c t khói (g/m3) was assumed as follows: designed capacity of Song
(see EPA-454/R-03-004); CTerrRes is the N ng đ theo tr ng Hau 1 TPP was 1,200 MW (2 × 600MW) (Table 4).
th i đ a h nh c a c t kh i (g/m3) (see EPA-454/R-03-004); Capacity of Song Hau 2 and Song Hau 3 TPPs
f is the plume state weighting function; and, φp is the frac- were 2,000MW (2 × 1,000MW) (Table 5). Fuel of
tion of the plume mass. the plants was imported bituminous coal; stack
height was designed so that it had to meet tech-
Table 4. Input parameters of air dispersion modeling
nical criteria (dispersion of air pollutants was the
software—Song Hau 1 TPP (capacity 1,200 MW). best) and economic efficiency. The calculated stack
height was 200 m, including 02 stacks with inner
Song Hau 1 TPP diameter of 6.2 m. Velocity of exhausted gas was
21 m/s at 82.05°C; and, components of exhausted
Emission rate Concentration gas: all three plants Song Hau 1, Song Hau 2 and
Parameter (g/s) (mg/Nm3) Song Hau 3 were installed dust removal systems
Dust 117.25 116.39 with treatment efficiency respectively as 99% to
meet QCVN 22:2009/BTNMT in the stack mouth.

Table 5. Input parameters of air dispersion modeling software—Song Hau 2 and Song Hau 3 TPPs (capacity 2,000
MW).

Conc. before Proposed Conc. after Emission rate after


Emission rate treatment efficiency treatment treatment
Parameter (g/s) (mg/Nm3) (%) (mg/Nm3) (g/s)
Dust 18,950 11,639 99 116.39 189.50

299
Main and common wind direction in the project Song Hau PC and the Song Hau 1 TPP (NCHMF.
area was the Southeast in the dry season and the 2009). And, topography in the project area was
Southwest in the rainy season. The report used real plain with elevation varying from −0.1 to +2 m, so
meteorological data in all months from 2004 to 2008 it could be relatively flat, and altitude in all points
of the Can Tho meteorological station to calculate were considered as at the same (PECC4. 2009).
dispersion of pollutants in exhausted gas of the

3 RESULTS AND DISCUSSION


Table 6. Emission rate and dust concentration in
exhausted gas of the Song Hai 1 TPP.
Calculation results were presented in Table 6.
QCVN 22:2009/ Exhausted gas of the plant had to meet QCVN
BTNMT 22:2009/BTNMT on concentration of air pollut-
(Cmax = Ctc*Kp*Kv) ants in stack mouth, and QCVN 05:2009/BTNMT
Calculated Emission Concentration v i Kv = 1.2; on concentrations of air pollutants in ambient air.
parameter rate (g/s) (mg/Nm3) Kp = 0.85 (mg/Nm3) Table 7 showed that concentration of dust
Dust 11,725.3 11,639 204 was over permitted value as stipulated in QCVN
22:2009/ BTNMT. To meet QCVN 22:2009/

Table 7. Dust concentration of before and after.

Emission
Conc. before QCVN 22:2009/ Conc. after rate after
Calculated treatment BTNMT Required Eff. Selected Eff. treatment treatment
parameter (mg/Nm3) (mg/Nm3) (%) (%) (mg/Nm3) (g/s)
Dust 11,639 204 98.25 99 116.39 117.25

Table 8. Dust concentration in ambient air affected by the Song Hau 1 TPP.

Calculated highest Concentration in


average concentration ambient air (included QCVN 05:2009/ Coordinates
Month Average in (μg/m3) background) (μg/m3)* BTNMT (μg/m3) (m; m)

Jan. 1 hr 20.88 86.38 300 20750 24750


24 hrs 3.83 38.52 200 28000 12500
Feb. 1 hr 20.71 86.21 300 18000 22500
24 hrs 3.87 38.56 200 13500 12500
Mar. 1 hr 12.60 78.10 300 18250 22250
24 hrs 2.88 37.57 200 13500 27000
Apr. 1 hr 18.82 84.32 300 25500 15000
24 hrs 4.29 38.97 200 15500 25000
May 1 hr 19.77 85.27 300 25500 19750
24 hrs 4.43 39.12 200 28500 12000
June 1 hr 18.80 84.30 300 15500 25000
24 hrs 4.89 39.58 200 29000 11500
July 1 hr 17.38 82.88 300 25750 24750
24 hrs 4.21 38.90 200 28250 27250
Aug. 1 hr 21.33 86.83 300 18000 17000
24 hrs 3.79 38.48 200 20750 27250
Sep. 1 hr 20.86 86.36 300 22500 19750
24 hrs 4.56 39.25 200 19000 21500
Oct. 1 hr 21.04 86.54 300 17000 19750
24 hrs 5.18 39.87 200 12500 19750
Nov. 1 hr 19.55 85.05 300 16000 19750
24 hrs 4.49 39.17 200 13250 12250
Dec. 1 hr 20.79 86.29 300 23750 16750
24 hrs 4.62 39.31 200 20750 8500

300
BTNMT, removal systems of dust needed be in- after installing the dust removal system (99%),
stalled with their treatment efficiency as below. exhausted dust of the plant met National Tech-
Therefore, after installing removal systems of dust nical Regulations QCVN 22:2009/BTNMT in
(with the treatment efficiency is 99%), dust con- the stack mouth and QCVN 05:2009/BTNMT
cen-tration in exhausted gas met permitted level in on ambient air quality.
QCVN 22:2009/BTNMT. Contour maps on concentration of dust calcu-
The calculation results of air pollutants from lated from air dispersion modeling software for
dispersion modeling software were presented in Song Hau 1 TPP were as follows:
Table 8. To forecast comprehensively concentration of pol-
Table 8 showed that concentration of pol- lutants in the ambient air affected by exhausted gas of
lutants in ambient air met QCVN 05:2009/ the Song Hau power complex. The report considers the
BTNMT. Like this, the Song Hau PC in the operation of the Song Hau 2 and Song Hau 3 TPPs. The
phase 1 with operation of the Song Hau 1 TPP, result was as follows the concentration of pollutants in

Figure 2. Contour map of dust dispersion by the Song Hau 1 TPP. (a) Contour map of highest 1 hr average concen-
tration of dust—March; (b) Contour map of highest 24 hrs average concentration of dust—March; (c) Contour map
of highest 1 hr average concentration of dust—September; (d) Contour map of highest 24 hrs average concentration
of dust—September.

301
Table 9. Dust concentration in ambient air affected by the Song Hau PC in the phase 2.

Calculated high- Concentration


est average con- in ambient air
centration (μg/ (included back- QCVN 05:2009/
Month Average in m3) ground) (μg/m3) * BTNMT (μg/m3) Coordinates (m; m)

Jan. 1 hr 54.61 120.11 300 20500 24750


24 hrs 10.04 44.73 200 27750 12750
Aug. 1 hr 55.33 120.83 300 17750 17000
24 hrs 9.89 44.58 200 20500 27250

Notes: Above table shows the calculated result of 2 months: January (dry season) and August (rainy season); concen-
trations of pollutant are calculated in the most unfavorable scenario (the plants operate in full capacity and coal is fuel.
The Song Hau 1 and Song Hau 2 TPPs installed the dust removal system (treatment efficiency 99%) to meet QCVN
22:2009/BTNMT for exhausted gas in stack mouth; *C = (Ccalculated + Cbackground) with Cbackground is result analysed by
SITES II in Aug. 2009; bolted data is higher than permitted value in QCVN 05:2009/BTNMT.

Table 10. Treatment efficiency of exhausted dust of the plants in the phase 2.

Conc. after Emission rate


Conc. before treatment QCVN 22:2009/ Required Selected Eff. treatment after treatment
(mg/Nm3) BTNMT (mg/Nm3) Eff. (%) (%) (mg/Nm3) (g/s)

Song Hau 1 TPP


11,639 204 98.25 99.0 116.39 117.25
Song Hau 2 TPP
11,639 204 98.25 99.0 116.39 189.50

Table 11. Dust concentration in ambient air affected by the Song Hau PC in the phase 2 after installing the SCR
system.

Calculated highest Concentration in


average concentra- ambient air (included QCVN 05:2009/ Coordinates
Month Average in tion (μg/m3) background) (μg/m3) * BTNMT (μg/m3) (m; m)

Jan. 1 hr 54.61 120.11 300 20500 24750


24 hrs 10.04 44.73 200 27750 12750
Aug. 1 hr 55.33 120.83 300 17750 17000
24 hrs 9.89 44.58 200 20500 27250

Notes: Above table shows the calculated result of 2 months: January (dry season) and August (rainy season); Pollut-
ants concentration is calculated in the most unfavorable scenario (the plants operate in full capacity and coal is fuel;
the Song Hau 1 and Song Hau 2 TPPs installed the dust removal system (treatment efficiency 99%); * C = (Ccalculated +
Cbackground) with Cbackground is result analysed by SITES II in Aug. 2009.

Table 12. Dust concentration in ambient air affected by the Song Hau PC in the phase 3.

Calculated highest Concentration in


average concentration ambient air (included QCVN 05:2009/
Month Average in (μg/m3) background) (μg/m3)* BTNMT (μg/m3) Coordinates (m; m)

Jan. 1 hr 88.42 153.92 300 20500 24750


24 hrs 16.27 50.96 200 27750 12750
Aug. 1 hr 88.31 153.81 300 17750 17250
24 hrs 16.02 50.71 200 20500 27500

Notes: Above table shows the calculated result of 2 months: January (dry season) and August (rainy season); Pollutants
concentration is calculated in the most unfavorable scenario (the plants operate in full capacity and coal is fuel. All 3
plants installed the dust removal system (treatment efficiency 99%) to meet QCVN 22:2009/BTNMT for exhausted gas
in stack mouth; * C = (Ccalculated + Cbackground) with Cbackground is result analysed by SITES II in Aug. 2009; Bolted data is
higher than permitted value in QCVN 05:2009/BTNMT.

302
Table 13. Treatment efficiency of exhausted gas of the plants in the phase 3.

Conc. before QCVN 22:2009/ Conc. after Emission rate


treatment BTNMT Required Selected treatment after treatment
(mg/Nm3) (mg/Nm3) Eff. (%) Eff. (%) (mg/Nm3) (g/s)

Song Hau 1 TPP


11,639 204 98.25 99 116.39 117.25
Song Hau 2 and Song Hau 3 TPPs
11,639 204 98.25 99 116.39 189.50

Table 14. Concentration of air pollutants in ambient air affected by the Song Hau power complex in the phase 3 after
installing the SCR system.

Calculated Concentration in
highest average ambient air (included
concentration background) QCVN 05:2009/ Coordinates
Month Average in (μg/m3) (μg/m3) * BTNMT (μg/m3) (m;m)

Jan. 1 hr 88.42 153.92 300 20500 24750


24 hrs 16.27 50.96 200 27750 12750
Aug. 1 hr 88.31 153.81 300 17750 17250
24 hrs 16.02 50.71 200 20500 27500

Notes: Above table shows the calculated result of 2 months: January (dry season) and August (rainy season); Pollutants
concentration is calculated in the most unfavorable scenario (the plants operate in full capacity and coal is fuel; The 3
TPPs installed the dust removal system (treatment efficiency 99%); * C = (Ccalculated + Cbackground) with Cbackground is result
analysed by SITES II in Aug. 2009.

the ambient air affected by exhausted dust of the Song mouth and QCVN 05:2009/BTNMT on ambient air
Hau PC with operation of the Song Hau 1 and Song quality.
Hau 2 TPPs. Results from Table 9 showed when the
Song Hau 1 and Song Hau 2 TPPs operated.
After the Song Hau 1 and Song Hau 2 TPPs 4 CONCLUSION
install the SCR systems as mentioned in the
Table 9, the calculation result was as Table 10. The results showed that the Song Hau PC in the
Table 11 showed that dust concentration in phase 1 with operation of the Song Hau 1 TPP,
ambient air met QCVN 05:2009/BTNMT. Like after installing the dust removal system (99%),
this, the Song Hau PC in the phase 2 with opera- exhausted dust of the plant met National tech-
tion of the Song Hau 1 and Song Hau 2 TPPs, nical regulations QCVN 22:2009/BTNMT in
after installing the dust removal system (99%), the stack mouth and QCVN 05:2009/BTNMT
exhausted dust of the plants met National tech- on ambient air quality. Besides, the Song Hau
nical regulations QCVN 22:2009/BTNMT in the PC in the phase 2 with operation of the Song
stack mouth and QCVN 05:2009/BTNMT on Hau 1 and Song Hau 2 TPPs, after installing the
ambient air quality. The concentrations of dust in dust removal system (99%), exhausted gas of the
the ambient air affected by exhausted gas of the plants met National technical regulations QCVN
Song Hau PC with operation of all 3 plants Song 22:2009/BTNMT in the stack mouth and QCVN
Hau 1, Song Hau 2 and Song Hau 3. Table 12 and 05:2009/BTNMT on ambient air quality. The
Table 13 showed that dust concentration in ambi- dust concentrations in the ambient air affected by
ent air met QCVN 05:2009/BTNMT. exhausted gas of the Song Hau PC with opera-
After the plants install the SCR systems as mentioned tion of all 3 plants of Song Hau 1, Song Hau 2
in the Table 11, the calculation result was follows: and Song Hau 3.
Table 14 shows that dust concentration in ambi- With coal as main fuel, the Song Hau 1 TPP
ent air met QCVN 05:2009/BTNMT. Like this, the had some impacts on air quality. In order to met
Song Hau PC in the phase 3 with operation of all 3 National Regulation QCVN 22:2009/BTNMT
plants, after installing the dust removal system (99%), on exhausted gas of power plants and QCVN
exhausted gas of the plants met National technical 05:2009/BTNMT on ambient air quality for all
regulations QCVN 22:2009/BTNMT in the stack plants of the Song Hau PC, it was necessary to

