Environmental Pollution, Toxicity Profile

and Treatment Approaches for Tannery

Wastewater and Its Chemical Pollutants

Gaurav Saxena, Ram Chandra, and Ram Naresh Bharagava

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2 Leather Production and Chemicals Used in Tanning Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3 Tannery Wastewater: Nature and Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4 Environmental Pollution and Toxicity Profile of Tannery Wastewater . . . . . . . . . . . . . . . . . . . . 36
5 Treatment Approaches for Tannery Wastewater and Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.1 Physico-Chemical Treatment Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.2 Biological Treatment Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5.3 Emerging Treatment Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
5.4 Combinatorial Treatment Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
6 Waste Minimization, Operation, Treatment and Management in Leather Industries . . . . . . 51
6.1 Solid Waste Generation, Treatment and Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
6.2 Gaseous Emission and Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
6.3 Clean Technologies for Hazards Minimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
7 International Legislations Scenario for Tannery Wastewater and Chemicals . . . . . . . . . . . . . 53
7.1 Legislations for Discharge Limits of Tannery Wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
7.2 Legislations for Leather Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
8 Challenges and Future Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
9 Summary and Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

G. Saxena • R.N. Bharagava (*)

Laboratory for Bioremediation and Metagenomic Research (LBMR),
Department of Environmental Microbiology (DEM), School for Environmental Sciences (SES),
Babasaheb Bhimrao Ambedkar University (A Central University),
Vidya Vihar, Raebareli Road, Lucknow 226 025, Uttar Pradesh, India
e-mail: [email protected]; [email protected]
R. Chandra
Environmental Microbiology Section, Environmental Toxicology Group, Council of Scientific
and Industrial Research (CSIR), Indian Institute of Toxicology Research (IITR),
Post Box 80, M.G. Marg, Lucknow 226 001, Uttar Pradesh, India

© Springer International Publishing 2016 31

P. de Voogt (ed.), Reviews of Environmental Contamination and Toxicology,
Volume 240, Reviews of Environmental Contamination and Toxicology 240,
DOI 10.1007/398_2015_5009
32 G. Saxena et al.

1 Introduction

Leather industries (LIs) play an important role in the national economy of many
developing countries like India, China, Turkey, Brazil, Ethiopia, Pakistan and
Bangladesh (Leta et al. 2004; Lefebvre et al. 2006; Kurt et al. 2007; Verma
et al. 2008; Haydar and Aziz 2009; Lofrano et al. 2013; Chowdhury et al. 2013;
Wang et al. 2014). Approximately, 22,700.5 M ft2 (or 2108.94 M mt2) of leather is
produced annually in the world (FAO 2008) and the world trade for the leather
sector is estimated as US$100 billion per year (UNIDO 2010). The demand for
leather and leather products is ever increasing and independent of supply. The
United States, Germany and other European countries are the major importers
whereas the countries like India, China, Pakistan, Egypt, Brazil, Thailand and
Indonesia are the major exporters of leather and leather products.
Unfortunately, LIs are also one of the major polluters worldwide because of the
complex nature of their wastewaters. During leather production, a variety of
chemicals with large volumes of water are used to convert the raw hide/skins into
leather or leather products generating large volumes of high strength wastewater,
which are a major source of environmental pollution. The wastewater generated is
characterized by a high chemical oxygen demand (COD), biological oxygen
demand (BOD), Total dissolved solids (TDS), Total suspended solids (TSS),
chromium (III) and phenolics with high pH, strong odor and dark brown color
(Durai and Rajasimmam 2011; Suganthi et al. 2013; Dixit et al. 2015). Apart from
high organic content, tannery wastewater (TWW) also contains various nutrients
such as nitrogen and phosphorus that can lead to eutrophication of water bodies
(Rai et al. 2005; Durai and Rajasimmam 2011; Raj et al. 2014). In addition, the dark
brown color of wastewater hinders the photosynthesis process by blocking the
sunlight penetration and it is therefore deleterious to aquatic life (Aravindhan
et al. 2004; Rai et al. 2005; Kongjao et al. 2008; Mwinyihija 2010; Durai and
Rajasimmam 2011). However, the major pollutants present in TWW include
chromium, tannins or syntans (STs), phenolics, phthalates and azo dyes (Kumar
et al. 2008; Lofrano et al. 2013; Dixit et al. 2015).
The high concentration and low biodegradability of pollutants present in TWW
is a major cause of serious environmental concern (Di Iaconi et al. 2002; Schrank
et al. 2009) and thus, it is imperative to adequately treat the TWW before its final
disposal in the environment. However, the increasingly stringent environmental
regulations are also forcing the LIs to improve the treatment processes applied at
wastewater treatment plants (WWTPs) and also explore the alternative methods for
the better treatment and management of TWW.
Therefore, this paper highlights the environmental impacts and toxicity profile of
TWW and chemicals and provides a detailed review on the existing treatment
approaches for its safe disposal into the environment. The emerging treatment
approaches have been discussed with their merits and demerits. Further, the emerg-
ing anammox technology for the removal of ammonia from TWW and constructed
wetlands (CWs) for wastewater treatment has been discussed. In addition, the clean
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 33

technologies (CTs) for waste minimization, control and management in LIs are
discussed. Moreover, the international legislation scenario on discharge limits for
TWW and chemicals has also been discussed country wise with discharge standards
to prevent the environmental pollution.

2 Leather Production and Chemicals Used

in Tanning Process

LIs are specialized in processing of hide (skins of large animals like cows, buffaloes
and horses) and skins (skins of small animals like sheep, goats and calves) for
leather production. The tanning process used to convert the hide/skins (a highly
putrescible material) into stable and imputrescible products termed as leather,
which is used for various purposes (Dixit et al. 2015). Tanning processes are
classified into vegetable or chrome tanning depending on the type of tanning
reagent (tannins or chromium) applied (Ram et al. 1999; Mannucci et al. 2010)
(Table 1). The steps and overall process of leather production are well described in

Table 1 Comparison between vegetable tanning and chrome tanning process

S. No. Parameters Vegetable tanning Chrome tanning
1. Tanning agent Vegetable tannins (VTs) Chromium salt
2. Nature Organic tanning Inorganic (mineral) tanning
3. Action Slow process Fast process
4. Cost Costly affairs Cost effective
5. Time Time consuming Less time consuming
6. Geographical Used in developed countries and Used in developing countries
use few developing countries
7. Products Heavy leather like shoe soles, Light weight leathers like shoe
luggage, saddlery and belt etc. uppers, garments and bag etc.
8. Product Higher thermal stability and Softer and more pliable leather
characteristics water resistant
9. Processing All the steps are same as in Additionally, retanning, dyeing
steps chrome tanning process and fatliquoring are usually
performed to produce finished
leather and a preliminary
degreasing step may be neces-
sary when using animal skins,
such as ship skins
10. Environmental Does not require prior prepara- Generation of chromium
Impact tion of pickling and therefore containing sludge and wastewa-
contribution to pollution load ter is still a major environmental
from sulfate salts are lower hence problem of chrome tanning
ecofriendly, but VTs are hard to process
biodegrade. Thus, waste bearing
VTs degrade slowly
34 G. Saxena et al.

the literature (Thanikaivelan et al. 2005; ILTIP 2010; Lofrano et al. 2013; Dixit
et al. 2015). However, the tanning process involves different steps and chemicals
for different end products and the kind and amount of waste generated may vary in a
wide range of quantity and nature (Lofrano et al. 2013).
During the tanning process, a large amount of chemicals such as acids, alkalis,
chromium salts, tannins, sulfates, phenolics, surfactants, dyes, auxiliaries,
sulphonated oils and biocide etc. are used to convert the semi-soluble protein
“collagen” present in hide/skins into highly durable commercial forms of leather,
and the chemicals used are not completely fixed by the hide/skins and end up in
wastewater (Lofrano et al. 2008; Mannucci et al. 2010). The poor uptake of
chromium salt (50–70 %) during the tanning process results in the material wastage
on one hand and disturbance of the ecological balance on the other hand
(Saravanbahavan et al. 2004; Dixit et al. 2015). Moreover, the sulfonated oils and
synthetic tannins or syntans (STs) (an extended set of chemicals such as phenol,
naphthalene, formaldehyde, melamine and acrylic resins) are also used in tanning/
retanning process to make the leather more softer (Lofrano et al. 2008, 2013).
Many regulations have been passed to avoid the use of hazardous chemicals in
industrial processes such as Integrated Pollution Prevention and Control Directive
(96/61/EC 1996; 2008/1/EC 2008). The Directive (REACH) (EC 1907/2006) for
European Regulatory Framework on chemicals namely Registration, Evaluation,
Authorization and Restriction of Chemical substances directed the LIs to avoid the
use of those leather auxiliaries and basic chemicals, which are not registered and listed
in the Safety Data Sheet (Lofrano et al. 2013). Moreover, the Directive (2003/53/EC)
restricted the marketing and use of products/product formulations containing >0.1 %
of nonyl ethoxyphenol (NPE) or nonylphenol (NP) and their use in making of the
leather products in Europe (Lofrano et al. 2008). In addition, the Directive (1999/815/
EC) has directed the industries to label the products if they contain >0.5 % phthalates
(benzyl butyl phthalate, di-butyl phthalate and di-ethyl hexyl phthalate) due to the
reproductive toxic potential of the phthalates (EU 2003). The use of o-phenyl phenol
is restricted for leather finishing due to its carcinogenic potential (EPA 2007) and the
use of formaldehyde (a cross liker casein top coats) due to its carcinogenic potential
has been also restricted (EU 1998). The inorganic compounds such as cadmium
sulfate and lead chromate (fastening agents) are highly toxic in nature (IARC 2004;
ATSDR 2008). Further, the EU Azo Colorants Directive (2002) has prioritized several
azo dyes and restricted their use in LIs due to higher toxicity but there is no any
particular restriction to use STs yet in LIs worldwide (Dixit et al. 2015).

3 Tannery Wastewater: Nature and Characteristics

Water is crucial for life and also used in many industrial processes. In the tanning
process, a large quantity of water and chemicals are used to treat raw hide/skins and
approximately 30–35 m3 of wastewater is generated per ton of raw hide/skins
processed (Lofrano et al. 2008; Islam et al. 2014). However, the wastewater
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 35

generation depends on the nature of raw material, finishing product and production
processes applied (Tunay et al. 1995; Lofrano et al. 2013). This presents two major
problems for LIs: First, the availability of good quality of water and second is the
adequate treatment of such a large volume of highly contaminated wastewater.
Tannery wastewater (TWW) is a basic, dark brown coloured waste having COD,
BOD, TDS, chromium (III) and phenolics with high pH and strong odor (Durai and
Rajasimmam 2011; Suganthi et al. 2013; Dixit et al. 2015). However, the charac-
teristics of TWW may vary from industry to industry, raw materials and chemicals
used, type of final product and the production processes adopted by LIs (Apaydin
et al. 2009; Rameshraja and Suresh 2011; Lofrano et al. 2013).
During leather production, the beamhouse and tanning operation are the high
pollution causing steps because beamhouse operation contributes high organic and
sulfide content whereas tanning operation contributes high salts (of chloride, ammo-
nium, chromium and sulfate) concentrations in TWW (Cooman et al. 2003;
Rameshraja and Suresh 2011). Hence, the beamhouse wastewater is characterized
by an alkaline pH and tanning wastewater by a very acidic pH as well as a high COD
value (Lofrano et al. 2013). Generally, TWW is highly rich in nitrogen, especially
organic nitrogen, but very poor in phosphorous (Durai and Rajasimmam 2011). The
retanning streams relatively have a low BOD and TSS (Total suspended solids), but
high COD and contain trivalent chromium (III), tannins, sulfonated oils and spent
dyes whereas the wet finishing, retanning, dyeing and fat liquoring processes con-
tribute low fractions of salt in TWW that is predominantly originating from the hide/
skins in the soak liquor (USEPA 1986; Lofrano et al. 2013). Further, BOD5/COD
(due to inhibitors) or BOD5/TOC (due to high sulfide and chloride concentration)
ratio is used for the biodegradation study of TWW (Lofrano et al. 2013). The data on
wastewater generation and pollution load of each step during the processing of raw
hide/skins are presented in Table 2.

Table 2 Pollution load and quantity of wastewater generated during the processing of per ton raw
hide/skins
Processing operation (load kg/ton of raw hide/skins)
Unhairing/ Deliming Chrome Post-
Pollution load Soaking liming and bating tanning tanning Finishing
Wastewater 9.0–12.0 4.0–6.0 1.5–2.0 1.0–2.0 1.0–1.5 1.0–2.0
generated
(m3 or kL)
TSS 11–17 53–97 8–12 5–10 6–11 0–2
COD 22–33 79–122 13–20 7–11 24–40 0–5
BOD 7–11 28–45 5–9 2–4 8–15 0–2
Cr – – – 2–5 1–2 –
Sulphides – 3.9–8.7 0.1–0.3 – – –
NH3-N 0.1–0.2 0.4–0.5 2.6–3.9 0.6–0.9 0.3–0.5 –
TKN 1–2 6–8 3–5 0.6–0.9 1–2 –
Chlorides 85–113 5–15 2–4 40–60 5–10 –
Sulfates 1–2 1–2 10–26 30–55 10–25 –
Adapted from Dixit et al. (2015)
36 G. Saxena et al.

4 Environmental Pollution and Toxicity Profile of Tannery

Wastewater

TWW is ranked as one of the major environmental pollutants among all the
industrial wastewaters (Verma et al. 2008; Gupta et al. 2012). The presence of a
variety of toxic and hazardous chemicals such as chromium, chlorophenols, form-
aldehydes, STs, oils, resins, biocides, detergents and phthalates etc. in TWW
creates a negative image of LIs (Lofrano et al. 2013; Dixit et al. 2015). The toxicity
of chemicals used during leather processing is summarized in Table 3. The waste-
water generated from Common Effluent Treatment Plant (CETP) contains high
BOD, COD, TDS and a variety of toxic heavy metals especially chromium, which
makes it potentially toxic for humans and other living beings (Mondal et al. 2012;
Lofrano et al. 2013; Dixit et al. 2015). In addition, TWW also contains a mixture of
chemical compounds, which are used during leather processing and are not get
properly degraded even after the conventional treatment and have a negative impact
on living organisms and environment (Alvarez-Bernal et al. 2006; Oral et al. 2007;
Kumar et al. 2008; Tigini et al. 2011; Siqueira et al. 2011; Shakir et al. 2012;
Lofrano et al. 2013; Saxena and Bharagava 2015).

Table 3 Applications, toxicity and LD50 for chemicals used during leather production in leather
industry (Adapted from Kumar et al. 2008; Dixit et al. 2015)
LD50 in
rats (oral
Name of chemicals Applications mg/kg) Target organs
Pentachlorophenol Applied as a biocide in 2000 Eyes, nose, skin, respiratory
(PCP) (a carcinogen) preservative for raw hides/ tract, blood, kidney, liver,
skins immune system and repro-
ductive system
Di-butyl phthalate Applied as a plasticizer in 7499 Eyes, lungs, gastrointestinal
(DBP) (a endocrine artificial leather (GI) tract and testes
disrupting chemical) manufacturing
Benzyl butyl phthal- Applied in preparation of 2330 Eyes, lungs, liver and repro-
ate (BBP) micro-porous artificial ductive system
(a endocrine leather coating/water
disrupting chemical) vapour-permeable sheet
materials
Bis(2-ethylhexyl) Applied as a plasticizer in 30,000 Liver and testes
phthalate (DEHP) artificial leather
(a endocrine manufacturing
disrupting chemical)
Short chain, chlori- Additive for leather treat- 3090 Liver, kidney and thyroid
nated paraffin’s ment (gives smoothness),
leather clothing and belts
and as oiling agent
(continued)
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 37

Table 3 (continued)
LD50 in
rats (oral
Name of chemicals Applications mg/kg) Target organs
Anthracene Additive during tanning 16,000 Kidneys and liver
(a carcinogen)
Nonyl phenol Applied during finishing 1475 Blood. Lungs, eyes, skin,
(a endocrine central nervous system
disrupting chemical (CNS), kidneys and testes
and xenoestrogen)
N-methyl Applied as a coalescene, 3914 Eyes, kidneys, lymphatic
pyrrolidone plasticizers and wetting system, liver, lung and testes
agents
Methyl Applied as biocide 1800 Skin and eyes
isothiazolinone
(a carcinogen)
Organotin com- Applied as a catalyst 175 GI tract and liver
pounds (Dibutyl tin)
(a carcinogen)
Azo dyes (Orange II) Applied as a dyeing agent 3418 Blood, liver and testes
(a carcinogen)
Hexachlorobenzene Applied for raw hide/skins 10,000 Reproductive system
(a carcinogen) preservation
Chromium Applied as a tanning agent 3250 Kidneys, CNS and hemato-
(a carcinogen) poietic system
Formaldehyde Applied in finishing of 100 Eyes and lungs
(a carcinogen) leather
Arsenic Applied in finishing of 763 Liver, kidneys, skin, lungs
(a carcinogen) leather and lymphatic system
Sodium dichromate Applied in preparation of NA Blood, kidneys, heart, lungs
chrome-tanning salts and eyes
Cobalt dichloride Applied in dyeing and 80 Skin, lungs, liver, kidney and
finishing heart
Cadmium sulfate Applied as fastening 280 Lungs, liver, tissues and
(Pigment) agents and used in marking reproductive system
and surfacing of material.
Lead chromate Applied as fastening 1000 Lungs, liver, tissues and
(pigment) agents and used in marking reproductive system
and surfacing of material.
NA not available