303
install an exhausted gas treatment system with NCHMF. 2009. Meteorological and Hydrographic Data
efficiency. of Can Tho Station. National Centre for Hydro-Mete-
orological Forecasting, Vietnam.
PECC4. 2009. Topography and Geology Report of Song
Hau 1 Thermal Power Plant Project. Power Engi-
ACKNOWLEDGEMENT neering and Consulting Joint-Stock Company No.4,
Vietnam.
We would like to thank Power Engineering & Con- PECC4. 2010. Construction Investment Project Report of
sulting Joint-Stock Company No.3 for helping Song Hau 1 Thermal Power Plant Project. Power Engi-
with the database. neering and Consulting Joint-Stock Company No.4,
Vietnam.
Tran, N.C. 2000. Air Pollution and Exhausted Gas Treat-
REFERENCES ment, Volume No.1. Science and Technology Publisher,
Vietnam.
de Nevers, N. 1995. Air Pollution Control Engineering, TSERM. 2011. Report on Dispersion of Pollutants in
2nd Edition. McGraw-Hill, Inc. Exhausted Gas of the Song Hau 1 TPP. Technology
Electricité De France and PECC4. 2008. Report on Plan- and Sciences of Environment Resources Manage-
ning of the Song Hau Power Complex. Power Engi- ment, Vietnam.
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Environment, Hau Giang.

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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Current needs for further developments toward a circular economy—


specifically in the Central European Region

V. Kočí
University of Chemistry and Technology, Prague, Czech Republic

ABSTRACT: This article is focused on the current environmental challenges and many aspects of a
circular economy. A circular economy is a novel concept of material and energy management within all
industrial societies. Contrary to a linear economy, a circular one aims to minimize the amounts of wastes
produced, using and re-using them as secondary materials. The article briefly discusses consequences
of a circular economy within the Central European region, with a special focus on the Czech Republic.
This region was selected as a template for implementation of a circular economy in other developing
countries and emerging economies. In the article, the main obstacles and challenges for realization of a
circular economy are outlined. The article summarizes environmental, social and economic issues dealing
with upgrade of the economy into the circular one. Finally, practical aspects of introducing the circular
economy into national and international economies are outlined. Main contribution of the paper is in
summarization of actual challenges dealing with change of current state of economy, based on linear
approach into circular one, which is currently understand as necessary tool for sustainable development.

1 INTRODUCTION spheres), it is dominated by subjects involved in


waste management or the development and imple-
Currently, the concept of a circular economy, mentation of waste water recycling technologies,
through which the world’s developed economies as well as subjects focused on monitoring the
have sought to strengthen the sustainability of environmental impacts of human activities on the
their economies, is well developed. The starting environment. It is interesting to note that currently
point of this concept is to replace the linear econ- a minimum of professionals in Central Europe
omy, which is based on the current linear model have become involved and focused on the design
(Take → Make → Use → Dispose); replacing it or eco-design of new products and services; entail-
with a circular model in which potential wastes is ing a few subjects in the agrarian sector, and some
returned back to the economic process and thus professionals engaged in research on the behavio-
closes up the loop. Therefore, we discuss the tran- ral factors of individuals and society. For the circu-
sition to a circular economy which maximizes the lar economy to become a viable concept, it really
reuse of materials, and eventually of energy flows must be a mutual interplay of the stakeholders at
too (George, Lin & Chen 2015). In the circular all stages of the products' life cycle and services
economy concept, the material outputs that are (Cundy et al. 2013). If the circular economy is pri-
currently perceived as waste would be recycled to marily developed by those entities involved in the
the greatest extent possible, thus becoming second- final/end-of-life stages of the life cycle of a linear
ary raw materials (Ongondo, Williams & Whitlock economy (waste management) it will not be easy to
2015). In the Czech Republic, a public debate was put the concept of a circular economy into practice
opened this year, aimed at staring to bring a cir- (Swart & Groot 2015). Although it has been shown
cular economy into practice; thus fulfilling the that implementation of a circular economy is ben-
anticipated requirements of the European Union eficial for the entire supply chain, from produc-
(Communication from the Commission to the ers to the end-of-life managers (Zhu, Geng & Lai
European Parliament, the Council, the European 2011), so far, a sufficient number of success stories
Economic and Social Committee, and the Com- from several countries have not yet been published
mittee of the Regions) (Roadmap to a Resource that would be sufficient to motivate governments
Efficient Europe, COM 2011, 571). Although a or policy makers, thus far, only slightly interested
wide range of subjects take part in the implementa- in a circular economy.
tion of a circulatory economy (from governmental This review strives to summarize the more sig-
to academics, in both not-for-profit and business nificant assumptions and starting points that are

305
necessary to consider when introducing a circular the concept of a circular economy. To these three
economy into countries with still-developing mar- aspects we will add another dimension, reflecting
ket economies. As a model region Central Europe the practical issues involved in implementing a cir-
was selected, with a particular focus on the Czech cular economy.
Republic. The Central European region was delib-
erately chosen for the purposes of this article. It
is a region with a strong tradition of industrial 3 ENVIRONMENTAL ISSUES
production and well as developed follow-up indus-
tries such as water and waste management, energy The primary reason we strive to realize a circular
industry, and the like. However, it is also a region economy is to reduce the environmental impacts of
that in recent years and decades has undergone sig- our industrial activities. Although a circular econ-
nificant changes in its economic system. After the omy is focused on the entire lifecycle of products,
fall of the communist regime in the decade before reflecting upstream, core, and downstream eco-
the end of the 20th century, the region underwent nomic processes; it is currently perceived primarily
development of a liberal society with an open mar- as a challenge for waste management, packaging,
ket. However, there are still stereotypes, especially and recycling technologies. Addressing the issue of
on the importance of the environmental manage- waste can be a good springboard for the implemen-
ment industry, which have prevented rapid devel- tation of the circular economy. Of course, when
opments in this field, similar to those that can be introducing the circulatory economy, we must also
observed in the USA, Western Europe, or Japan. not forget the other stages of products’ life cycles,
For this reason, we perceive the Central European especially their design and planning. In the follow-
region as a good example for other countries in the ing paragraphs we will focus on a few issues related
world that are in a period of economic development to the end-of-life phases of the lifecycle.
and the concurrent structural changes. Unlike the Waste represents significant amounts of mate-
strong emerging economies such as China, which rials, which are still largely perceived as a burden
also begin to be interested in a circular economy to be gotten rid of under the lowest material and
(Mathews & Tan 2011; Wen & Li 2010; Yuan, Bi & energy costs; plus, of course, with the lowest pos-
Moriguichi 2006), the Central European region sible adverse impacts on the environment. Waste
cannot rely on an intense economy, yet in a rela- represents great material flows, yet it is also nec-
tively short time it must adapt as much as possible essary to get rid of them with the lowest possible
to the principles of a circular economy not only public health impacts. Waste management offers
within its territory, but also in the economic, tech- the possibility of using material flows and energy
nological, legislative, and environmental contexts content (Park & Chertow 2014). In order to realize
of both neighbor and non-neighboring countries. the concept of a circular economy, the waste should
be seen as a flow containing recoverable materials
and energy, and to be utilized to the greatest extent
2 ASSUMPTIONS OF THE FLOWS IN possible (Pan et al. 2015). The circulation of waste
A CIRCULAR ECONOMY flows within a circular economy also brings several
challenges that need to be appropriately addressed.
A sustainable economy is a strategy well known Separation or sorting of waste components to
for decades. It requires a means of meeting peo- increase material recovery of waste flows is already
ple’s needs, while also ensuring a long-term bal- a fairly widespread process, which allows for separa-
ance between the environment and human society. tion of the more usable material components from
Although more specific tools and techniques the less usable. Currently, it is fairly well accepted
strengthening the implementation of sustainability to consider waste materials as sources of valuable
into practice have been proposed, it is often not raw materials (Morel et al. 2001; Zabaleta & Rodic
enough of a specific strategy in the view of indus- 2015) or of energy resources (Wagland et al. 2013).
trially oriented stakeholders. The concept of a cir- In incineration plants for mixed municipal waste it
cular economy is more concrete compared with is possible to utilize the thermal energy contained
sustainability strategies, resulting in more realistic in the waste at a level corresponding to the incin-
requirements in practice, and creating clearer ideas eration of low-grade coal (lignite). Thus, the uti-
of how to put them into practical effect. A sustain- lized waste is not considered as recycled, but use
able strategy calls for harmony and balance within of the energy contained within it brings indisput-
a societies environmental, social, and economic able benefits, and represents savings in fossil fuels
aspects. We often talk about these as the three pil- (Fujii et al. 2012). In the process of changing over
lars of sustainability. These three pillars can be to a circular economy in Central Europe (but also
applied to formulate the requirements and needs in other emerging economies), increasing the recy-
in practice, and within economies to introduce cling of plastics is particularly needed. The use of

306
plastics increases, but the efficiency of their recy- components, especially regarding research, devel-
cling lags. At the current time we recycle less than opment, and innovation). An important tool in the
25% of the collected plastic waste, and about 50% implementation of a circular economy, in terms of
ends up in landfills. waste and secondary raw materials, is the cascad-
However, supporting the use of wastes con- ing use of resources; that is first the systematic use
tained in materials such as paper and plastics can of all those materials for products with a higher
have its unwanted effects. Sorting out those waste added value, and then using them repeatedly as a
components that have considerable calorific val- source for other product categories. This is linked
ues (paper, plastics) reduces the energy yield from to a rigorous adherence to a waste management
waste incinerators; therefore, reducing their envi- hierarchy that will ensure the limiting of waste
ronmental benefit. Reduction of the calorific value production and maximum use of the wastes pro-
of the incinerated waste also has technical implica- duced. If we cannot avoid the generation of waste
tions. The combustion technology of incinerators or recycle it, in most cases it is more appropriate
are usually optimized for a certain specific calorific both environmentally and economically to use its
value of the fuel. Reduced fuel efficiency conse- energy than the choice of landfilling. Recovering
quently leads to a deterioration of the combus- the energy from waste can therefore find its place,
tion process, and also usually to higher amounts and create synergies with the energy and climate
of undesirable emissions. Implementation of a policies; however, it will always be necessary to
circular economy will therefore have a significant remember the waste management hierarchy.
impact on those entities engaged in waste manage- One of the most significant environmental rea-
ment. Reducing the amount of waste produced sons for introducing the circular economy is the
should be implemented in the prevention phase, issue of climate change and enhancing the green-
not just in their subsequent transformation into house effect of the atmosphere. A significant shift
secondary materials. The biggest obstacle to the in the global perception of the issue of limiting
development of a circular economy consists in the CO2 release and reducing fossil fuel combustion
limited ability of Central European industry to has occurred in recent years, and especially after
reuse materials from end-of-life products, packag- the COP21 Paris Summit at the end of 2015. The
ing, etc. The current practice of exporting useful environmental reasons for measures to reduce
raw materials outside of the European Union is greenhouse gas emissions had already long been
unacceptable from the perspective of the Central held by the scientific community. Yet, efforts
European economy. Current waste management is thus far to reduce the consumption of fossil fuels
not recycling, but only separating, and at dispro- for energy and fuel purposes have not yet come
portionately high costs. The waste management to the daily agendas of industrial enterprises in
hierarchy should be transformed so that it is not Central Europe. The causes for this behavior
a dogma, but recommendations to: 1) reduce the are related more to social and economic aspects.
amount of waste; 2) and where the waste arises, it Therefore, we will focus on them in the following
is used in the domestic economy; 3) gradually pro- paragraphs.
hibit the landfilling of waste of particular mate-
rials, according to how the structure of the waste
utilization shall be built. On a global perspective, 4 SOCIAL ISSUES
in many countries, landfilling is seen as a better
option (for example in Brazil). Is it more economi- For the purposes of this article, we chose among
cal to recycle, incinerate, or landfill? A very impor- the social aspects those that are related to the per-
tant aspect that needs to be considered is the level ception of this issue by the general public, espe-
that the material is recyclable (incl. disassembly), cially the interested parties. In order to raise public
and also increasing the content of recycled mate- awareness about the concept of a circular economy
rials into new products. Increased support of the there should be an emphasis on environmentally-
raw materials markets from the recycling industry oriented marketing and communication with the
is needed, as well as an increased rate of reused public. It is important that the public accepts the
and recycled municipal wastes. The question “what idea of a circular economy as its own issue, and
is more economical?” can be always answered with perceives it as a natural part of their lifestyle. In the
it being most economical to limit waste generation. Central European region, the new environmental
And if this occurs, it is economical to use it in a requirements and regulations are often perceived
closed cycle; however, in a manner that in terms as unnecessary and burdensome by the public, and
of economic development makes economic sense. therefore also by the policy-makers and industrial
In its individual components it works in the long- managers. The reasons for this attitude are skep-
term without subsidies (although at the beginning ticism, economic priorities, and ignorance of the
there may be some subsidies to support certain problem.