TWW is a major source of water and soil pollution. The dark brown color blocks
the sunlight penetration, and thus, reduces the photosynthetic activity and oxygen-
ation of receiving water bodies and hence, becomes detrimental to aquatic life
(Song et al. 2000; Kongjao et al. 2008; Bakare et al. 2009; Mwinyihija 2010;
Carpenter et al. 2013). In addition, the depletion in dissolved oxygen encourages
the anaerobic condition, which leads to the putrefying odour of receiving water
bodies (Rai et al. 2005; Sahu et al. 2007; Verma et al. 2008). TWW also causes
38 G. Saxena et al.

eutrophication of polluted water bodies and thus adversely affecting the ecological
functioning of aquatic resources (Rai et al. 2005; Durai and Rajasimmam 2011;
Schilling et al. 2012; Dixit et al. 2015). The high concentration of heavy metals in
sediments of the Ganga river and its tributaries has been reported (Singh et al. 2003;
Tare et al. 2003; Bhatnagar et al. 2013). The increase in the salinisation of rivers
and groundwater has led to the reduction in soil fertility and quality of drinking
water in Tamil Nadu, India (Money 2008). It has been estimated that over 55,000 ha
of land has been contaminated by TWW and around five million peoples are
affected by low quality of drinking water and social environment (CSIRO 2001;
Sahasranaman and Jackson 2005). TWW is also reported to inhibit the nitrification
process (Szpyrkowicz et al. 2001; Trujillo-Tapia et al. 2008; Lofrano et al. 2013) as
well as to cause a huge foaming problem on surface waters (Schilling et al. 2012).
Moreover, the treated/partially treated TWW causes severe toxic effects in fishes
and other aquatic organisms. The genotoxicity and mutagenicity of water polluted
with TWW has been evaluated by the micronucleus test and the comet assay by
using fish Oreochromis niloticus (Matsumoto et al. 2006). De Nicola et al. (2007)
have studied the toxicity of mimosa tannin and phenol-based syntans on sea urchin
(Paracentrotus lividus and Sphaerechinus granularis) during the early develop-
mental stages and on marine algal cell growth (Dunaliella tertiolecta) and reported
the sea urchin embryogenesis was affected by vegetable tannins and syntan water
extracts at a level of 1 mg L
1. Afaq and Rana (2009) also studied the impact of
leather dyes (Bismarck brown and acid leather brown) on the protein metabolism in
fresh water teleost, Cirrhinus mrigala (Ham.) and reported a significant decrease in
total protein content in teleost treated with leather dyes. In addition, the toxic
effects of TWW on the survival and histopathological parameters in the different
organs of fishes Channa punctatus and Oreochromis mossambicus have been
studied (Mohanta et al. 2010; Navaraj and Yasmin 2012). However, the toxic
effects of TWW on the hematological parameters of a common fish Tilapia
mossambica and fresh water fish, Labeo rohita (Hamilton) has also been recently
studied (Lesley Sounderraj et al. 2012; Praveena et al. 2013). Further, TWW was
also reported to interfere with the metabolic processes by altering the activity of
oxidative enzymes in different organs of guppy fish, Poecilia reticulate and thereby
causing cellular injury as a result of exposure (Aich et al. 2011, 2015).
Further, the presence of pathogens in water and wastewater has been reviewed
by many workers (Bharagava et al. 2014; Saxena et al. 2015). TWW are also highly
rich in organic and inorganic constituents and thus, may provide a chance to a
variety of pathogenic bacteria to flourish and contaminate the receiving water
bodies as these constituents may act as a source of nutrients (Verma et al. 2008;
Bharagava et al. 2014). Recently, Chandra et al. (2011) have reported the presence
of various types of organic pollutants (OPs) and bacterial communities in two
aeration lagoons of a CETP used for the degradation and detoxification of TWW
in India and also tested the toxicity of TWW on mung bean (Phaseolus mungo) in
terms of seed germination and seedling growth. In addition, various authors have
also assessed the bacteriological quality of TWW and reported the presence of a
variety of pathogenic bacteria remained in TWW even after the secondary treat-
ment process (Verma et al. 2008; Ramteke et al. 2010; Bharagava et al. 2014).
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 39

Generally, LIs discharges their wastewater into nearby canals/rivers, which are
directly/indirectly being used by farmers for the irrigation of agricultural crops
(Trujillo-Tapia et al. 2008; Gupta et al. 2012). This practice leads to the movement
of potentially toxic metals like chromium from water to crop plants that ultimately
reach into the human/animal body and cause toxicity (Sinha et al. 2008; Chandra
et al. 2009). However, the chromium toxicity mainly depends on the chemical
speciation and thus, the associated health effects are influenced by the chemical
forms of exposure (Rameshraja and Suresh 2011). It is well reported that chromium
(VI) is a potent carcinogen for humans, animals, plants as well as microbes as it
enters the cells via surface transport system and get reduced into chromium (III)
form and causes various genotoxic effects (Ackerley et al. 2004; Aravindhan
et al. 2004; Matsumoto et al. 2006; Tripathi et al. 2011; Raj et al. 2014). Thus,
the use of Cr loaded TWW for the irrigation of agricultural crops disrupts the
several physiological and cytological processes in cells (Shanker et al. 2005;
Chidambaram et al. 2009; Gupta et al. 2012) leading to the reduction in root and
shoot growth and biomass, seed germination, seedling growth (Lopez-Luna
et al. 2009; Hussain et al. 2010), and also induces the chlorosis, photosynthetic
impairment and finally leading to the plant death (Akinici and Akinci 2010; Asfaw
et al. 2012). However, the effect of TWW on seed germination and seedling growth
is governed by its concentration and it is crop-specific. In a recent study conducted
on mung bean (Vigna radiate (L.) wilczek) by Raj et al. (2014), the percent
inhibition of seed germination was 90 % and 75 %, when seeds were treated with
25 % untreated and treated TWW, respectively. Moreover, it is also reported that
treated and adequately diluted TWW can be used for the irrigation of agricultural
crops as it provides a reliable source of water supply to farmers and contains
valuable plant nutrients especially N, P, K and also add organic matter to soil
(Trujillo-Tapia et al. 2008; Durai and Rajasimmam 2011; Asfaw et al. 2012;
Sangeetha et al. 2012; Kohli and Malaviya 2013). Further, the genotoxic and
mutagenic effects of TWW and agricultural soil irrigated with TWW has been
recently studied (Alam et al. 2009, 2010).
In addition, the inappropriate discharge of TWW also leads to significant levels
of soil pollution as well as acidification because of high salt loads in wastewater
(Chowdhury et al. 2004; Alvarez-Bernal et al. 2006; Mwinyihija 2010; Raj
et al. 2014). High sulfide content in TWW also causes the deficiency of some
micronutrients in soil such as Zn, Cu and Fe etc. (Raj et al. 2014). However, Cr
(VI) alters the structure of soil microbial communities and reduces their growth and
finally retards the bioremediation process and if it enters into the food chain, causes
skin irritation, eardrum perforation, nasal irritation, ulceration and lung carcinoma
in humans as well as animals along with accumulation in placenta impairing the
fetal development in mammals (Cheung and Gu 2007; Chandra et al. 2011; Asfaw
et al. 2012). In addition, the exposure to chlorinated phenols is possible particularly
to pentachlorophenol (PCP), which is highly carcinogenic, teratogenic and muta-
genic in nature and causes toxicity to living beings by inhibiting the oxidative
phosphorylation, inactivating the respiratory enzymes and damaging the mitochon-
drial structure (Jain et al. 2005; Verma and Maurya 2013; Tripathi et al. 2011).
40 G. Saxena et al.

The high concentration of PCP can also cause the obstruction in circulatory system
of lungs, heart failure and damage to central nervous system (USDHHS 2001;
Tewari et al. 2011; Dixit et al. 2015).
In addition, TWW also contain azo dyes that are highly persistent in nature due to
their complex chemical structure and xenobiotic nature leading to the environmental
pollution (Nachiyar and Rajkumar 2003; Gurulakshmi et al. 2008; Mahmood
et al. 2013; Baccar et al. 2011; Patel et al. 2012; Preethi et al. 2013; Dixit
et al. 2015). Thus, the removal of azo dyes from TWW is essential because of their
high mutagenicity, carcinogenicity and intense coloration problems of contaminated
aquatic resources (Osugi et al. 2009; Saratale et al. 2010). The discharge of azo dyes
into the surface water also leads to the aesthetic problems and obstruct the light
penetration and oxygen transport into the water bodies and finally affecting the aquatic
life (Khalid et al. 2008; Chen et al. 2011). Moreover, these dyestuffs have been also
reported to cause some other serious problems such as dermatitis, skin and eye
irritation and respiratory problems in human beings (Keharia and Madamwar 2003).
Further, there has been an increasing concern regarding the release of many
endocrine disrupting compounds (EDCs) along with TWW in environment. EDCs
disturb the delicate hormonal balance and compromise the reproductive fitness of
living beings and ultimately may lead to carcinogenesis (Dixit et al. 2015). Kumar
et al. (2008) have detected many EDCs like nonylphenol (NP), 4-aminobiphenyl,
hexachlorobenzene and benzidine in TWW collected from the northern region of
India and tested their toxicity on the reproductive system of male rats. However, the
presence of phthalates (EDCs) such as bis(2-ethylhexyl)phthalate (DEHP), dibutyl
phthalate (DBP), bis(2-methoxyethyl)phthalate in TWW has been also reported
(Alam et al. 2009, 2010). Therefore, the adequate treatment of TWW prior to its
final disposal into the environment is required.

5 Treatment Approaches for Tannery Wastewater

and Chemicals

TWW is a major source of soil and water pollution and it is therefore essential to
adequately treat the TWW prior to its safe disposal into the environment. This can
be achieved by using physical, chemical and biological methods either alone or in
combination.

5.1 Physico-Chemical Treatment Approaches

5.1.1 Coagulation/Flocculation

Coagulation is the destabilization of colloids by neutralizing the forces that keep

them apart. Cationic coagulants provide positive charge to reduce the negative
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 41

charge (zeta potential) of the colloids. As a result, the particles collide to form
larger particles (flocs) whereas flocculation is the action of polymers to form
bridges between the flocs, and bind the particles to form large agglomerates or
clumps. There are a number of coagulants such as aluminium sulfate (AlSO4), ferric
chloride (FeCl3), ferrous sulfate (FeSO4) etc. that are used to reduce the organic
load (COD) and suspended solids (SS) as well as to remove toxic metals mainly
chromium from TWW (Lofrano et al. 2013).
However, coagulants are pH specific and their effectiveness largely depends on
their type and concentration and characteristics of the wastewater to be treated
(Song et al. 2004). Ates et al. (1997) reported >70 % removal of COD and <5 mg L
1
of total chromium from TWW using alum and FeCl3 based-CF. Song et al. (2004) also
reported 30–37 % removal of total COD, 74–99 % of chromium and 38–46 % of SS
by using 800 mg L
1 of alum at pH 7.5 from TWW containing 260 mg L
1 of
suspended solids, 16.8 mg L
1 of chromium, 3300 mg L
1 of COD at pH 9.2 and
finally concluded that FeCl3 based CF proved better results than alum based-CF.
Chowdhury et al. (2013) have reported 92 % removal of COD and 96 % of
chromium from TWW using FeCl3 at the concentration of 150 mg L
1 at pH
7 followed by sand-stone filtration process. In addition, Shegani (2014) also
reported 81.60 %, 98.34 %, 92 %, 75.00 %, 70.00 %, 69.20 % and 50 % removal
of COD, ammonia, nitrate, hexavalent chromium, phosphate, chloride and H2S,
respectively by using coagulants Ca(OH)2 and FeSO4 · 7H2O, but a low reduction
in sulfate (19.00 %) and TSS (13.00 %) and an increase in TDS (15.60 %) were
observed.
Moreover, some coagulants such as poly-aluminium chloride (PAC), poly-
aluminium silicate (PASiC) and poly-aluminium ferric chloride (PAFC)
([Al2(OH)nCl6-n]m.[Fe2(OH)nCl6-n]m) have been developed with improved coag-
ulation efficiency to minimize the residual coagulants in treated wastewater (Gao
et al. 2004; Lofrano et al. 2013). Lofrano et al. (2006) reported >75 % removal of
COD and >95 % of TSS from TWW at all doses of alum (800–900–
1000–1200 mg L
1) using PAFC (900 mg L
1) at pH 8.5. Yoganand and Umapathy
(in press) have also applied a green methodology for the recovery of chromium
(VI) from TWW using newly synthesized quaternary ammonium salt and reported
99.99 % removal of chromium (VI) from TWW.

5.1.2 Adsorption

Adsorption is typically used for the removal of toxic metals especially chromium
from TWW. There are a number of studies available on the use of adsorbents such
as bentonite clay, cement kiln dust, activated carbon etc. for the treatment of TWW
(Fadali et al. 2004; Fahim et al. 2006; Tahir and Naseem 2007). Further, the use of
chitin-humic acid based hybrid and ground shrimp shells as adsorbent for the
significant removal of Cr(III) from TWW has been reported (Santosa et al. 2008;
Fabbricino et al. 2013). Moreover, the use of lime/bitten based coagulants and
activated carbon as a post treatment of TWW is also suggested (Ayoub et al. 2011).
42 G. Saxena et al.

5.2 Biological Treatment Approaches

Biological approaches are the eco-friendly methods for the treatment of industrial
wastewaters and involve the stabilization of waste by decomposing them into
harmless inorganic solids either by aerobic or anaerobic processes. The most
commonly used processes for the biological treatment of TWW are the Activated
sludge process (ASP) and Upflow Anaerobic Sludge Blanket (UASB) process
(Durai and Rajasimmam 2011).

5.2.1 Aerobic Treatment

In an aerobic treatment process, the waste decomposition rate is fast and also not
characterized by unpleasant odours but a large amount of sludge is generated. There
are several studies on the aerobic treatment of TWW using ASP as has been
reported earlier by many workers (Jawahar et al. 1998; Eckenfelder 2002; Tare
et al. 2003; Vidal et al. 2004; Hayder et al. 2007; Ramteke et al. 2010) and some of
the important findings are summarized in Table 4.
TWW is highly saline in nature due to high load of salts, which are used for the
preservation of raw hides/skins (Sundarapandiyan et al. 2010) and therefore, causes
some serious problems in the biological treatment of TWW. The major problems
include (Sivaprakasam et al. 2008): (a) limited adaptation of conventional cultures due
to higher salt concentration (>3–5 % w/v), that therefore could not effectively treat
TWW (b) salt adaptation of cultures is easily lost when subjected to salt free medium,
and (c) changes in the ionic strength (salt concentration from 0.5 to 2 % w/v) cause cell
disruption even with the acclimatized cultures and finally lead to system failure.
However, the high concentration of poorly biodegradable compounds such as tannins
and other toxic metals inhibit the biological treatment processes (Schrank et al. 2004). Cr
(VI) is reported to inhibit the growth of heterotrophs as well as nitrifying/denitrifying
bacteria (Stasinakis et al. 2002; Farabegoli et al. 2004). To overcome this problem, a
Sequencing Batch Reactor (SBR) is highly efficient to carry out the biological treatment
and nitrogen removal from TWW in the presence of inhibitors due to its low cost, flexible
operation and selection and enrichment of a particular microbial species (Farabegoli
et al. 2004; Ganesh et al. 2006; Murat et al. 2006; Durai and Rajasimmam 2011;
Rameshraja and Suresh 2011; Faouzi et al. 2013; Lofrano et al. 2013).
Moreover, the fluctuation in temperature range also has adverse effects on the
nitrification process. The fluctuation in the temperature range significantly affects
the removal of organic carbon and nitrogen from TWW whereas it has a minor
influence on COD removal efficiency (4–5 %) that has been studied for a full-scale
activated sludge process based treatment plant used for TWW (Gorgun et al. 2007).
Further, the improvement in the performance of the nitrification process through
increased aeration and total nitrogen removal efficiency (up to 60 %) at a temper-
ature range between 21 and 35  C during an intermittent aeration type of operation
has been reported (Insel et al. 2009).
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 43

Table 4 Microorganisms reported in the degradation of tannery wastewater

COD BOD Cr
removal removal removal
References Microorganisms (%) (%) (%)
Kim Brachymonas denitrificans 98.3 – 88.5
et al. (2014)
Noorjahan E. coli 90 90 63.8
(2014) Bacillus sp. 95.4 95.4 73.5
Elmagd and Mixed culture 98.3 98.4 98.3
Mahmoud
(2014)
Sharma and Fusarium chlamydosporium SPFS2-g 71.80 – –
Malaviya
(2013)
Yusuf B. subtilis 87.6 – –
et al. (2013) P. fragi 85.2
El-Bestawy Providencia vermicola W9B-11, 79.16 94.14 93.66
et al. (2013) Escherichia coli O7:K1 CE10, Bacillus sp.
58, Bacillus amyloliquefaciens T004,
Pseudomonas stutzeri M15-10-3, Bacillus
sp. PL47
Mandal Thiobacillus ferrooxidans 69 72 5
et al. (2010)
Nanda Nostoc sp. 37.8 48.6 –
et al. (2010)
Ramteke E. coli 98.46 90 –
et al. (2010) Vibrio sp. 87.5
Pseudomonas sp. 96.15
Sivaprakasam P. aeruginosa, B. flexus, E. homiense, 80 – –
et al. (2008) S. aureus
Vankar and Trichoderma sp. – – 97.93
Bajpai (2008)
Onyancha S. condensate – – >75
et al. (2008) R. hieroglyphicum
Srivastava Acenetobacter sp. – – 90
et al. (2007)
Rajasimman Mixed culture 46–85 65–93 –
et al. (2007)
Wang A. Thiooxidans – – 99.7
et al. (2007)
Srivastava and Aspergillus sp. – – –
Thakur (2006) Hirsutella sp. 70
Lefebvre Halophiles 95 – –
et al. (2005)
Thanigavel Mixed culture 89.5 – –
(2004)
Shakoori Bacterial strain – – 87
et al. (2000)
44 G. Saxena et al.