307
Besides the development of educational pro- system of government and state governance, based
grams in this area, it is necessary to develop a on democratic principles and a liberal market is
credible system of environmental labeling of prod- an important condition for the establishment of a
ucts, inclusive of Type I (ISO 14024), Type II (ISO circular economy. New legislation related to a cir-
14021-3), and Type III (ISO 14025). The general cular economy should be limited to establishing a
public, interested in these issues in the context of minimum legal framework for ensuring a competi-
the environment, tend to be susceptible to false tive environment and the most efficient use of raw
“green” advertising (greenwashing), and may thus materials.
be discouraged from active involvement in the A circular economy will impact all economic
development of a circular economy. It is necessary activities, particularly industrial production, con-
to cultivate and develop communication between struction, agriculture, as well as social, educa-
consumers and producers. In different regions of tional, and environmental areas. Undoubtedly, a
the world, various labels for recyclability are used, part of this process will also be sensible changes
sometimes in combination with identifications of within the framework of directives and regulations
the materials. This confuses consumers and also of individual countries. It will also lead to amend-
raises their suspicion. It would be helpful to create ments to legislation that will have to implement the
a unified international system of eco-labeling and relevant regulations.
environmental declarations. An extreme factor, which in principle blocks
Public distrust in the correct solutions to envi- development of a circular economy within a coun-
ronmental problems is another obstacle in the try, would be a state of war. Conventional methods
implementation of putting the circular economy of warfare are demanding on raw materials, and
into practice. In countries soon after a change in immediate priorities are given precedence; ques-
the economy, or in countries where insufficient tions about the quality of the environment become
freedom and transparency in business has devel- greatly lowered in importance. On the other hand,
oped, it is difficult to implement the principles of every conventional warfare is defined by the
a circular economy from above. An important pre- availability of key raw materials and resources.
requisite for the realization of a circular economy is Resources and raw materials are actually often the
an increased interest and trust of the general public cause of war. For this reason, it would be very use-
in possible solutions, and especially its assurance ful to understand the implementation of the circu-
that it will not compromise the quality or level of lar economy as a peacemaking tool. Nevertheless,
their lives. On the contrary, we should explain to one can reasonably see that political opponents
the general public that while the circular economy of states participating in the implementation of a
might bring about substantial changes in the stere- circular economy may perceive these efforts as an
otypes about energy and raw materials manage- instrument for escalating the mutual conflict. This
ment, it also brings with it increased societal living danger could be prevented from the beginning with
standards. Grant incentives and structural support introduction of a circular economy, and this issue
is sometimes not systematic, and undermines the sufficiently communicated worldwide.
natural flow of funds; therefore, also of the materi-
als and energy. For instance, the subsidy policies
for agricultural production in different countries 5 ECONOMIC ISSUES
is confusing, leading to uneven competition as
well as weakening the motivations to implement The economy wants to grow. Very often we hear that
meaningful measures or projects. Healthy levels of this or that measure, for example, aimed at protect-
regulation, strengthening of market principles and ing the environment “makes no economic sense.”
competitiveness, as well as putting emphasis on the A myopic economic view often does not cover the
responsibility of manufacturers should always be issue of externalities, or the Central European area
considered. lacks a sufficiently elaborated system for evaluat-
Another fairly critical point in implementa- ing the environment. By including these aspects in
tion of a circular economy often is the short-term the economic balance sheet, the circular economy
political vision of politicians who are involved in could begin to pay off even from an economic point
government and the drafting of laws. Especially of view; however, it need not necessarily be so in an
in countries that still search for a stable political manageable time. What needs to be changed in the
culture, whether because they are still developing interrelationship between economics and environ-
it, or in the preceding decades it was disrupted ment is the viewpoint of the superiority of these
(i.e., by a state of war or dictatorship), the policies systems. We should not ask whether this or that
adopted are usually short-term solutions within environmental action makes sense, but if it is nec-
the scope of the politician’s immediate political, essary to set the rules of the economy so as to pro-
economic, or power needs. A stable democratic mote an environmentally friendly economy, with a

308
circular one. The economics cannot be a measure not actually allow for adequate development of
of the acceptability for individual measures in any a circular economy, competing technologies, and
future environmentally-oriented economy, but it with the related creation of new jobs. Landfilling
must be a tool that allows us to achieve the desired is the cheapest way to eliminate waste, but it is a
goals. Economics alone cannot be the goal. This permanent loss of all usable materials from the
is a fairly well-accepted fact on a theoretical level, waste. Another strategic issue that should be tack-
but unfortunately the real Central European prac- led is the status of energy recovery in the circular
tice puts the economy, especially the short term economy. This method of waste recovery allows
economy, above most other criteria. In practice, for for savings of primary energy resources, techno-
the development of a circular economy, a sufficient logical progress, and innovation (as opposed to the
number of success-stories will be important; exam- landfill), as well as a strengthening of a countries
ples worthy of imitation, which would motivate energy security.
other stakeholders. Further, it is necessary to the An example of materials representing a large
dispel fears of the industrial sector that implemen- volume and weight flow within the waste man-
tation of a circular economy might reduce their agement sector are demolition wastes containing
competitiveness. concrete (Huuhka et al. 2015). The main constitu-
As a measure of an economy’s success, the GDP ents of the concrete waste are materials which can
is usually used (Leimbach et al.) at the state level, be converted into reusable aggregate for concrete
or profit (Meltzer & Richard 2015) at the level of production via suitable process (Morel et al. 2001).
organizations or individuals. It is expected that This results in a saving of a primary raw material—
GDP and profits will continue to grow. This is in natural gravel. The disadvantage of this procedure
fundamental conflict with the concept of a circular is its current low economic profitability. In many
economy. Economy, GDP, and profit cannot grow cases, primary aggregates are available on the mar-
indefinitely in a closed environmental (planetary) ket at very low prices; therefore, it is not sufficiently
and economic (world market) space (Bardi 2015; economically interesting to pursue. The reason is
Beaudreau & Lightfoot 2015). It is necessary to not only due to the low price of aggregates, but also
understand that political leadership at the level of the low price of landfilling in the case of concrete
national governments is absolutely crucial here. and demolition wastes. The environmental benefits
Politicians must understand that a circular econ- of the use of recycled aggregates are also not very
omy is an opportunity for the future. In the com- high, reaching values of 10%. Construction and
ing years, the generators of growth may change demolition activities generate the greatest amounts
in sector levels, thus it is necessary to look ahead. of waste in Europe. Annually, a ton of construc-
Implementation of a circular economy will require tion and demolition waste per capita is produced;
significant changes in the economy. It is important throughout the EU, this comes to 500 million tons
that national governments have the courage to per year. This waste is not usually sorted, and thus
enter into this long-term process and to deal with the valuable materials are not extracted. In this sec-
it, not only via pragmatic or cosmetic solutions tor the waste management of a circular economy
that are not too painful. could bring about significantly better results.
The price of human labor is significantly higher Developing a circular economy will therefore
than the cost of materials. This did not apply in largely depend on the adjustment of the economic
earlier economic systems, and thus it stimulated a prices of primary and secondary raw materials. The
greater degree of material recycling. In developed utilization of secondary raw materials still only
countries, the current cost of labor is relatively makes up a small share in the EU and other coun-
high, and thus the raw material costs are relatively tries. Their expansion in the economy is prevented
lower. The price of primary raw materials thus by fairly substantial obstacles such as uncertainty
does not produce sufficient pressure on material regarding their composition and their technical
recycling. Nevertheless, human labor is not yet characteristics. The mere fact that a product is
included in the comprehensive tool chest for envi- made from recycled materials is not attractive to
ronmental cost evaluations (Kamp, Morandi & many customers. The most important aspects are
Østergård 2016). the quality and price.
Waste management is often very cheap in less Although the concept of a circular economy
developed countries. In well developed econo- cannot only be narrowed down to the issue of recy-
mies, which have decided to reduce landfill waste, cling, recycling is currently the main instrument,
the high cost of landfilling results in the creation and still the biggest technological challenge right
of space for other waste management technolo- now. To increase the efficiency of recycling of both
gies (technologies from higher levels of the waste materials and energy, it is necessary to include life-
hierarchy—prevention, recycling, energy recovery cycle thinking into the design phase. This can sig-
from wastes). The low price for landfilling does nificantly reduce the amount of necessarily recycled

309
flows. Nevertheless, in many cases, recycling is per- also applies when comparing waste management
ceived as unprofitable in Central Europe. Second- plans within individual states. There are even some
ary materials often have difficulty finding outlets. counties or federal states within a single state that
The low cost of primary raw materials makes recy- register wastes in different ways.
cling a relatively small share of the market. Does Many countries with emerging economies lack
it pay to recycle from an economic point of view? sufficient qualified personnel who have sufficient
In the current situation, economic markets do not knowledge of both the technical and environmen-
experience a major shortfall of most raw materials, tal sciences. The educational sector’s intercon-
although there is information on the likelihood of nection between business and environment could
coming shortages of raw materials such as: crude become the foundation for this; however, it is often
oil (Ebrahimi & Cheshme Ghasabani 2015), phos- overlooked.
phorus (Ulrich & Frossard 2014), and rare metals Although we have so far focused more on the
(Frenzel, Tolosana-Delgado & Gutzmer 2015). So end-of-life stage of lifecycles and waste issues, it
far, they are available, and even thought they are is clear that further development of the circular
perceived by some stakeholders as a cause for some economy will need to focus on issues of design and
alarm, they are not perceived this way by industries drafting proposals. Support for ecodesign tools
in Central Europe at the current time. Of course, will be especially needed, also through legislation.
this may change, not only with depletion of the Ecodesign is currently not understood in the same
raw materials, but also due to their non-availability way in different countries, which is also reflected in
on the market, which can be caused by any one of their varied legislation. Unless ecodesign is applied
several relatively rapid and unexpected political uniformly in different countries, it could happen
developments. that certain solutions from one country will not be
From an economic perspective, the development accepted as ecodesign in another country. A uni-
of a circular economy will support the introduction fied market of easy wheelchair access is also a nec-
of new, resource-efficient business models based essary condition for promotion of the repairability
on leasing and sharing the means of production of products.
and products, which will mean sales and mainte- When determining support tools for the intro-
nance services instead of the selling of the prod- duction of a circular economy, it would be better to
uct itself. Leasing creates a stable revenue flow for promote the “soft” tools versus binding targets as
companies, encouraging businesses and consumers it is a entire societal process. A prescriptive legisla-
to reduce resource utilization, and to maintain a tive approach would cause an undesirable “loss of
good quality product. momentum” of this social process, because it would
pre-define the actors, as well as what exactly needs
to be achieved without having the necessary eco-
6 PRACTICAL ASPECTS OF nomic data available today. The measures adopted
INTRODUCING THE CIRCULAR must also respect the different starting positions
ECONOMY INTO NATIONAL AND of different countries and manufacturers, yet also
INTERNATIONAL ECONOMIES must not be discriminatory in this regard. Creating
a functional circular economy is a systemic change
A circular economy requires cooperation and col- in value chains and a significant development of
laboration at the international level. Therefore, innovations—both technological and social in their
the condition of internationalizing the solution nature. An analysis of the impacts on individual
is a common approach, in particular in legisla- member states that would take into account their
tion and the methods of collecting and recording specific economic structures should be prepared
environmental, industrial, and economic data. If before setting any goals (incl. non-binding ones).
material flows are recorded differently in different However, it is essential that the proposed specific
countries (such as the characterization of waste), activities and possible legislative changes, includ-
then it will not be possible to uniformly evaluate ing the requirements for reporting, are analyzed in
the circular economy. For example, in the EU, detail in order to not increase the administrative
there is no relevant data for waste management. and financial burdens on businesses. New activities
Each country has its own way of reporting and and proposals should be primarily directed towards
statistics. It is necessary to unify the methodol- improving the competitiveness of European indus-
ogy in the EU, otherwise we will be comparing try, reducing dependence on primary raw materi-
“apples with oranges.” In Germany, in contrast to als, and improving the use of waste as a source of
the Czech Republic, the municipal waste statistics raw materials.
also include retail outlets, including supermar- To monitor the main steps in the transition to a
kets. As a result, Germany has a higher recycling circular economy, we will need to propose a sim-
rate than the Czech Republic. A similar problem ple and efficient framework. This should include