5.2.2 Anaerobic Treatment

The use of anaerobic treatment processes to treat TWW is an interesting option as

compared to aerobic treatment process because of low energy consumption and
sludge production. However, its full scale application has several drawbacks
(Mannucci et al. 2010): i) continuous production of sulfide (from sulfate reduction)
in absence of alternative electron acceptors such as oxygen and nitrate; ii) high
protein content affects the selection of biomass, slow down the kinetics of hydro-
lysis and also inhibit the sludge formation, and iii) requirement of an additional
aerobic treatment to meet the high COD removal.
The sulfide mainly inhibits the methanogenesis process during the anaerobic
treatment of TWW and this might be due to the direct toxicity of sulfide, substrate
competition between the sulfate reducing bacteria and methanogenic bacteria and
precipitation of trace elements (Midha and Dey 2008; Rameshraja and Suresh 2011;
Mannucci et al. 2014). However, the mechanisms of sulfide toxicity are not well
understood.
The anaerobic treatment of TWW is mainly performed by using either the
anaerobic filters (AF) composed of both upflow anaerobic filters (UAF) and
down-flow anaerobic filters (DAF) or Upflow Anaerobic Sludge Blanket (UASB)
reactors (Lefebvre et al. 2006; Rajasimman et al. 2007; El-Sheikh et al. 2011; Dixit
et al. 2015). Beside these, the use of expanded granular sludge bed (EGSB) and
anaerobic baffled reactor (ABR) for the treatment of TWW is also suggested
(Zupancic and Jemec 2010).
In addition, the anaerobic treatment of TWW is more favorable in tropical
countries having higher temperatures such as India, Pakistan, China, and Brazil
etc. as compared to European countries (Durai and Rajasimmam 2011; Mannucci
et al. 2014). In these countries, the spread of new and large industrial areas to
establish the LIs favor the development of centralized WWTPs. However, the
application of anaerobic treatment processes at large scale makes it possible to
balance the high operation and management costs with energy saving over the
traditional aerobic treatment processes.

5.2.3 Constructed Wetlands and Treatment Ponds

Constructed wetlands (CWs) are man-engineered, eco-friendly systems designed to

remove the pollutants from highly polluted industrial and municipal wastewaters.
The use of CWs for the treatment of industrial wastewater has developed rapidly in
current years and is now successfully employed to remove a diverse array of
pollutants from wastewaters.
The proper functioning of a wetland system depends on the complex relationship
between the plants, microorganisms, soil, wastewater characteristics and opera-
tional parameters (Aguilar et al. 2008). In this regard, several efforts have been
made to select the suitable plant species capable to tolerate and remove the
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 45

pollutants from TWW (Mant et al. 2004; Calheiros et al. 2007, 2008, 2012),
selecting the suitable supporting media/substrate for proper growth and develop-
ment of wetland plants (Calheiros et al. 2008), as well as to study the bacterial
community dynamics in CWs (Aguilar et al. 2008; Calheiros et al. 2009a, b). The
plant roots and rhizomes are the major sites of microbial degradation/transforma-
tion of pollutants and subsequently the purification of wastewater because microbes
form a biofilm on root surface and substrates (Stottmeister et al. 2003; Gagnon
et al. 2007; Munch et al. 2007). However, the availability of nutrients or other
environmental parameters affects the biofilm formation (Kierek-Pearson and
Karatan 2005). Therefore, the detailed profiling of complex microbial populations
is required to understand the proper functioning of CWs and phytoremediation
processes (Chandra et al. 2015). Culture-dependent techniques are known to be
insufficient to study the microbial community structure because numerous micro-
organisms are unculturable in lab conditions (Ward et al. 1990). Hence, molecular
techniques such as random amplified polymorphic DNA (RAPD), polymerase
chain reaction (PCR) and denaturation gradient gel electrophoresis (DGGE), is
used for the study of microbial community structure, composition and diversity in
CW system (Calheiros et al. 2009a, 2012).
Mant et al. (2004) have studied the phytoremediation potential of Penisetum
purpureum, Brachiaria decumbens and Phragmites australis in CWs for the
removal of chromium (ranging from 10 and 20 mg Cr dm
3) from TWW. In
addition, the potentials of Canna indica, Typha latifolia, P. australis, Stenotaphrum
secundatum and Iris pseudacorus in CWs for the treatment of TWW under two
different hydraulic loading rates at 3 and 6 cm/day has been studied and it was
found that only P. australis and T. latifolia were able to establish successfully
(Calheiros et al. 2007). Further, these authors also evaluated Arundo donax and
Sarcocornia fruticosa in two series of horizontal subsurface flow CWs used to treat
TWW received from a conventional biological treatment plant and reported the
removal of COD (51 and 80 %) and BOD5 (53 and 90 %) for COD inlet:
68–425 mg L
1 and for BOD5 inlet: 16–220 mg L
1 (Calheiros et al. 2012). In
addition, the use of TWW as a growth medium for Arthrospira (Spirulina) has been
recently suggested (Dunn et al. 2013). However, the chromium salt can be retained
in wetlands with non-specialized supporting media (Dotro et al. 2012).
On the other hand, the use of treatment ponds for the treatment of TWW can also
be an effective approach. The effect of different environmental parameters like pH,
temperature and dissolved oxygen on the efficiency of a pilot-scale advanced
integrated wastewater treatment pond system (AIWTPSs) used to treat TWW has
been reported by Tadesse et al. (2004). They also suggested a combination of
advanced facultative pond (AFP), secondary facultative pond (SFP) and maturation
pond (MP) in a series for the effective treatment of TWW. Recently, Kumar and
Sahu (2013) have designed the anaerobic pond (AP) for the treatment of TWW in
Egypt.
46 G. Saxena et al.

5.3 Emerging Treatment Approaches

The TWW discharged even after the conventional treatment process still contains
many refractory and recalcitrant organic pollutants (ROPs) and thus, require further
treatment for environmental safety. Therefore, in order to overcome this problem,
the use of emerging treatment technologies is increasing in recent years.

5.3.1 Membrane Technologies

Membrane technologies (MTs) are used for the mechanical separation/purification

of industrial wastewater with the help of permeable membranes. MTs operate
without heating and therefore use less energy than conventional thermal separation
processes such as distillation, sublimation or crystallization. The use of MTs in LIs
is becoming popular in current years because of continually reducing cost and ever
extending application possibilities.
The MTs offer many economic benefits to the LI, especially the recovery of
chromium from TWW (Lawanda et al. 2009; Ranganathan and Kabadgi 2011) and
are used for purification/reuse of wastewater and chemicals of deliming/bating
liquor (Gallego-Molina et al. 2013), reduction of pollution load due to unhairing
and degreasing (De Pinho 2009; Wang et al. 2011), removal of salts as well as in the
biological treatment of TWW for its reuse (Lofrano et al. 2013). Several
membrane-based technologies such as cross flow microfiltration (MF), ultrafiltra-
tion (UF), nanofiltration (NF), reverse osmosis (RO) and supported liquid mem-
branes (SLMs) can be used for the removal of pollutants from TWW (Lofrano
et al. 2013; Dixit et al. 2015). However, the use of reverse osmosis (RO) with a
plane membrane has been suggested as a post treatment for the removal of refrac-
tory compounds such as chlorides and sulfates, and resulted in the production of
high quality of permeate that allowed the reuse of tannery wastewater within the
production cycle and thus, reduced the groundwater consumption (De Gisi
et al. 2009). The economical evaluation of membrane filtration technologies has
been discussed in detail by Scholz and Lucas (2003). The successful integration of
MTs in a conventional purification process for TWW streams has been recently
reported by Stoller et al. (2013).

5.3.2 Membrane Bioreactors

A membrane bioreactor (MBR) is the combination of a membrane process like

microfiltration or ultrafiltration with a suspended growth bioreactor, and is now
widely used for municipal and industrial wastewater treatment. MBRs offer several
advantages over the conventional activated sludge treatment process (CASTP) such
as elimination of sludge from settling basins, independence of process performance
from filamentous bulking or other phenomena that affect the sludge settleability
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 47

(Munz et al. 2008; Suganthi et al. 2013; Dixit et al. 2015). The presence of tannins
in TWW reduces the kinetics of nitrification without large differences between the
biomass selected with either the CASTP or the MBR used (Munz et al. 2009).
However, the major drawbacks of membrane application are the significant fouling
due to clogging, adsorption and formation of cake layer by pollutants like residual
organics, dyes, and other impurities onto the membrane (Srinivasan et al. 2012;
Stoller et al. 2013). However, the extensive work is in progress to reduce the
bio-fouling problem in MBRs. Further, a hybrid membrane bioreactor (HMBR),
which is the integration of various treatment technologies, may be a solution to
overcome the bio-fouling problem of MBRs. More recently, the efficiency of
HMBR (activated sludge process + electro-coagulation) for the effective removal
of COD and color from TWW satisfying the discharge limits set by Tamil Nadu
Pollution Control Board (TPCB) India has been evaluated (Suganthi et al. 2013).