310
indicators for areas such as the security of the sup- raw materials, in terms of their characteristics, are
plies of key raw materials, repair and reuse, waste comparable with the primary raw materials. This
production, waste management, trading in second- may also be helped by advanced product design,
ary raw materials, and the use of recycled materials which takes into account environmental aspects,
in production. It would also be useful to establish while choosing the materials as well as in devel-
a common methodology for measuring the volume oping those components of designed products
of food waste and the establishment of appropri- that will be easier to repair and reuse. An integral
ate indicators. part of a circular economy’s implementation into
practice will be the systematic promotion of waste
prevention. This, however, must come primarily
7 CONCLUSIONS from manufacturers and designers. The individu-
als dealing with waste management are unlikely
If we consider the current economic activities in to rigorously implement these efforts to the extent
terms of the characteristics of a circular economy, needed, since waste management is their source
we can conclude that the current economic policy of income.
in many countries is not yet directed towards a cir- Implementation of a circular economy is also
cular economy. Setting goals, processes, and tools impossible without setting up an economic envi-
totally depends on setting a strategy for the tran- ronment in which the circular systems of the vol-
sition to a circular economy. Strategic documents umes of materials and energy are economically
for different areas are prepared, but are not specifi- advantageous. This will probably require develop-
cally directed towards the realization of a circular ment of an environmental system of taxation and
economy. There is a fundamental need to focus evaluations of the environment, including quanti-
on areas such as business conditions in individual fication of the actual costs associated with inclu-
countries, economic reporting, patterns of con- sions of externalities. Without this step, striving
sumption, consumer habits, waste management, to enhance the cyclicity of the linear economy will
and other related areas; such as to the innovation be inefficient, and will lead to the development of
of new products and services which are resource new technologies, whose particular benefits within
efficient, with support for the demand for these once monitored parameters (such as the removal
products, tax systems, education and awareness via of CO2 from the flue gases of power plants) will
so-called “soft” instruments. be outweighed by unintended consequences in
A circular economy represents a concept of a other industries or in other environmental com-
contemporary economic approach of humanity partments. Besides taking into account exter-
to materials and energy which is approximating a nalities, it is necessary for the development of the
natural manner, where the outputs from one proc- circulatory economy to change one important fac-
ess become inputs into the next process. In human tor. This factor is the requirement of continuous
history the management of energy and materials economic growth. The current economic model
were closely associated with natural cycles, and assumes alternating periods of economic stagna-
this concept was long a common practice. Today, tion and periods of economic growth; however, it
when the planet is inhabited by a population more is assumed that the fluctuations are around a con-
than 50% situated in urban areas, the effort to stantly improving performance of the economy. As
return to a circular economy becomes a big chal- long as the performance of the economy is based
lenge. Increases in human population becomes an on consumption of materials and energy, the con-
important factor influencing the demand for raw cept of a circular economy is not viable. Unless all
materials as well as the amounts of waste emis- interested stakeholders have demonstrable answers
sions released. The transition from the current to the issues outlined above, it will not be easy to
linear economy to a circular economy will not implement this very necessary concept from a sus-
only need changes in technological procedures, tainable point of view.
but also in consumer behaviors and customer-
supplier relationships. A circular economy is not
replacing waste management by its recycling. If ACKNOWLEDGMENT
the development of new recycling technologies
are without interconnections to the design of This experimental work was carried out with the
products, then their production and use will not financial support of Norwegian Grant (Project Nr.
lead to significant benefits in terms of savings in NF-CZ08-OV-1–005–2015 “Research of high tem-
raw materials and energy. Recycling is in principle perature CO2 sorption from flue gas using carbon-
desirable and necessary; however, recycling tech- ate loop”). Author is not in any sources conflict of
nologies should not be too demanding on energy interest that might be perceived as influencing an
or materials. It is also necessary that the secondary author’s objectivity.

311
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Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Modern ecological—economic status and sanitary conditions


in Vietnam

V.H.P. Nguyen
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

V.I. Chernusov
Ecological Faculty, Peoples’ Friendship University of Russia, Moscow, Russia

ABSTRACT: Environmental impact assessment according to traditional methods is evaluated through


the variation of soil, water, air and ecosystems. Such monitoring activities require a lot of time and oper-
ating costs. In contrast, when using indirect method like demographic assessment and evaluation, such
costs can be reduced. This method uses demographic data systems such as population density, urbaniza-
tion factors, birth rate, death rate, and incidence of occupational diseases, etc. The demographic data
system has close linkage altogether in an information system of a given area. In this paper, we calculated
the demographic factor, namely Demographic Tension Index (DTI), for Vietnam from 1995 to 2011. The
results show that the Vietnam’s DTI increased from 1.803 to 3.262, which means the environmental state
of Vietnam from 1995 to 2011 are declining rapidly and can tend to become more polluted in the coming
years. This demographic assessment method has been applied within Russian Federation, Ukraine, and
Belarus, etc., so its scientific influence is not widespread. Moreover, the required data for the DTI calcula-
tion should be accurate and reliable.

Keywords: industrialization, environmental pollution, environmental impact assessment, demographic


tension index

1 INTRODUCTION the environment through an indirect method based


on the demographic evaluation.
The use of outdated technologies in industrial pro- The demographic assessment method is built
duction is the core pollution source affecting the based on the comparison and evaluation of the
state of the environment and especially on human environmental situation and the impact of human
health. Moreover, the wasteful use of natural on the environment. In which, a synthesized
resources also caused the rapid deterioration of assessment is conducted from the following ele-
the environment. ments: number of population, industrial produc-
As a result, this paper aims to assess the envi- tion capacity, ecosystems and human impacts, etc.
ronmental impact in Vietnam from 1995 to 2011 These elements are independent but closely
and identify the environmental deterioration by linked to each other. For example, the perform-
the following main reasons: ance of technology affects directly or indirectly
to human health and the environment, while the
− The strong adverse impact from all economic
cost of ensuring safety depends on the number and
sectors;
production capacity of the human, etc. So these
− The influence of industrialization and urbanization.
elements are in the same information field and
allows us to assess the state of the environment in
2 LITERATURE REVIEW the same territory.
The performance of these indices is not only
Currently, the environmental impact assessment used to assess but also to develop the environmen-
in the area, the city and country in the world is tal policy orientation.
often measured by traditional methods, through Researches on demographic assessment method
the environmental assessment of soil, water and were conducted and applied within some coun-
air. Meanwhile, this paper does not follow those tries such as the Russian Federation, Ukraine,
traditional methods, rather than assess the state of Belarus, etc. and has not been well-known in the

313
international science community. Thus, reviewing utilities; ρ—Population density, people/km2;
those studies and applying them to a new area for Z—the total annual incidence of the popula-
environmental impact assessment is essentially tion (1000); P—fertility (1000); C—total mortal-
needed, so that we can collate and compare with ity (1000); Cd—infant mortality rate (per 1,000);
other traditional methods that are currently used v = 10−4 the scale factor at which the DTI = 1.
in most of countries in the world. (Akimova 1994; Akimova and Khaskin 2000;
This method has been practically tested in the Chernuk et al. 2013).
study of DTI in different territories of Russia and
recommended by the Ministry of Justice of Russia − Population density is the average population
for forensic examination (Akimova 1994; Akimova changes in each particular year from 1995 to
and Khaskin 2000; Chernuk et al. 2013). 2011;
− Coefficient of urbanization is urban expansion
coefficient, which is the level of urbanization of
the territory is calculated by percentage.
3 METHODOLOGY

The expression through population density and 4 RESULTS AND DISCUSSION


human health in a given area is expressed through
the coefficient having important value in assessing Through the demographic assessment method, we
the state of the environment. The value (ratio) is determined the environmental status of Vietnam
selected according to the statistical methods and from 1995 to 2011, which is worsening indicated by
experience of professionals to make the compari- the increasing of the DTI coefficient (from 1.803
son of the demographic characteristics and the to 3.206). It means that the environmental pollu-
incidence of occupational diseases in a given area. tion is 1.803 to 3.206 times over the standard and
Thus, the quantitative assessment of these criteria tend to increase in the coming years by the main
is called coefficient on demographics (Demographic causal aforementioned above.
Tension Index-DTI). In this study, we used morbidity data from the
This method reflects the integrated assess- annual health reports and other statistics from
ment taking into account not only the impact of the Ministry of Health, Ministry of Statistics and
demographic and tension due to the degree of General statistics office ([Link]).
urbanization of the territory, but also allows us to Figure 1 shows the change of demographic
comprehensively analyze the specific indicators, tension in Vietnam for more than 15 years (from
such as the degree of urbanization of the territory; 1995 to 2011). In 1995, Vietnam’s DTI exceeded
population density; the total annual incidence of the regulatory permissible value about 1.803 times,
the population; fertility; as well as the annual pop- and increased to 2.644 times in 1999, 2.809 times
ulation and infant mortality rate. These parameters in 2002, 3.017 in 2005, 3.169 times in 2009, and
are evaluated in order to provide a comprehensive 3.262 times in 2011. These changes were caused
assessment for the environment condition of the by the urbanization process as well as the slight
studied areas. increase in fertility, reduction in mortality, herit-
In this study, we collected data from economic age, exceeded to an increase in population.
and social development reports as well as the eco- The results show that, in Vietnam there was
logical status of the country from 1995 to 2011. an observable adverse trends in the health of the
These data was analyzed in order to check the con- population that related to the social, economic,
sistency of the information. ecological status of the country that can be
Index demographic tension (DTI) represents regarded as the actual personal distress.
the integral feature of the complex environmental
impacts on human population. DTI calculation
takes into account the population and child mor-
tality, fertility, morbidity, population density, and
urbanization territory.
The actual value of the DTI for a particular area
is calculated using the formula:

T Y lg ρ ( ,1Z
DTI 2 P + C ) Cd2v

Y—the degree of urbanization of the territory:


the proportion of land area (from 0 to 1), includ-
ing busy urban buildings, industrial facilities and Figure 1. Dynamics of changes in DTI.

314
Calculations show that DTI Vietnam from 1995 Vietnam; Friedland 1964; Vietnam Problem of
to 2011 exceeded the permissible value DTI stand- Environmental Pollution).
ard in 1.803 times–3.262 times and show worsen- Comparison of natural and socio-economic fac-
ing environmental situation from 1995 to 2011. tors in the formation of the ecological situation
Over the past 15 years on the territory of the shows that the most serious adverse changes in
Republic of Vietnam have been significant nega- natural systems occur under the influence of man.
tive changes in the parameters of fertility and mor- Water resources: The main sources of pollu-
tality. And the negative effects not only affect the tion of the hydrosphere in Vietnam are the fol-
demographic situation but also indirectly affect the lowing activities: Flow regulation, the creation
deterioration of the environment in Vietnam and of reservoirs and irrigation facilities, water use in
tend to become worse in the coming years. the forestry, agriculture, and municipal and indus-
trial production, urbanization (Le 1984; Nguyen
1994).
4.1 Demographic and environmental status of
Land resources: About 50% of the total land area
Vietnam in 1995–2011
of the country (of which 3.2 million ha is located in
In the 1995–2011 periods, the demographic situ- the plains and coastal zones, and 13 million ha in
ation in Vietnam has rapidly changed. Birth rate mountainous areas). Since 1986, Vietnam’s econ-
increased slightly from 18, 600 people in 1995 to 20, omy and its foreign trade turnover grew steadily
100 people in 2011. Meanwhile, mortality increased mainly due to the increase in imports. Besides, the
from 5, 900 people in 1995 to 6, 900 people in 2011. main export items are mineral raw materials and
The number of patients has increased at especially products of tropical agriculture (Nguyen 1994;
high occupational diseases (from 815, 000 in 1995 Nguyen and Nguyen 1998; Nguyen 1987).
to 1, 125 thousand in 2011). Labor force migration For soils of Vietnam characters following envi-
from rural to urban areas grow rapidly, largely con- ronmental problems: leaching, erosion of river-
centrated in the industrial zone. banks and coastlines and loss of soil productivity.
And most of them are lacking of work safety Soil degradation is greatly increased both the speed
conditions that caused the occupational disease and the scale, mainly due to economic factors
rate increased rapidly. The labor migration to the (Friedland 1964).
urban areas with many industrial parks in order to Anthropogenic changes in natural systems: The
satisfy the needs of the people but it leads to rapid document allows the comparison on the formation
population growth and tend to lose the control on of the ecosystem, the environment in Vietnam was
employment and population. created in 2010 (Vietnam Problem of Environmen-
The decline of the environmental situation tal Pollution).
of the country in the past decades have seen the Land degradation: Violation of the soil for vari-
disease in the population growth of Vietnam ous reasons: leaching, erosion, degradation, fertil-
(50%–cardiovascular diseases, 25%–lung disease, ity reduction, salinization, acidification, drought,
25%–of infectious diseases). (General Statistics desertification, floods, etc. (Nguyen 1994; Nguyen
Office of Vietnam). and Nguyen 1998; Nguyen 1987).
Forest degradation: In 1943, Vietnam had about
14.3 million ha forest (43% of the total area of
4.2 Ecological and environmental status of
the country). By 2010, the total forest land area
Vietnam
decreased to 9.6 million ha (28.8% of the total area
This section summarizes the environmental per- of the country). (Le 1984; Nguyen 1994).
formance of Vietnam since 1995 and analyzes the Water pollution. Inland waters: rapid urbaniza-
anthropogenic impact on the environment over the tion and industrialization have led to a growing
past decade. demand for water use. However, water supply is
Status of the atmosphere: In many cities, the not complete, will create competition among con-
atmosphere is polluted by wastes from main indus- sumers and its mining operations. Moreover, water
tries, including cement, paper, leather, textile, pollution, and reduce the supply of water (Nguyen
chemical and food processing. The air in big cities 1994).
like HCMC, Hanoi, Haiphong, and Danang is Air pollution. Dust: Most urban areas in
most polluted. Vietnam are polluted by dust, and some of them
The main transport modes in Vietnam are are contaminated to a catastrophic degree. Average
motorcycle and car, which are major sources of air dust concentration often 1.3—2 times higher than
pollution. As every year the number of cars and the allowable limit. SO2, NO2, CO contamination
motorcycles is growing rapidly, there is increas- in most urban centers (Le 1984; Nguyen 1994).
ing consequence caused by the harmful emis- Lead (Pb) pollution: lead contamination was
sions from transport (General Statistics Office of found on the streets, but the concentration of lead