5.3.3 Anammox Technology

The anammox technology is used for the anaerobic removal of ammonia from
TWW and it is currently emerging because of its low cost and energy consuming
nature (Anjali and Sabumon 2014). It involves the anoxic oxidation of ammonia
with nitrite as a preferred electron acceptor and consumes 50 % less oxygen, 100 %
less organic carbon and saves 90 % of operational costs in sludge disposal as
compared to the conventional nitrification/denitrification processes (Anjali and
Sabumon 2014). Therefore, industries, producing wastewaters having a high con-
centration of ammonia, are showing increased interest in the anammox process.
However, the long start-up time and inhibitive nature in the presence of organic
carbon and NH4-N limits its field applications. Therefore, it is imperative to
develop the mixed consortium capable of anammox in the presence of organic
compounds. Further, the development of mixed microbial consortium consisting of
ammonia oxidizing bacteria, anammox bacteria, and denitrifying bacteria is also
expected to treat the wastewaters containing both ammonia and organic carbon.

5.3.4 Advanced Oxidation Processes

Advanced oxidation processes (AOPs) refers to the set of chemical treatment pro-
cesses that use strong oxidizing agents (O3, H2O2) and/or catalysts (Fe, Mn, TiO2) and
sometimes also use the high-energy radiation, e.g., UV light (Schrank et al. 2004;
Naumczyk and Rusiniak 2005; Srinivasan et al. 2012; Dixit et al. 2015). AOPs are
based on the production and utilization of hydroxyl radicals, which are strong oxidiz-
ing agents and quickly and non-selectively oxidize a broad range of recalcitrant
organic pollutants such as benzoquinone, benzene, phenols, chlorophenols, dyes and
formaldehyde in less time (Lofrano et al. 2013; Dixit et al. 2015). Generally, the AOPs
are used to treat the secondary treated wastewater and therefore known as tertiary
treatment (Audenaert et al. 2011). In this, most of the pollutants get converted into
48 G. Saxena et al.

stable inorganic compounds such as H2O, CO2 and salts, i.e. they undergo minerali-
zation (Rameshraja and Suresh 2011). The treatment efficiency of AOPs is mostly
evaluated in terms of COD removal however, TOC is a more suitable parameter to
study the state of mineralization (Schrank et al. 2004, 2005; Costa et al. 2008;
Monteiro Paschoal et al. 2009). There are various types of AOPs such as fenton
oxidation, photo-oxidation, photo-fenton oxidation, ozonation, photocatalysis and
electrochemical treatment processes that are applied to treat the TWW (Rameshraja
and Suresh 2011; Lofrano et al. 2013; Dixit et al. 2015). The overall goal of AOPs used
for TWW treatment is to reduce the pollution load and toxicity to such an extent that
the treated TWW may be reintroduced into the receiving water bodies or reused during
the process. The important findings of various AOPs applied to treat the TWW are
presented in Table 5.

Table 5 Findings of some advanced oxidation processes (AOPs) applied for the treatment of
tannery wastewater
Influent
Wastewater COD Operation parameters and
References AOPs type (mg L
1) reduction in pollutants
Modenes Photo-Fenton Equalized 11,878 COD removal (90 %), TSS
et al. (2012) (UV/Fe2+/H2O2) tannery removal (50 %), Fe2+
wastewater (0.4 g L
1) and H2O2
(15 g L
1), Irradiation time
(540 min)
Houshyar Ozone Pre- 2177 COD removal (30–70 %),
et al. (2012) alkalized Time (120 min), Ozone
tannery flow rate (1–8 g/h)
wastewater
Di Iaconi Ozone Biologically 2900 COD removal (97 %), TSS
et al. (2010) treated tan- removal (96 %), TKN
nery removal (91 %), Surfactants
wastewater removal (98 %), Color
removal (96 %)
Sundarapandiyan Electrochemical Synthetic 10,715 COD removal (89 %), pH
et al. (2010) treatment tannery 3–9, Current density
wastewater (0.006–0.024 A cm
2),
Time (120 min)
Preethi Ozone Raw tannery 5000 COD removal(60 %), O3 flow
et al. (2009) wastewater rate (2  10
3 m3 min
1),
Time (20–120 min) and pH
(4)
Espinoza- Electrochemical Equalized 17,618 COD removal (51–56 %),
Quinones treatment tannery TSS removal (30–70 %),
et al. (2009) wastewater Electric current flow rate
(0–10 A at 0–30 V), Time
(30–45 min)
Costa Electrochemical Equalized 1005 Maximum phenol removal
et al. (2008) treatment tannery (TOC) (83.9 %), Maximum TOC
wastewater removal (40.5 %), Time (5 h
of electrolysis)
(continued)
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 49

Table 5 (continued)
Influent
Wastewater COD Operation parameters and
References AOPs type (mg L
1) reduction in pollutants
Kurt et al. (2007) Electrochemical Raw tannery 2810 COD removal (70 %),
treatment wastewater Electric current (15.0 W),
Time (10 min) and pH (3)
Pokrywiecki UV/H2O2 Coagulated 200–800 COD removal (60 %), H2O2
Sauer tannery (0.5 h L
1), Time (4 h)
et al. (2006) wastewater
Schrank Fenton reagent Coagulated 130 COD removal (80 %),
et al. (2005) tannery H2O2/Fe2+ (500/100 w/w),
wastewater Time (2 h)
Schrank Photocatalysis Coagulated/ 2365 COD removal (6 % at pH
et al. (2004) (UV/TiO2) Flocculated 3), TOC removal (11 % at
tannery pH 3), BOD removal (15 %
wastewater at pH 7)
Dogruel Ozone Biologically 835 COD removal (30 %),
et al. (2004) treated tan- Ozone flow rate
nery (42.8 mg min
1), Time
wastewater (5 min)
Dantas Fenton reagent Raw tannery 1803 COD removal (70 %), Time
et al. (2003) wastewater (20 min), pH (2.5) and
Temperature (25  C)

Despite of a broad range of applications, AOPs also have some drawbacks that
should also be considered before its applications. The presence of scavenger
compounds such as an excess amount of H2O2 sometime can act as a hydroxyl
scavenger instead of hydroxyl radical source, which interferes with the COD
determination and reduces the reaction kinetics making the process uneconomical
(Kang 2002; Lofrano et al. 2013). Further, the TWW also contains a significant
amount of chromium, which may be oxidized from trivalent to hexavalent form, a
more toxic form during oxidation treatment and thus, it is highly recommended to
evaluate the possible effects of oxidation on the transformation of chromium atoms
in different oxidation states (De Laat et al. 2004; Dogruel et al. 2006; Rameshraja
and Suresh 2011; Lofrano et al. 2013). For these reasons, AOPs should be applied
more properly to the segregated streams of wastewater containing high amount of
aromatic compounds for fenton treatments or high content of salts for electrochem-
ical treatment.
Moreover, AOPs still have not been put commercially at large scale (especially
in the developing countries) even upto today mostly because of the relatively high
costs. Nevertheless, their high oxidative capability and efficiency make AOPs
popular techniques for the tertiary treatment of recalcitrant organic and inorganic
pollutants. The increasing interest in wastewater reuse and more stringent regula-
tions regarding the water pollution prevention and control are currently accelerating
the implementation of AOPs at large scale.
50 G. Saxena et al.

5.4 Combinatorial Treatment Approaches

In the previous section, various treatment approaches applied for TWW have been
discussed. However, these treatment approaches have some serious limitations that
need to be addressed further. The presence of residual organics, dyes, and other
impurities in TWW even after the biological treatment processes followed by the
RO based membrane technologies have been reported as the major drawbacks
leading to membrane fouling and finally failure of treatment processes (Srinivasan
et al. 2012). Therefore, a combined application of physico-chemical treatment
methods with biological treatment methods or various oxidation processes is
generally preferred for the effective TWW treatment. Some of the combined
treatment methods applied for TWW is presented in Table 6.