315
in the big crossroads close to the maximum value and tends to rise more rapidly in the coming years.
of the permissible limit (0.005 mg/m3). (Vietnam The use of indirect methods, demographic assess-
Problem of Environmental Pollution; Nguyen ment, method, is expected to be a representative
1994). index for evaluating the unsafe change of the envi-
Compared with 1995 and 2011, the value of ronment in Vietnam.
DTI increased. It is possible that this is due to the From 1995 to 2011, the demographic assess-
fact that considerably worsened the environmental ment methods have shown that there is a tendency
stops in Vietnam and the increased burden on the to be detrimental to the human health due to eco-
population trend. nomic development and the general degradation
The application of demographic assessment of the environment. This can be regarded as the
method may face some common limitations as real problem consequence of that urbanization
followed: and industrialization can bring cause to developing
countries.
− The use of large amounts of data requiring
At the same time, we should pay special atten-
statistical data and accurately cite sources and
tion to the quality of the natural environment of
reputation such as: data from environmental sta-
Vietnam in the future, since the intensive economic
tus reports and annual national health data the
development and population growth can interact to
General statistics Office, data from the Ministry
cause critical adverse changes to the environment.
of Health, etc.
In this paper, the calculation of DTI coefficient
has not included the effect of labor migration from REFERENCES
region to region, which can alters the coefficients
such as population density, and the number of Akimova, T.A. 1994. Comparative analysis and evaluation
occupational diseases (for example, a person got of the ecological state of the Moscow region, Moscow.
sick from working in one region but then moved to Akimova, T.A., Khaskin, V.V. 2000. Ecology. Human—
the other region). Some occupational diseases that Economy—Biota—Ecology. Textbook for High Schools,
Moscow: UNITY—DANA.
have affected over a long process or take a number Chernuk, N.A., Zykov, V.N., Chernyshov, V.I. 2013. Envi-
of time to appear. Thus, such diseases may not ronmental certification of natural and economic areas.
appear immediately outside, thereby determining A textbook for the forensic examination of the envi-
the number of people infected during the migration ronment, Moscow: People’s Friendship University.
will also make changes to the DTI coefficients. Friedland, V.M. 1964. Pochvy and weathering crust humid
tropics (in the example of North Vietnam). Moscow:
The science.
5 CONCLUSIONS General Statistics Office of Vietnam. URL: [Link]
[Link]/
Le, D.D. 1984. Geomorphology Vietnam. Doctoral
A change in the economic system that changed the dissertation, Moscow.
face of the country is represented with many plants, Nguyen, K.V. 1994. Bio Climate Vietnam. Moscow.
factories, buildings and industrial parks springing Nguyen, D.N., Nguyen, T.H. 1988. Vietnam Climate
up. The rate of urbanization rose abruptly replaced Resources. Science and Technology Publishing House,
the agricultural rate. Besides, these changes are still Hanoi.
negatively affecting the habitats and ecosystems. Nguyen, Q.M. 1987. The Erosion of the Soil of Vietnam.
The average concentration of CO2, SO2, CO, NO2 Doctoral dissertation, Moscow.
etc. in major cities increased rapidly and exceeded Vietnam Problem of Environmental Pollution. URL:
the national standard. [Link] 10278. html
The direct and indirect causes negatively effects
on the environment in Vietnam from 1995 to 2011

316
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

An overview of forest transition and its environmental impacts


in Vietnam

V.V. Nguyen
Faculty of Agriculture and Forestry, Vietnam National University of Forestry—Second Campus, Ho Chi Minh
City, Vietnam

T.T.T. Phan
Faculty of Forest Resources and Environment Management, Vietnam National University of Forestry—Second
Campus, Ho Chi Minh City, Vietnam

N.B.D. Thi
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: This study reviewed the driving forces of forest change in Vietnam from 1945 to 2014. The
current covering rates of forest in each region are also reviewed. The relationship between coving rate of
forest and biodiversity conservation revealed that forest area are increasing unequal with the forest quality
which resulted in the loss of many species in Vietnam Red List of threatened species. Besides, the negative
impacts caused by the loss of forest and climate change issue were also discussed. The related forestry
policies were reviewed to help Vietnamese Government strengthens capacity to respond to climate change
impacts. Finally, some appropriate suggestions were recommended in order to help strengthening forest
protection activities.

Keywords: biodiversity conservation, climate change, deforestation, forest, reforestation, rehabilitation

1 INTRODUCTION • Over-exploitation of non-timber forest products


• Pollution
Forests not only plays an important role in • Infrastructure development without proper
Vietnamese economic, and also provides many eco- impact avoidance or mitigation measures
logical benefits, such as climate change prevention, • Weak protected area management
biodiversity conservation, maintaining soil stability • Weak enforcement of existing legislation.
and quality, limiting floods, droughts, soil erosion
prevention, which mitigates many of natural disas-
ters. However, in recent decade, the covering rate of 2 STATUS OF VIETNAM’S FOREST AREA
Vietnamese forests has been decreased crittically;
especially the quality and quantity of natural for- This study reviews a various data of Vietnam’s for-
ests have been decreased. That led to major threats est area from 1945 to 2014. That helps to figure
of climate change and increasing natural disasters. out the status of Vietnam’s forest area by time.
In 2013, forests are estimated to cover about Figure 1 presents the Vietnam’s forest area by
13.8 million ha of Vietnam’s land surface, among years, which shows that in the period 1945 to 1995,
these areas, natural forests account for approxi- the total forests areas were decrease critically, while
mately 10.2 million ha (74%), planted forests the natural forests areas decreased, the planted for-
accounts for another 3.5 million ha (35%), and est areas gradually increased. When the total forest
the primary forests are estimated to represent only area reached the lowest value in 1990, the Govern-
0.08 million ha (1%) (Joao et al. 2013). There are ment had to decide to close the natural forest for
some main drivers causing the loss of Vietnamese conservation by issuing Directive 90/CT in 1992.
forest and biodiversity include (Joao et al. 2013): Besides, the Government started the program 327
of reforestation in the same year 1992. As results,
• Land-use change since 1990, the total forest areas began to increase,
• Illegal trade in wildlife especially with the development of restoration
• Illegal logging forests and bamboo forests. However, from 2010 to

317
Issues
Issues
Issues
Issues
Issues

Helping Children Face Tough Issues


Figure 1. Covering rate and forest area in Vietnam from 1945 to 2014. [2].

Children
Issues
Issues Issues

Issues

Issues

Issues Issues Issues Issues Issues


Issues
Figure 2. Sharing percentage of forests’s covering rate by regions in 2014.

2014, natural forests did not keep increasing rap- human and insect) and the expansion of agricultural
idly but the opposite tends to decrease. The reasons land from forest land (land-use change) (Bernard
are results of the conversion of land use purposes, and De Koninck 1996). Table 1 presents the change
changing natural forest into planted forest, which in forest areas of Vietnam from 2002 to 2013.
mainly focused on rubber plantations. The above results show that the reasons of increas-
Figure 2 shows the covering rate of forests in the ing forest area in the period 2002–2013 include reforest-
five largest region of Vietnam in 2014, including ation, rehabilitation, and other causes, which is mainly
Northern midland and mountainous, Central Coast, reported about 56.6%, 30,6%, and 12.7%, respectively.
Central Highlands, Southeast, and Mekong River The total forest area increased the highest in 2012,
Delta. Among all regions, Mekong River Delta has this year is also recorded the highest increase of total
the lowest forests’s covering rate (5.9%). As results, rehabilitation forest area. The major causes of forest
there are many places in Mekong Delta are facing area reduction during the period 2002–2013 includes
with negative impacts to adapt the climate change. exploitation, forest fires, insect-caused deterioration,
deforestation, and land-use change. Two main rea-
sons of deforestation in this period are forest exploita-
3 DRIVERS OF FOREST DEGRADATION tion and changing land-use change purposes, which
IN VIETNAM account for 41.2% and 35.3% of total, respectively. The
rests are other reasons (16.3%), deforestation (5.5%),
There are many reasons causing the direct loss of fire (1.7%) and insect-caused deterioration (0.1%). Up
forests, including changed land-use purpose from to now, Vietnam still has to face with the illegal forest
natural forest to cultivated land, and especially the use exploitation and illegal trade in wildlife causing a huge
of chemical weapons by the US military during the decreasing of total current forest resources. Therefore,
Vietnam war (before 1975) and forest fires, but these it is demonstrated that Vietnam needs to clarify the
direct reasons did not cause much damages in com- environmental law enforcement to strengthen conser-
pare with the forest exploitation, deforestation (by vation activities through the country.

318
Table 1. The change in forest areas of Vietnam in period 2002–2013.

2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013Totalgain Totalloss

Total changed
562.938 221.125 316.538 266.322 46.507 -14.952 133.913 519.240 388.611 380.969 1.040.940 277.230 7.194.805 -3.055.420
forestarea

Deforestation -75.545 -5.799 -3.699 -10.636 -13.839 -2.145 -3.833 -10.378 -11.826 -20.109 -6.510 -3.613 0 -167.932

Land-use
-76.292 -74.235 -36.374 -76.227 -88.973 -119.566 -67.038 -115.908 -139.557 -72.206 -177.515 -34.625 0 -1.078.515
change

Rehabilitation 366.018 169.241 175.818 192.525 77.946 19.762 30.548 232.267 320.704 161.595 228.630 228.437 2.203.490

Others -47.714 -59.695 21.486 26.116 -76.046 -55.090 31.700 43.731 -210.752 154.711 682.050 -3.976 916.064 497.005

Totalgain 785.186 383.257 379.389 378.980 253.055 198.204 245.371 815.988 913.418 713.298 1.432.118 696.541

Totalloss -222.248 -162.133 -62.851 -112.658 -206.548 -213.156 -111.457 -296.748 -524.807 -332.325 -391.178 -419.311

4 FOREST AREA INCREASED UNEQUAL


WITH THE FOREST QUALITY

From 1990, since the depletion of forest resources


in Vietnam, the Government issued the Directive
90/CT which officially decided to “close its forests”
to logging and completely prevented natural for-
ests. However, based on the Government’s statistics
in 2004, there are only 7% of primary forest and
nearly 70% of secondary forest (Forest Protection
Department 2004). Wood capacity has never met
the increasing needs of timber production, wood
processing, domestic use and export. The decreas- Figure 3. Some extinct species of animals and plants
ing of forest quality is also presented in the decline in vietnam. a) Sumatran rhinos (Dicerorhinus sumatren-
of forest protection capacity of coastal forest, pro- sis); b) Tapir (Tapirus terrestris); c) Estuarine Crocodile
(Crocodylus porosus); d) Slipper orchids (Cypripedilum
tection forests and biodiversity depletion. tibeticum).
Before 1945, total wood reserves of Vietnam’s
forests was estimated about 200–300 m3/ha, which
wood species had high economical value such First List of threatened species and Vietnam Red List,
quality wood (Markhamia stipulata), Iron-wood which reveals that the conservation status of the
(Erythrophlocum fordii), Lauan meranti (Madhuca vast majority of threatened species is downwards.
pasquieri), Lauan (Shorea roxburghii), Apitong According to the IUCN Red List 2004, it is reported
(Vatica tonkinensis), Rose-wood (Garcinia far- that there are approximate 407 species of animals
graeoides). These species hardwood trees have and 450 species of plants facing with extinction.
large diameter about 40–50 cm and accounted for In 2007, Vietnam had 882 species (418 species of
40–50% of total forest reserves. animals and 464 species of plants) are threatened
In addition, the reduce of forest quality is also in the wild nature. Among these species, there are
the loss of many species in International Union 116 species of animals was in “critical” list, and 196
for the Conservation of Nature (IUCN) Red plant species was in “endangered” list. Especially,

319
there are 9 species are not found in Vietnam and • Forest exploitation, deforestation and land-use
be extincted are Sumatran rhinos (Dicerorhinus change are main drivers causing forest degrada-
sumatrensis), Wild ox (Bos sauveli), Tapir (Tapi- tion in Vietnam.
rus terrestris), Otter civet (Cynogale bennettii), • To strengthen administrative controls, the Gov-
Carps (Procypris merus), Japanese eel (Anguilla ernment need to build and reenforce policies
japonica), Carps (Cyprinus multitaeniata), Estua- related forest management, and promote people
rine Crocodile (Crocodylus porosus), Sika deer to improve forest protection in the whole coun-
(Cervus nippon) and Slipper orchids (Cypripedilum try. Besides, Vietnam needs to issue policies on
tibeticum). (Vietnamese Government 2007). infrastructure construction, forestry, land allo-
cation and implementation of forest policies to
improve benefits for communities, create more
5 CLIMATE CHANGE jobs, increase many outputs of agroforestry
products and agricultural products.
Vietnam is one of the world’s five most vulnerable • Enhance joint forest protection and management
countries to climate change (The US Forest Serv- programs between the Government and house-
ice 2011). While the area of forested land is gradu- holds to improve benefit sharing from the forests.
ally reducing by years, the protection capacity of • Forestry technical solutions are also need to
nature land will be weaker, and as results there are implement to support afforestation, forest regen-
many typhoons and severe storms will easily occur eration, and and conserve biodiversity species.
associating with storm surges, salt water intrusion, Based on different geology characteristic, suitable
flooding, landslides and damage to coastal infra- plants should be selectted to grow in oder to pro-
structure and coastal communities. In addition, vide both economic and environmental benefits.
annual seasonal rainfall distribution is also chang- • The local governments, private nonindustrial
ing, leading to increased storm flows in the wet forest and forest management organizations
season and decreased hydrological discharge in the need to set up clear strategy and plan to improve
dry season. The altered flow regime would cause efficient in forest protection. The Government
negative impacts on agriculture and potable water should support forestry managers and rangers
supply. It is predited that the sea level rise has strong powerful equipment to protect and man-
amounted to 20 cm for the past 50 years and a sea age forests resources.
level rise will continue rise up to 100 cm by 2100.
Hence, many serious impacts would directly affect
to at least 10% of Vietnam’s population (The US ACKNOWLEDGEMENTS
Forest Service 2011). If the sea level rises 100 cm,
the flooded areas are predicted about 40% of area The authors gratefully acknowledge the finan-
in Mekong Delta, 11% of area in Red River Delta cial supports by Ton Duc Thang University and
and 20% of the area in Ho Chi Minh city. Besides, Vietnam National University of Forestry—Second
approximately 10–12% of Vietnamese population Campus for this study.
will be directly affected and lost about 10% of
GDP (Decision 2139. 2011).
Currently, there are some action plans in order to REFERENCES
strengthen forest protection and forest management
in Vietnam, including the National Strategy on Envi- Bernard, S., De Koninck R. 1996. The retreat of the for-
ronmental Protection Programe to 2010 and Vision est Southeast Asia: A cartographic assessment. Singa-
to 2020, the National Target Programme to Respond pore Journal of Tropical Geography, 7:1–14.
Forest Protection Department. 2014. Annual forest data
Climate Change, and the National Programe for (in Vietnamese).
Disaster Prevention. The main objective of these Joao, S. de Q., Daniel, G., Nguyen, D.T., Patrick, H.
programs focus on forests and biodiversity conser- 2013. Vietnam tropical forest and biodiversity assess-
vation to reduce the degradation and exhaustion of ment. Sun Mountain International and the Cadmus
natural resources and reduce the rate of decline of Group, Inc., Ecuador; p.79.
biodiversity, and strengthen the capacity to respond Ministry of Agriculture and Rural Development. 2015.
to climate change impacts (Joao et al. 2013). Decision No. 3135/QD-BNN-TCLN dated August 6,
2015, on declare for the status of national forests in
2014. Vietnam.
Prime Minister Nguyen Tan Dung. 2011. Decision 2139/
6 CONCLUSIONS QĐ-TTg on National strategy on climate change (in
Vietnamese). Vietnam.
This review provided a broad spectrum of forest The US Forest Service. 2011. Climate change in Vietnam:
transition and its environmental impacts in Vietnam. Assessment of issues and options. USAID funding. p. 75.
There are some main points are concluded following: [Vietnamese Government. 2007. Vietnam Red Data Book.

320
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Control of noise level and its effects on workers in Hiep Phuoc cement
grinding plant, Holcim Vietnam

X.T. Thai
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

P. Kučera
Faculty of Safety Engineering, VSB—Technical University of Ostrava, Ostrava, Czech Republic

ABSTRACT: Cement industry is one of the industries with noise induced hazards. The aim of this study
was to evaluate the noise level in Hiep Phuoc Cement Grinding Plant, Holcim Vietnam. This research was
implemented by surveying noise level at production areas where remaining high noise level, then calculat-
ing the permissible exposure time to noise level in these areas based on Vietnam Technical Regulation on
noise level in the workplace, and finally, suggesting the exposure time to Hiep Phuoc Cement Grinding
Plant for their additional control of noise effects on workers. The noise level obtained in mill areas in Hiep
Phuoc Cement Grinding Plant fluctuated from 88.2 dBA to 105.1 dBA at which could potentially lead
to ill-health effects if under long-term exposure. In order to reduce the risk of health effects on workers
due to high noise level exposure. Additionally, the controls of noise level and its effects were suggested for
Hiep Phuoc Cement Grinding Plant.

Keywords: noise level, cement grinding, exposure, control

1 INTRODUCTION In order to reduce the risk of ill-health effects


due to noise level, the exposure time with high
Noise is defined as all sound in the workplace, noise level in these production areas were addi-
whether wanted or unwanted (Beno 2012) or noise tional considered beside current technical counter-
as annoying and unwanted sound (Qiu and He measures. In Vietnam, noise level in the workplace
2013). In cement industry, noise is one of the most is regulated in decision 3733/2002/QĐ-BYT effec-
typical hazardous factors that can lead to ill-health tive from October 25th 2002 and will be replaced
effects. Noise can lead to ear damage on a tempo- by Circular 24/2016/TT-BYT “National technical
rary (acute) or permanent (chronic) basic. There regulation on noise—permissible exposure lev-
are three principal acute effects including tempo- els of noise in the workplace” on December 01st
rary threshold shift, tinnitus and acute acoustic 2016. In this decision, noise level was regulated
trauma. Occupational noise can also lead to one of at 85 dBA for 8 hours exposure per working day.
the following three chronic hearing effects includ- According to this approach, the purpose of this
ing noise-induced hearing loss, permanent thresh- research is to (1) calculate the permissible exposure
old shift and tinnitus (Hughes and Ferrett 2011, time in production areas based on current meas-
European Agency for Safety and Health at Work urement of sound noise level and Vietnam Tech-
2005). Noise-induced hearing loss is one of the nical Regulation on noise; (2) suggest controls of
occupational diseases regulated by Vietnam legal noise level and its effects for Hiep Phuoc Cement
requirement and employer in any enterprises are Grinding Plant.
responsible to implement the control of noise level
and its effects on worker in order to prevent occu-
2 MATERIAL AND METHODS
pational deafness from occurring.
In cement grinding plant, noise was mainly
2.1 Study site
generated from main machines, equipment dur-
ing operation period such as horizontal ball mill, Noise level was surveyed at horizontal ball mill
air compressor, roller press, etc. The noise levels areas where workers are potential to exposure to
in these areas were fluctuated from 89 dBA to high noise level during their working hours in Hiep
105 dBA at which can cause ill-health effects under Phuoc Cement Grinding Plant, Holcim Vietnam.
long-term exposure. Hiep Phuoc Cement Grinding Plant located in

321
Hiep Phuoc Industrial Park with the following by other factors such as raining, traffic activities,
flowsheet (see Figure 1). etc. Because the operation activities are as same as
amongst shifts so 04 working hours were selected
in the first shift to represent for the rest shifts.
2.2 Sampling and sample processing
In order to measure noise level at study site, noise
On July 2016, noise level at 20 points around two measuring meter Quest SoundPro® SE/DL—USA
ball mill sites and at 04 different working hours was used. This meter was calibrated by Vietnam
in the first shift (06:00–14:00) were measured and Metrology Institute and valid until May 31st 2017.
recorded. At each measuring point, noise level was
measured in the worker’s hearing zone (Work Safe
BC. 2007) at the height of 1.4 m from the ground 2.3 Data analysis
which is as same high level as or close to worker’s Sound noise level was measured, collected and then
ears and was 03 m far from noise sources where calculated the equivalent noise level (Leq) to repre-
worker can exposure to noise level in these areas. sented noise level of working shift with four times
The details of noise measuring points were illus- measuring (n = 4) by using the formula (Work Safe
trated in the following Figure 2. BC. 2007, Anwr and Ilham 2014):
Noise level was measured at 07:30, 09:30, 11:30,
13:30 in one day with 02 parameters (LMax, Leq) ⎛ 1 ⎞
and recorded in paper sheet. During measurement L eq =10log ⎜ [10 0 1L 10 0 1L 10 0 1L ] ⎟ (1)
⎝ n ⎠
time, noise level was measured and recorded in
normal operational conditions without interfering
Where: Leq: A-weighted, is the equivalent steady
sound level of a noise energy-averaged over time;
and Ln: the nth sound level of n sound levels
(n = 4).
Next, calculating Leq to represented noise level
of working shift with 10 measuring point in each
mill area and using the same formula with n = 10.
Next, basing on Leq to represented noise level of
working shift and basing on Vietnam Technical Reg-
ulation on noise at the workplace of working shift
(08 hours), then calculating the permissible exposure
time by using formula (Work Safe BC. 2007):

⎛ Dose 8 ⎞
L eq =10Log ⎜ × ⎟ + 85 dBA (2)
⎝ 100 T⎠
Figure 1. Process flowsheet of Hiep Phuoc Cement
Grinding Plant.
Where: Dose = a noise exposure dose, in%,
acquired in T hours. In this research, dose was
selected as 100% for an exposure of 85 dBA in 08
working hours per shift according to Vietnam Tech-
nical Regulation on noise coded 3733/2002/QĐ-BYT;
and Leq: A-weighted, is the equivalent steady sound
level of a noise energy-averaged over time.
Finally, according to permissible exposure time
(T) from above calculations, the controls of noise
level and its effects on workers were suggested for
Hiep Phuoc Cement Grinding Plant in order to
reduce the risk of ill-health effects.

3 RESULTS AND DISCUSSION

3.1 Noise level at mill sites


The noise level at 20 points with 04 different hours
were measured and showed in the following table
Figure 2. Noise measuring points. (see Table 1, 2):

322
Table 1. Equivalent noise level at ball mill no. 1. Table 3. Equivalent noise level represented to 04 hours
at mill 1.
7:30 9:30 11:30 13:30
TLV-TWA* Reduction
Mill 1 Lmax Leq Lmax Leq Lmax Leq Lmax Leq Mill 1 Leq (dBA) (dBA) (dBA)

S1 92.2 91.3 94.9 92.8 91.9 90.6 91.7 90.3 S1 91.4 85 6.4
S2 92.5 91.2 92.8 91.3 92.6 91.1 92.6 90.7 S2 91.1 85 6.1
S3 94.6 91.6 95 91.5 94.5 92.1 94.2 92.0 S3 91.8 85 6.8
S4 95.2 92.4 97.7 92.3 94.7 92.3 94.5 92.1 S4 92.3 85 7.3
S5 90.2 88.2 90.4 88.6 90.1 88.2 89.6 87.8 S5 88.2 85 3.2
S6 89.6 87.8 89.7 88.1 89.5 87.2 89.5 87.6 S6 87.7 85 2.7
S7 103.2 100.4 103 100.8 103.3 100.2 104.0 100.0 S7 100.4 85 15.4
S8 103.8 100.8 103.6 101.1 104.1 100.5 105.1 100.1 S8 100.6 85 15.6
S9 93.6 91.2 93.4 91.1 93.4 91.1 93.6 91.0 S9 91.1 85 6.1
S10 92.8 90.1 92.9 89.9 93.1 92.6 94.2 92.5 S10 91.5 85 6.5

*TLV-TWA: Threshold Limit Value—Time Weighted


Table 2. Equivalent noise level at ball mill no. 2. Average is 85 dBA per 08 working hours per day accord-
ing to Vietnam Technical Regulation on noise coded
7:30 9:30 11:30 13:30 3733/2002/QĐ-BYT.