Table 6 Combined treatment approaches reported for tannery wastewater

Combined treatment
References applied Pollutants Optimum parameters
Suganthi Hybrid membrane COD and Color Electric current density (15 mA/cm2),
et al. (2013) bioreactor Electrocoagulation time (15 min),
Membrane area (0.0143 m2),
Membrane spacing (0.22 μm),
pH (7.4 and 9)
Srinivasan Biological treatment COD and color Ozone flow rate (3 g/h), Time (24 h),
et al. (2012) with ozonation pH (12), Hydraulic retention time
(36 h), sludge age (10 days)
Mandal Biological treatment COD, BOD, Fenton reagent (6 g FeSO4 and 266 g
et al. (2010) with fenton Chromium, H2O2), Time (30 min: fenton oxida-
oxidation Sulphide and tion, 72 h: biological oxidation), pH
Color (2.5), Temperature (30  C)
Iaconi SBBR with COD, BOD, Sludge production (0.4 kg TSS/kg
et al. (2009) ozonation TSS, TKN and COD), Time (5760 and 2160 h)
color
Rodrigues Photo-electrochemi- COD and Electric current density (36 mA/cm2),
et al. (2008) cal treatment with NH4-N Ti electrode, Membrane area
electrodialysis (1.72 dm2), Membrane spacing
(0.75 mm)
Dogruel Biological COD Ozone flow rate (20 g/h), Reaction
et al. (2006) treatment time (30 min)
+ ozonation with
biological treatment
Naumczyk AOP with fenton COD and Fenton reaction time (30 min)
and Rusiniak reagent Ammonia
(2005)
Szpyrkowicz Electrochemical COD and Sludge production (1.37 kg/m3/day),
et al. (2005) treatment with bio- Ammonia Electrolysis time (49 min)
logical treatment
(continued)
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 51

Table 6 (continued)
Combined treatment
References applied Pollutants Optimum parameters
Kennedy CAACO system COD, BOD, Volumetric loading rate (0.7376 m3/m3
et al. (2004) Sulphide and day), Surface loading rate
sulfate (0.2438 m3/m3/day)
Iaconi SBBR with ozone COD, TKN and Sludge production (0.05 kg VSS/kg
et al. (2004) oxidation TSS COD)
Iaconi SBBR with COD, TKN and Sludge production (4 kg/kg COD),
et al. (2003) ozonation TSS Organic loading (2.6 kg COD/m3/day)
Di Iaconi SBBR with ozone COD, Ammo- O3 flow rate (8.7 mg O3/min), Sludge
et al. (2002) oxidation nia and SS production (4 kg TSS/kg COD)

6 Waste Minimization, Operation, Treatment

and Management in Leather Industries

6.1 Solid Waste Generation, Treatment and Management

In LIs, apart from liquid waste, a large amount of chromium containing tanned solid
waste (non-biodegradable sludge) is also generated during leather processing (Dixit
et al. 2015). The waste generated finds very limited applications and its disposal
causes serious environmental problems (Mwinyihija 2010, 2012). The types and
quantity of solid waste generated during the processing of 1 t of raw hide/skins have
been presented in Table 7.
However, the conventional treatment and disposal of solid waste is not environ-
mentally feasible because of transformation and leaching of Cr(III) from tanned
waste to Cr(VI) and groundwater, emission of nitrogen oxide (NOx), hydrogen
cyanide (HCN) and ammonia (NH3) (Fathima et al. 2012; Dixit et al. 2015).
Therefore, the combination of aerobic treatment (for degradation of low molecular
weight compounds) with anaerobic treatment (for further degradation of metabo-
lites) may be a suitable treatment option for tannery waste. The methodologies for
the treatment of liquid tannery waste using solid tannery waste have been recently
discussed by Fathima et al. (2012). Further, after treatment the remaining waste can
be recycled and utilized as useful by products and raw materials. Some of the
technological options, which are proposed for the handling and management of
solid waste, are presented in Fig. 1.
52 G. Saxena et al.

Table 7 Nature and Nature of solid waste generated Quantity (kg)

quantity of solid waste
Salt from handshaking 80
generated during the
processing of 1 t of Salt from solar pans (not realized) 220
raw hide/skins Hair (pasting ovine) 100
Raw trimmings 40
Lime sludge (mostly bovine) 60
Fleshing 120
Wet blue trimmings (grain splits) 30
Chrome splitting (bovine) 65
Chrome shaving (mostly bovine) 95
Buffing dust (including shaving bovine after 65
crust)
Dyed trimmings 35
Dry sludge from CETPs 125
Adapted from Rao et al. (2004) and Thanikaivelan et al. (2005)

Tannery waste Biogas

Fat
Fleshings
Glue Bioferilizers
Trimmings

Annual Poultry Foods Cosmetics

Tanned Shavings
Chrome Recovery
Lime Shavings Bonded Leather Leather Boards

Chrome Sludge
Land Filling Brick Making Sulphide Recovery
Lime Sludge
Liqour Sound Proof Roofing Material
Buffling Dust
Artificial Suedge
Light Weight Bricks
Vegetable
Tannins
Briquetted Fuel Mud Thinner

Fig. 1 Technological options for handling and management of solid waste generated during
leather production (adapted from ILTIP 2010)

6.2 Gaseous Emission and Control

The emission of gaseous waste such as ammonia (during deliming, unhairing and
drying), hydrogen sulphide (released in TWW from sulphides if pH is >8), particu-
late matter (containing chromium from reduction of chromate or from buffling), and
volatile organic compounds (hydrocarbons, amines and aldehydes) from LIs during
the different steps of tanning processes may also cause atmospheric pollution (Dixit
et al. 2015). Therefore, the proper control of gaseous emission should be required.
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 53

6.3 Clean Technologies for Hazards Minimization

Environmental pollution due to LIs is a major cause of concern and its mitigation
requires some cleaner technologies (CTs) or also regarded as greener technologies
(GTs) for pollution prevention and hazards minimization. CTs utilize the processes
that avoid the use of harmful chemicals or promote the use of eco-friendly chemical
and cut or eliminate the gaseous emissions and wastes and therefore are cost-
effective. Various CTs for the tannery waste minimization and control have been
reviewed by many workers (Thanikaivelan et al. 2005; Lofrano et al. 2013; Islam
et al. 2014; Dixit et al. 2015).
The development and implementation of CTs at large scale require (a) careful
auditing and assessment of the toxicological effects of chemicals used in leather
processing, (b) to avoid the use of environmentally susceptible chemicals, (c) to
ensure the maximum uptake of chemicals used, (d) assessment of environmental
impact of waste generated during leather processing, and (e) optimization of pro-
cesses for the best economic returns. However, the success of CTs depends on the
following parameters: (a) reduction of pollution load in terms of quantity and quality,
(b) tanner’s benefit in terms of leather quality and/or cost reduction,
(c) reproducibility of the process, (d) economic feasibility of process (e) wide market
opportunities. Further, the use, assessment and selection of best available techniques
(BAT) for the tanning of hides and skins have been discussed (IPPC 2013).

7 International Legislations Scenario for Tannery

Wastewater and Chemicals

7.1 Legislations for Discharge Limits of Tannery Wastewater

In developing countries, according to the environmental pollution control regula-

tions set by various national and international environment protection agencies, LIs
are forced to set up the WWTPs either individually as ETP or collectively as CETP
and the treated wastewater should comply with the discharge standards. The
compliance with the discharge standards has not always been practical either
because the laws are too ambitious or unrealistic in case of certain parameters, or
they have lacked the effective instrumentation and institutional support. Some
environment protection laws have not succeeded because they do not match the
technical requirements and economic reality of the country or they do not have the
institutional support to implement them into consideration.
In India, during the 1990s, several LIs were ordered to close their units as these
could not meet the discharge standards, while many of them paid huge compensa-
tion for the damage caused due to the groundwater contamination (CSIRO 2001).
For the sake of LIs, the Indian government has offered subsidies to construct
54 G. Saxena et al.

Common Effluent Treatment Plants (CETPs) for the treatment of TWW. Notwith-
standing, the pollution problems are still common due to high operation and
management cost associated with CETPs and thus causing illegal dumping of
wastewater (Beg and Ali 2008). In Uganda, the main leather industry was found
to dump its wastewater directly into a wetland adjacent to Lake Victoria (The
Monitor 2009) whereas in Croatia, the pollution abatement cost exceeded the
compensation cost against the irresponsible behaviour of LIs (EcoLinks 2001).
The environmental pollution due to the discharge of TWW has become a serious
concern in recent years. For pollution prevention from TWW and its chemicals, the
United Nations Industrial Development Organization (UNIDO) has compiled the
standard limits for the discharge of TWW into water bodies and sewers from
several countries worldwide (UNIDO 2000, 2003). The discharge standards for
some of the countries are presented in Table 8. The discharge limits for TWW may
vary from country to country and are either related to the quality of treated
wastewater or the quality of receiving water bodies (Dixit et al. 2015).

7.2 Legislations for Leather Chemicals

A variety of chemicals are used during the leather processing, which are highly
toxic to living beings and cause environmental pollution. In this view, some
countries have also made regulations for the production, import and sale of leather
products containing harmful chemicals. The chemicals and their permissible limits
in leather and leather products approved in some countries are summarized in
Table 9. However, the European Chemical Agency (ECHA) has also prioritized
and restricted the use of a few chemicals in LIs under Substances of Very High
Concern (SVHC), which are considered to be hazardous for environment and
human beings (UK REACH 2009). However, all the chemicals are still used in
leather making and therefore their proper control is urgently required.