Mill 2 Lmax Leq Lmax Leq Lmax Leq Lmax Leq


Table 4. Equivalent noise level represented to 04 hours
A 92.3 89.2 92.8 89.5 92.1 89.3 92.0 89.4 at mill 2.
B 94.2 90.4 95.2 90.8 93.9 90.6 93.8 90.7
C 95.4 94.2 95.6 94.5 95.4 94.4 95.6 94.5 TLV-TWA Reduction
D 95.3 94.1 95.3 94.2 96.8 95.2 97.1 96.1 Mill 2 Leq (dBA) (dBA) (dBA)
E 92.2 89.9 92.1 89.9 93.8 91.1 95.1 91.5
A 89.4 85 4.4
F 92.6 90.1 92.5 90.2 93.8 90.7 94.0 91.0
B 90.6 85 5.6
G 90.8 88.8 91.1 88.9 90.5 89.2 90.3 89.1
C 94.4 85 9.4
H 91.3 89.4 91.2 89.5 91.4 89.2 91.2 89.3
D 95.0 85 10.0
I 93.4 91.6 93.1 91.6 93.2 91.5 93.0 91.5
E 90.7 85 5.7
K 92.2 91.3 92 91.1 92.1 91.2 92.0 91.1
F 90.5 85 5.5
G 89.0 85 4.0
H 89.4 85 4.4
The equivalent noise levels in ball mill sites I 91.6 85 6.6
were so high that over noise level in the work- K 91.2 85 6.2
place for normal working shift (85 dBA) regulated
in Vietnam Technical Regulation on noise (QĐ
3733:2002/QĐ-BYT). The noise levels in these The equivalent noise level measured in mill
areas were fluctuated from 88.2 dBA to 105.1 dBA 2 sites showed that the lowest equivalent noise level
at which can potentially lead to ill-health effects if was 89.0 dBA and the highest equivalent noise
under long-term exposure. level was 95.0 dBA in which equivalent noise level
was higher than noise level regulated in Vietnam
3.2 Equivalent noise level at mill sites Technical Regulation on noise coded 3733/2002/
QĐ-BYT.
Equivalent noise levels represented to 04 hours Then the equivalent noise level represented to
at mill sites were calculated and showed in the 10 measuring points in each mill site were analyzed
Table 3, 4. and showed in the following table.
The equivalent noise level measured in mill Basing on Leq to represented noise levels of
1 sites showed that noise level at all surveyed sites
working shift in mill 1 & mill 2 sites and basing on
have exceeded noise level regulation (85 dBA) for
noise level in the workplace regulated in Vietnam
08 working hours per shift. The lowest equiva-
Technical Regulation for 08 hours per working
lent noise level in mill 1 sites was 87.7 dBA, while
shift, then the permissible exposure time was cal-
the highest equivalent noise level in this area was
culated by using formula (Work Safe BC. 2007):
100.6 dBA. So that the exposure time of equivalent
noise level in mill 1 sites must be reduced as follow-
⎛ Dose 8 ⎞
ing calculation in order to reduce the risk of noise- L eq =10Log ⎜ × ⎟ + 85 dBA (2)
induced hearing loss and meet legal requirement. ⎝ 100 T⎠

323
Figure 5. The relationship between the equivalent noise
Figure 3. Equivalent noise level at mill 1 sites. level and the permissible exposure time in mill 1 sites.

Figure 4. Equivalent noise level at mill 2 sites.


Figure 6. The relationship between the equivalent noise
level and the permissible exposure time in mill 2 sites.
Where: Dose is 100% for an exposure of 85 dBA
in 08 working hours per shift according to Vietnam Table 5. Equivalent noise level represented to 10 meas-
Technical Regulation coded 3733/2002/QĐ-BYT. uring points in mill 1 and mill 2.
So the permissible exposure time at each site in Site Leq per shift (dBA) TLV-TWA (dBA)
mill 1, 2 were calculated and showed in the follow-
ing tables. Mill 1 95.1 85
The relationship between the equivalent noise Mill 2 91.6 85
level and the permissible exposure time in mill 1,
mill 2 sites were showed in the Figure 5, 6.
Basing on the equivalent noise level represented Vietnam Technical Regulation of noise level in
to 08 working hours per shift as calculated and the workplace (85 dBA) for 08 working hours per
mentioned in table 5, the permissible exposure time shift and the potential risk of hearing loss, it was
in mill 1, 2 areas were calculated as following table. necessary for management team of Hiep Phuoc
The statistical data treatment showed that the Cement Grinding Plant to review and imple-
equivalent noise levels in ball mill sites were so high ment some enforced countermeasures in order
(91.6 & 95.1 dBA) as comparison to Vietnam Techni- to reduce the effect of noise exposure on work-
cal Regulation on noise level (85 dBA per 08 working ers. Worker who are potential at risk of noise-
hours per shift). Basing on the equivalent noise level induced hearing loss or occupational deafness if
at mill 1 area was 95.1 dBA and mill 2 was 91.6 dBA, they are under continuous exposure to noise level
the permissible exposure time in mill sites were cal- in excess of 85 dBA (Hughes and Ferrelt 2011,
culated and suggested that workers should perform Strank 2008).
their works in mill 1 about 0.78 hour or in mill 2 about When determining risk controls, consideration
1.73 hours without hearing protection within a work- shall be given to reducing the risks according to
ing shift to reduce the effects of noise on workers. the following hierarchy: elimination; substitution;
engineering controls; administrative controls; per-
sonal protective equipment (BS OHSAS 18001.
3.3 Approaches for control of noise effects
2007). Beside that we can use a simple hierarchy
According to obtained noise survey in mill sites in of noise control techniques including reduction of
which the equivalent noise levels were higher than noise at sources; reduction of noise level received

324
Table 6. The Permissible Exposure Time (PET) at mill Table 8. The permissible exposure time for 08 working
1’s sites. hours per shift in mill 1, 2.

Leq PET PET Permissible Permissible


Mill 1 (dBA) (hr/shift) (Minute/shift) exposure exposure
time time
S1 91.4 1.8 111 Leq/shift TLV-TWA (hours/ (minutes/
S2 91.1 2.0 118 Area (dBA)a (dBA) working shift) working shift)
S3 91.8 1.7 100
S4 92.3 1.5 90 Mill 1 95.1 85 0.78 47
S5 88.2 3.8 229 Mill 2 91.6 85 1.73 104
S6 87.7 4.3 259
S7 100.4 0.2 14 implementation of this regulation via disci-
S8 100.6 0.2 13
plinary procedures. (c) Implementing health
S9 91.1 2.0 118
surveillance for current employees who were
S10 91.5 1.8 108
exposed to high noise level and new recruitment
employees who will perform their activities
within these areas so that we can find out the
Table 7. The permissible exposure time at mill 2’s sites. suspended cases with noise-induced hearing loss
and then arrange them the proper work prop-
Leq PET PET erly. (d) Installing warning signs, poster within
Mill 2 (dBA) (hr/shift) (Minute/shift) plant in order to enhance the knowledge on the
effects of noise on worker.
A 89.4 2.9 176 − Personal Protective Equipment (PPE): Using
B 90.6 2.2 131
hearing protection equipment such as ear-
C 94.4 0.9 55
muff or earplug that can reduce the noise level
D 95.0 0.8 48
received by employee. Using earplug can reduce
E 90.7 2.2 130
noise up to 30 dBA, while earmuff can reduce
F 90.5 2.2 135
the noise from 40 to 50 dBA (Anwar and Ilham
G 89.0 3.2 191
H 89.4 2.9 176
2014). So that employee who works in mill areas
I 91.6 1.8 106
will be in safe exposure range of noise level dur-
K 91.2 1.9 116 ing their working shift if they use earmuff or
earplug correctly.
However, in order to ensure the lowest risk of
by the employee; use of personal protective equip-
exposing to high noise level in mill areas, manage-
ment (Hughes and Ferrelt 2011).
ment team of Hiep Phuoc Cement Grinding Plant
Basing on these noise control approaches and
must apply and enforce all overall above recom-
the nature of noise level at Hiep Phuoc Cement
mended countermeasures.
Grinding Plant that we cannot eliminate or sub-
stitute the noise sources, some other control tech-
niques were recommended as following:
4 CONCLUSION
− Engineering control in order to reduce noise
level at source by improving the maintenance The permissible exposure time with equivalent
regime by regular lubrication of bearings; utiliz- noise levels in production sites have been calcu-
ing the grinding process by adjusting the opera- lated basing on surveyed equivalent noise levels
tion speed and proper rate of ball mill; in mill sites. The equivalent noise levels in produc-
− Administrative control: (a) reducing the noise tion sites were recorded, analyzed and fluctuated
level received by employee by reducing the noise from 88.2 dBA to 105.1 dBA which over noise level
exposure time in production areas, especially in (85 dBA) in the workplace as regulated by Viet-
mill areas. As above calculation, employees are nam Technical Regulation on noise (Decision no.
recommended to exposure to noise level in mill 3733:2002/QĐ-BYT). The permissible exposure
1 about 0.78 hour or in mill 2 about 1.73 hours. time with noise level in mill 1 was 0.78 hour and in
However, to ensure employee know and follow mill 2 was 1.73 hours.
up the exposure time during their working shift, Additional, the control techniques of noise level
Hiep Phuoc management team must delivery and its effects on workers including engineering
this message throughout training, daily toolbox controls, administrative controls and PPE were also
talk or mentioned clearly in operational work suggested to Hiep Phuoc Cement Grinding Plant in
instructions. (b) Supervising and enforcing the order to reduce the effects of noise on workers. The

325
obtained study results could be applied not only in Beno, G. 2012. Physical hazards—Noise and Vibration.
cement factories but also in other manufacturing Victoria: Safety Institute of Australia Ltd.
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BSI Standards.
European Agency for Safety and Health at Work. 2005.
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Hughes, P. and Ferrett, E. 2011. Introduction to health
I would like to thank Management team of Hiep and safety at work, 5th edition. Abingdon: Routledge.
Phuoc Cement Grinding Plant, Holcim Vietnam Qiu, J. and He, X. 2013. Evaluation of noise reduction
for their supports during working and measuring in a cigarette factory, China, International Journal of
period. I also would like to thank Dr. Pham Anh Physical Science, Vol. 8, no. 44, pp: 2035–2039.
Duc, Faculty of Environment and Labor Safety, Strank, J. 2008. Health and Safety at Work, revised 8th
Ton Duc Thang University for his valuable help. edition. London: Kogan Page Limited.
Work Safe BC. 2007. Occupational noise survey, second
edition. Vancouver, Canada.
Worrk Safe BC. 2007. Basic noise calculations. Vancouver,
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Proposal of a method for predicting and taking measures against soil


slips generating debris flows in a case study of the 2014 Hiroshima
sediment disasters

Y. Ooka, H. Umezawa, R. Sawada & A. Tameike


Toa Grout Kogyo Co. Ltd., Aichi, Japan

Y. Ishikawa
Tokyo University of Agriculture and Technology, Tokyo, Japan

Q.D. Dang
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Vietnam

ABSTRACT: The previous studies indicated that most of debris flows are generated by the soil slips in
zero-order basins. If the places of soil slips are predicted accurately before occurrence of them, we can
conduct more effective countermeasures against soil slips than ordinal countermeasures such as check
dams for capture the large amount of debris for preventing disasters. The purpose of this study is to pro-
pose a method of predicting the places of soil slips and propose the way for preventing occurrence of soil
slips or trapping the small amount of debris in the upper reaches of streams. The places of soil slips are
examined in case study of the 2014 Hiroshima sediment disasters. The results indicate that about half of
soil slips occurred in the zero-order channels and most of soils slips generated debris flows. We proposed
that effective measures against the soil slips in zero-order channels to prevent debris flow disasters.

Keywords: soil slips, debris flow, zero-order channel, slope stability work, flexible debris flow barrier

1 INTRODUCTION method for predicting and taking measures against


generation of debris flows, which we report here.
According to research by Tsukamoto et al., soil slips Our research covered two geographic areas,
that cause debris flows are highly likely to occur namely Mt. Abu (about 585 meters above sea level)
in zero-order basins.1) Tsukamoto et al. defined all and Mt Takamatsu (about 340 meters above sea
depressions seen on mountainside slopes that have level), where debris flows have frequently occurred.
not grown into first-order channels as zero-order
channels (under-first-order channels), and made
it clear that soil slips in zero-order channels are 2 OUTLINE OF THE SEDIMENT
widely distributed. However, if one is to predict the DISASTER IN HIROSHIMA
causes of debris flows and consider measures to be
taken against them, the area of causes of debris From 3:00 to 4:00 AM on Aug. 20th, maximum
flows must be limited because the scope of predic- hourly rainfall of 101 mm (AMeDAS Miiri
tion of points of soil slips is widely distributed, Observatory) occurred in the northwestern part of
and cost superiority cannot be maintained. Hiroshima City, almost at the same time, many soil
Against such a background, in this paper we slips occurred in the headwater of streams around
have classified the points of soil slips which gener- Mt. Abu and Mt. Takamatsu, triggering debris
ate debris flows by geographic feature in consid- flows (Figure 1, Photo 1, Photo 2). The debris flows
eration of the August 2014sediment disasters due containing boulders flowed down streams and
to heavy rainfall in Hiroshima Prefecture with the generated great quantities of sediment and woody
aim of predicting the generation of debris flows debris by eroding the stream bank and stream bed
with high probability, and we have calculated the in the middle and upper reaches. The debris flows
ratio of such occurrences. Then, based on the flooded on the alluvial fans and caused great injury
results thereof, we conducted basic research on a with 74 fatalities, and great damage, with 133 totally

327
Children

Children

Children

Children
Figure 1. Study area.

Figure 2. Reading conditions of Mt. Abu (top) and Mt.


Takamatsu (bottom) (Provided by Aero Asahi Corp.).

of disasters in the areas covered by our research


Photo 1. East side of Mt. Abu where many debris flows (Figure 2). In conformity to the set definitions, we
occurred (Photo taken by the Geographical Survey Insti- classified the points of occurrence of soil slips and
tute, Japan). calculated the ratios thereof. Moreover, we classi-
fied the soil slips in zero-order channels into three
categories to narrow down the areas to predict and
then calculated the ratios thereof.