8 Challenges and Future Prospects

Today’s the LIs are facing some serious challenges posed by the public and
governments mainly due to the environmental pollution and there is a public outcry
against the industry. The major challenges faced by LIs include:
(a) Increased cost of leather production per unit area due to the stringent environ-
mental regulations.
(b) Increasing demand of raw material i.e. raw hides, skins and semi-finished
leathers.
(c) Lack of advanced processing techniques and waste treatment technologies in
developing countries.
Table 8 Discharge limits for tannery wastewater into water bodies and sewers in some countries
Italy Turkey Netherlands Argentina Brazil Egypt China Vietnam Indonesia Bangladesh India Pakistan
S. No. Parameter Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb *Sa Sb Sa Sb Sa **Sb
1. pH 5.5–9.5 5.5–9.5 6–9 6–10 6–10 6.5–10.0 5.5–10 5.5–10 5.0–9.0 6.0–9.0 6.0–9.0 6.0–9.0 6.0–9.0 5.5–9.0 5.5–9.0 6.0–9.0 5.5–9.0 5.5–9.0 6.0–9.0 6.0–9.0
2. Temperature 30–35 30–35 40 40 45 45 <40 40 35 0 35 40 45 40–45 40–45 40

C
3. Conductivity
(μS/cm)
4. Suspended 40–80 200 150 350 150 350 30 500 70– 400 100 200 150 150 500 100 600 200
solids (mg/L) 150
a
5. Settleable 0.5 0.5 1.0 5–10 10
solids
6. BOD5 (O2 40 250 100 250 5 250 50 200 60 20–30 400 20– 600 50 100 150 150 250 30 500 80
mg/L) 100
a a
7. COD (mg/L) 160 500 200 800 250 700 30–40 700 100– 1000 100 400 300 300 400 250 150
300
8. TDS (mg/L) 800– 2000 2100 2100
1200
a a
9. Sulphide 1 2 1 2 1 0.2 5 1 10 1 10 0.5 1.0 2.0 2 2 1
(S2
) (mg/L)
10. Chrome (III) 4 1 5 1.5 2.0 1.0 2.0 2 2
(mg/L)
a a
11. Chrome 0.2 0.2 0.3 0.5 0.5 0.1 0.1
(VI) (mg/L)
12. Total Chrome 2 4 2 5 0.05 2 0.5 2 0.5 0.05 5–10 1.5 1.5 2.0 2.0 2 2 2.0 2 2 1
(mg/L)
a a a a a
13. Chloride 1200 1200 200 1000 1000 1000
(mg/L)
a a a
14. Sulfates (mg/L) 1000 1000 1700 3 1000 1000 1000 1000
15. Ammonia 10–15 30 3 10 5 100 100 10 10 50 50 40
(mg N/L)
a a a a
16. TKN 100 10 30 10 60 60
(mg N/L)

(continued)
Table 8 (continued)
Italy Turkey Netherlands Argentina Brazil Egypt China Vietnam Indonesia Bangladesh India Pakistan
S. No. Parameter Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb Sa Sb *Sa Sb Sa Sb Sa **Sb
17. Phosphorous 1
(mg P/L)
18 Oil/grease 20 40 20 100 100 100 20–30 100 100 100 10–15 100 10 30 5 5 20 10 20 10
(mg/L)
a a a
19. Phenol (mg/L) 0.5 1 10 0.5 0.5 0.1–0.5 0.001– 0.5 2.0 1 5–50 5–50 0.3
0.002
20. Detergents 1.5
(mg/L)
21. Solvents
(mg/L)
21.1. Hydrocarbons 0.2 0.4
(mg/L)
21.2. Nitrogenous 0.1 0.2
(mg/L)
21.3. Chlorinated 1 2 1 2 5
(mg/L)

Sa: Surface, Sb: Sewer, *Sa: Bangladesh has no discharge standards for tannery wastewater into surface water, **Sb: Pakistan has no discharge standards for tannery
wastewater into sewer
a
Spaces left blank indicate that parameters which are not specified and considered as specific requirements that need to be fulfilled
Table 9 Maximum permissible limits of chemicals of leather products in some countries (adapted from Dixit et al. 2015)
Residual substances limits for chemicals European Union Germany Austria Denmark France Netherlands Switzerland
Azodyesa 30 ppm
Pentachlorophenol 30 ppm 5 ppm 30 ppm 30 ppm 30 ppm 30 ppm
Phthalates 0.1 % 0.1 % 0.05 %
PCBs and PCTsb Not to be used
Biocidesc 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 10 ppm
Hexavalent Chromium 3 ppm 10 ppm
Cadmium 100 ppm 75 ppm 100 ppm 100 ppm
Arsenic Nil
Lead 90 ppm
Organotin Compounds Nil
Specific Flame Retardants <0.1 %
Formaldehyde >1500 ppm >1500 ppm 200–400 ppm 120 ppm
a
Azo dyes: Biphenyl-4-ylamine; 4-aminobiphenyl xenylamine; Benzidine; 4-Chloro-o-toluidine; 2-Naphthylamine; o-aminoazotoluene; 4-amino-20 ,
3-dimethylazobenzene; 4-o-tolylazo-o-toluidine; 5-Nitro-o-toluidine; 4-chloroaniline; 4-methoxy-m-phenylenediamine; 4,40 -methylenediani-line;
3,30 -dichlorobenzidine; 3,30 -dimethoxybenzidine o-dianisidine; 3,30 -dimethylbenzidine 4,4-bi-o-toluidine; 4,4-methylenedi-o-toluidine; 6-methoxy-m-tolui-
dine; p-cresidine; 4,40 -methylene-bis-(2-chloroaniline); 4,40 -oxydianiline; 4,40 -thiodianiline; o-toluidine; 2-aminotoluene; 4-methyl-m-phenylenediamine;
2,4,5-trimethylaniline; o-anisidine 2-methoxyaniline; 4-amino-azobenzene
b
PCBs: Polychlorinated biphenyls; PCTs: Polychlorinated terphenyls
c
Biocides (23 approved): Human hygiene biocidal products; Private area and public health area disinfectants and other biocidal products; Veterinary hygiene
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety

biocidal products; Food and feed area disinfectants; Drinking water disinfectants; Preservatives; In-can preservatives; Film preservatives; Wood preservatives;
Fibre, leather, rubber and polymerised materials preservatives; Masonry preservatives; Preservatives for liquid-cooling and processing systems; Slimicides;
Metalworking-fluid preservatives; Pestcontrol; Rodenticides; Avicides; Molluscicides; Piscicides; Insecticides, acaricides and products to control other
arthropods; Repellents and attractants; Other biocidal products; Preservatives for food or feedstocks; Antifouling products; Embalming and taxidermist fluids;
Control of other vertebrates
57
58 G. Saxena et al.

(d) Lack of specific dedicated industrial areas for the positioning of LIs.
(e) Poor capacity utilization leading to the higher financial cost and overheads
charges.
(f) Lack of financial support from government.
The mitigation of these challenges requires the financial support at large scale
from the government for the upgradation of LIs, especially small scale industries
(Xu and Zhiping 2011). Hence, there is a need to revisit the leather processing again
for making the continued sustainability of LIs in near future because LIs are the key
drivers of many nation’s economy.

9 Summary and Conclusion

(a) LIs are one of the major sources of environmental (soil, water, air) pollution.
(b) TWW is a highly polluted wastewater among all the industrial wastewater.
(c) Currently, the processes used for leather making in several developing coun-
tries are traditional and required to be optimized for chemical and water
consumption.
(d) The search for some other suitable tanning agents to replace the chromium is
urgently required for eco-sustainable tanning process.
(e) Sulfide is highly toxic but the mechanism of toxicity is not well understood and
implementation of adequate technology for H2S desorption is required.
(f) Membrane bioreactors and constructed wetlands are the eco-friendly options
for the treatment of TWW and its management, but have some limitations that
need to be addressed in the future.
(g) The combinatorial approaches involving physical or chemical with biological
treatment process to treat the TWW may give satisfactory results as compared
to the individual treatment process.
(h) The emerging treatment approaches like membrane filtration and oxidation
processes are also currently using/under analysis.
(i) AOPs are much promising to remove the recalcitrant organic pollutants but
there is a still need to optimize these for best economic returns.
(j) The emerging anammox technology for the anaerobic removal of ammonia
from TWW is under research and further investigation is required.
(k) A complete understanding of toxicity profiles of TWW may also be helpful in
achieving the appropriate treatment solutions for future tanneries.
(l) Locating LIs in a planned industrial area is another common approach to abate
the environmental pollution in parallel to strengthen the discharge limits
for TWW.
(m) The use of eco-friendly chemicals, water minimization technologies and
wastewater treatment/purification and recycling as per the EU integrated
pollution prevention strategy and greening policy will be fruitful for solving
the environmental problems.
Toxicity of Tannery Wastewater and its Treatment for Environmental Safety 59

Thus, we can say that there is no treatment method at its best to treat TWW and
its chemicals. However, it is clear that continuous efforts are required in order to
search for the better treatment approaches for TWW in near future. Further, the
emerging treatment approaches like AOPs in combination with biological treatment
processes will remain an agenda for the policy makers and water sector profes-
sionals to apply the best pollution prevention solution for the future tanneries.

Acknowledgements Authors are extremely grateful to the “Science and Engineering Research
Board” (SERB), Department of Science & Technology (DST), Government of India (GOI), New
Delhi, India for financial support as “Major Research Project” (Grant No.: SB/EMEQ-357/2013)
for this work and the University Grant Commission (UGC) Fellowship received by Mr. Gaurav
Saxena is also duly acknowledged.

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