4 DEFINITIONS OF CATEGORIES IN THE


OCCURRENCE AREAS

The areas where soil slips were caused in surveyed


areas are classified as follows: Category I refers
to soil slips in zzero-order channels, Category II
to bank collapses, and Category III to other soil
slips (Figure 3). These definitions are elaborated
Photo 2. West side of Mt. Takamatsu where many below.
debris flows occurred (Photo taken by the Geographical
Survey Institute, Japan).
4.1 Zero-order channels (Category I)
destroyed houses and 297 houses half and partially Here, only the upper part of a basin that has
destroyed. The areas are geologically made up of grown into a first-order channels is classified
weathered granite and sedimentary rock. as a zero-order channels, which is defined as the
areas surrounded by the line of the basin divide
and straight lines which each open by 30 degrees
3 METHOD toward the right and left bank sides from an exten-
sion line that extends from the top end of the
The scars of the debris flows are shown in a 1/5,000 first-order channels. The points of soil slips in the
contour diagram by using aerial photographs areas of a zero-order channel are each divided by
taken (by Aero Asahi Corp.) after the occurrence 10 degrees from the 0-degree line toward the right

328
debris flows from two or more sources of soil slips
join together and flow down, in the same manner,
we measure the horizontal distance from each point
of soil slips to the point where the debris stop.

5 RESULTS

5.1 Assessment of points of soil slips


The number of points of soil slips surveyed was
181. According to the classification results, Cat-
Figure 3. Soil slip point categories. egory I had 96 points and the highest rate of
occurrence, about 53%. Category II had 18 points
and a rate of occurrence of about 10%, while Cat-
egory III had 67 points and a rate of occurrence
of about 37%. Of the Category III collapses, 64
points and about 35% occurred in depressed ter-
rain (hollow), showing the second highest rate of
occurrence after Category I (Table 1). Then, we
further sub-classified the Category I collapses. Of
the 96 points, Category (a) had 42, Category (b)
had 26, and Category (c) had 28. In zero-order
Figure 4. Zero-order channel categories. channels, Category (a) had the highest rate, about
44% (Table 2).
and left banks into three equal parts, and they are Moreover, the number of existing zero-order
classified as follows: Category (a) refers to less channels we read in the overall area was 155, and
than 10 degrees, Category (b) to at least 10 but less there were 73 points of zero-order channels that
than 20 degrees, and Category (c) to at least 20 but had soil slips. Thus, this value accounted for about
less than 30 degrees (Figure 4). The soil slips that 47% of all zero-order channels (Table 3).
widely extend to the 30-degree line are classified As to why the rate of occurrence of soil slips
as Category (a), while other soil slips that straddle increases in depressed terrain in Category I or III,
other lines are classified into the category where we think that because surface water concentrates
soil slips bounds are included more widely.
Table 1. Point of soil slips categories.
4.2 Banks (Category II)
Within the areas of a basin divide, the areas
surrounded by right and left riverbanks from
the trough line within a horizontal distance of
20 meters are classified as banks.

4.3 Others (Category III)


Areas that do not fall under either Category I or
II are classified as Category III. These areas are
further classified into rising terrain (ridge) or
depressed terrain (hollow) based on the terrain of
the points of soil slips.
Table 2. Zero-order channels categories.
4.4 Debris flows
We classify debris flows that move over a horizon-
tal distance of at least 100 meters as debris move-
ments. Such a movement distance refers to the
distance from the source of soil slips to the point
where the debris stop; it does not include areas
where debris spread out. Also, in the case in which

329
Table 3. Total No. of zero-order channels and rate of Table 4. Debris flows that moved by category.
occurrence.
Flowed-
stopped
Face Tough -down
Face Tough
Face Tough (1 0 ) No. of points of soil slips. 156 25
Face Tough Face Tough
(1 1) Total No. of points of soil slips. 181
Face Tough
Face Tough (1 2 ) Flowdown rate(%)
86.2 13.8
((1 0 x 1 1) x 100)
Face Tough Face Tough

Table 5. Debris flows that stopped by category.


in such terrain during times of rainfall, the sub- I n m
surface water that has concentrated in the surface
soil induces soil slips. Therefore, we considered at (1 3) No. of poins of soil slips. 6 4 15
which point where rainwater from the upper part
of the slope concentrates was most likely to soil (14) Total. 25
slips. So, we think that reading such points can
contribute to reducing the areas of prediction of (15) Rate of occurrrence(%)
24.0 16.0 60.0
((1 3)/(14) X 100)
points of soil slips.

5.2 Assessment of the flow-down distance of


soil slips at 2 points did not flow into first-order
debris flows
channels.
We measured the movement distance of debris
flows at all 181 points of soil slips. The results
indicate that soil slips at 156 points caused debris 6 PROPOSAL OF MEASURES AGAINST
flows, while at 25 points the soil slips stopped DEBRIS FLOWS
along the way. Thus, we found that about 86% of
soil slips that occurred developed into debris flows The most debris flows in Hiroshima were gener-
(Table 4). Nevertheless, regarding the categories of ated by soil slips triggered by the heavy rainfall.
the soil slips that occurred at 25 points where the As for measures preventing occurrence of debris
debris movements stopped along the way, Category flows, we propose that measures against the soil
I had 6, Category II had 4, and Category III had slips in zero-order channels, namely at the headwa-
15. Thus, we found that the rate that debris move- ter of streams are effective. In the areas surveyed in
ments in Category I and Category II stop along the this research, soil slips occurred in about half of all
way is very low (Table 5). zero-order channels in the surveyed areas, and most
As to why the Category I and Category II such soil slips developed into debris flows. So, we
soil slips developed into debris flows at a high consider that about half of such debris flows could
rate, one can point out that there the environ- have been prevented by taking measures against
ment is such that debris can move over a rela- soil slips in zero-order channels. When the debris
tively longer distance because of the presence generated by several soil slips flow together in the
of an area that has grown into a first-order middle reaches and the debris flows cause damage
channel, which leads debris directly below or to houses or loss of lives in the lower reaches, the
within a horizontal distance of 20 meters. How- measures against soil slips can decrease the volume
ever, regarding the Category I or Category II of harmful debris, even if the generation of debris
soil slips that did not develop into debris flows, flows are not completely prevented. As for which
there are two conceivable patterns, namely soil points to take such measures at, we think that the
slips that did not reach first-order channels, and places classified as Category (a) under Category I
soil slips that stopped within first-order chan- are important.
nels. Nevertheless, we think it necessary to fur- When the areas of Category (a) in the areas of
ther consider these by making use of inclination zero-order channels with high probability of soil
classification drawings and other materials. For slips are small, slope stability works are suitable for
reference, in Category III, collapses at 52 points the measures to prevent soil slips which generate
developed into debris flows, and among these, debris flows. Since the areas of Category (a) locate

330
the transportation of materials and construction
should be conducted in a simple way. Under this
construction conditions, the flexible debris flow
barrier used by high tensile strength steel nets are
suitable for .preventing debris flow disasters.
Both of the slope stability works and the flexible
debris flow barrier used by the high tensile strength
steel nets have many their record of construction
in Japan. Concerning the flexible debris flow bar-
rier, examples of capture of debris are reported as
shown in Photo 4. However, as both the number
and area of all zero-order channels are enormous,
we think it necessary to determine levels of impor-
tance by narrowing down the areas to be surveyed
Photo 3. An example of slope stability works used by based on which mountain streams have the possi-
high tensile strength steel net. bility of causing debris flows as well as the pres-
ence or absence of measures for mountain streams
and their lower reaches that may stop the debris
flows.

7 CHALLENGES TO ADDRESS IN THE


FUTURE

Zero-order channels are generally defined as terrain


whose depth is less than the frontages of depressed
contour line groups by using 1/25,000 topographi-
cal maps or large-scale topographical maps.2) How-
ever, we think that a clearer definition is needed
to extract, in a limited manner, those zero-order
channels that have a possibility of occurrence of
soil slips.
Photo 4. An example of capture of debris by the flex-
ible debris flow barrier.
REFERENCES

in the headwater of the streams, the construction Kaibori, M. et al. 2014. Sediment-related disasters
induced by heavy rainfall in Hiroshima City on 20th
of measures should be possible by human power August, 2014, Journal of the Japan Society of Erosion
and the materials for the measures should be light. Control Engineering, 67(4), 49–59.
Under this construction conditions, the slope sta- Tsukamoto, Y. et al. 1973. Study on the growth of
bility works used by high tensile strength steel net stream channel (III)—Relationship between 0 (zero)
as shown in Photo 3 are suitable for preventing soil order channels and landslides. Journal of the Erosion-
slips and debris flows. Control Engineering Society, 26(2), 14–20.
Whereas, if the areas of Category (a) are large, Water and Disaster Management Bureau of the Minis-
flexible debris flow barrier which catch the debris try of Land, Infrastructure, Transport and Tourism.
generated in the areas of zero-order channels 2007. Manual of Technical Standards for Establishing
a Sabo Master Plan for Debris Flow and Driftwood
located in the headwater of the streams is suitable and an Explanation Thereof, Edition of the National
for the measures, because when the slope stability Institute for Land and Infrastructure Management of
works are used, the large scale of structures is nec- the Ministry of Land, Infrastructure, Transport and
essary. However, in the construction of the flexible Tourism (Technical Notes of the National Institute for
debris flow barrier in the headwater of the streams, Land and Infrastructure Management, No. 364).

331
Environmental Technology and Innovations – Kočí, Ruml, Dao & Duc (Eds)
© 2017 Taylor & Francis Group, London, ISBN 978-1-138-02996-5

Author index

Andráš, P. 37, 137 Kyncl, M. 197 Phu, T.L. 271


Picková, E. 239
Bařinka, K. 31 Lai, M.F. 95 Piecha, M. 31
Bartacek, J. 3, 99 Lankova, D. 251 Pohořelý, M. 143
Beltrán-Prieto, J.C. 61 Lapčík Jr., V. 169 Pulkrabova, J. 17, 251
Beňo, Z. 143 Lapčík, V. 161, 169, 203,
Berka, J. 105 219, 271 Remešicová, E. 37, 137
Bernatík, A. 289 Lay, C.H. 7, 65, 133 Ruml, T. 17, 21
Brynda, J. 143 Le, D.K. 263 Rumlová, M. 21
Le, H.Q. 275
Chen, C.C. 65 Le, M.H. 149 Sawada, R. 327
Chernusov, V.I. 313 Le, T. 9 Skácel, F. 43, 71, 181
Chlupáčová, M. 77 Lee , T.M. 231 Skoblia, S. 143
Chu, C.Y. 127 Leu, H.J. 111 Šnajdrová, V. 177
Chuchrová, K. 31 Lin, C.Y. 7, 65, 111, Spiwok, V. 21
Ciahotný, K. 83, 87, 127, 133 Staf, M. 87
105, 177 Lin, J.H. 95 Stranska, M. 17
Lu, H.C. 7 Stupak, M. 251
Dang, M.T. 149, 203, 255 Luu, B.T. 275 Svarcova, A. 251
Dang, P.M. 255 Syu, J.J. 65
Dang, Q.D. 209, 327 Maneva, K. 71
Dao, T.S. 187, 203, 213 Moško, J. 143 Ta, D.T. 127
Dinh, Q.T. 255 Ta, T.M.N. 127
Do, T.K. 297 Ngo, N.P.D. 47 Tameike, A. 327
Dolejs, P. 3 Nguyen, H.B.S.L. 55, 61 Tekáč, V. 43
Duong, V.M. 181 Nguyen, H.H. 47, 55, 243 Thai, X.T. 321
Nguyen, K.H. 275 Thi, N.B.D. 155, 317
Hadravová, R. 21 Nguyen, P.L. 263 Tran, T.K. 111
Hajslova, J. 17, 251 Nguyen, Q.V. 271 Tran, T.N.S. 289
Hejnic, J. 3 Nguyen, T.D. 209 Trinh, T. 275
Heviánková, S. 197 Nguyen, T.L.C. 149, 283 Truong, T.T.O. 119
Hlinčík, T. 177 Nguyen, T.M.L. 187, 219
Huang, J.Z. 275 Nguyen, T.P.L. 213 Umezawa, H. 327
Hudský, T. 105 Nguyen, T.T. 55 Urbancova, K. 251
Hung, P.C. 133 Nguyen, T.T. 225
Nguyen, T.T.H. 187, 219, 297 Vilamová, Š. 31
Ishikawa, Y. 327 Nguyen, T.T.T. 55 Vo, T.K.T. 213
Nguyen, T.V. 297 Vojvodíková, B. 31
Janák, M. 83 Nguyen, V.H.P. 313 Vrbová, V. 87
Jenicek, P. 3, 99 Nguyen, V.M.T. 231 Vuong, D.H. 219
Jílková, L. 87 Nguyen, V.V. 317
Wu, D.M. 275
Király, A. 31, 37, 137 Ooka, Y. 327 Wu, J.Y. 65
Kočí, V. 239, 305 Wu, S.Y. 65
Kolomazník, K. 61 Parschová, H. 77
Kouba, V. 3 Pham, A.D. 149, 187, 203, Yeh, H.L. 65
Kučera, P. 321 219, 225, 297
Kůs, P. 77 Pham, V.M. 225 Zabranska, J. 99
Kutil, J. 99 Phan, T.T.T. 317
333

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