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Organic Pollutants in Tannery Wastewater and Bioremediation Approaches for

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Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 119

Chapter 4

Organic Pollutants in Tannery

Wastewater and Bioremediation
Approaches for Environmental
Safety

GAURAV SAXENA AND RAM NARESH BHARAGAVA1

ABSTRACT
Leather industries (technically called as tannery industries)
play an important role in the economy of developing
countries, but these industries are also the major source
of soil and water pollution due to the generation of huge
volume of wastewater, which contain a variety of toxic
organic pollutants and heavy metals. Since, there has been
a growing environmental concern regarding the release of
various organic pollutants in tannery wastewater, which do
not degrade much during the secondary treatment process
in industries. It has been shown that biological treatment
processes, which are currently regarded as the most eco-
friendly and cost effective approaches, but inefficient for
complete removal of recalcitrant organic pollutants from
tannery wastewater, which goes into the environment and
cause serious soil and water pollution along with serious

1. 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.
120 Bioremediation of Industrial Pollutants

health hazards to humans and animal life. Therefore, it

is imperative to adequately treat/detoxify the tannery
wastewater for environmental safety. The physico-chemical
approaches used for the remediation of tannery wastewater
are not efficient because these use a large amount of chemicals
and are not environmental friendly. In addition, the physico-
chemical treatment approaches are very costly generate a
very large amount of sludge in the environment, which create
causes pollution in the environment. To overcome the problem
of environmental pollution, bioremediation approaches may
be the suitable option for the better treatment of tannery
wastewater and its management. Therefore, this chapter
provides a detail account on the nature and characteristics
of tannery wastewater, environmental pollution and toxicity
profile of tannery wastewater and bioremediation approaches
for the degradation and detoxification of tannery wastewater
for environmental safety.
Keywords: Environment pollution, Toxic effects,
Bioremediation approaches and Phytoremediation.

Introduction
Leather industries (LIs) play an important role in the national economy
of developing countries like India, Pakistan, Bangladesh, Sri Lanka etc.
Approximately, 22700.5 M sq. feet of leather is produced annually in the
world (FAO, 2008), whereas the annual world trade for leather sector is
estimated as 80,000,000,000 US$ (ITC, 1999). 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 exporter of leather and leather products. In
developing countries, most of the tanneries are at the small-scale level
and cannot afford the expensive treatment plant at their own cost because
the effluent treatment plants (ETPs) are excessively costly to construct
and operate, and also produce a large quantity of sludge (Saxena and
Bharagava, 2015). Therefore, a common ETP (CETP) is used for the treatment
of wastewater generated from a cluster of tannery industries. The CETP
is an activated sludge process (ASP)-based treatment plant that receives
wastewater from cluster of tanneries through pipelines or tanks and after
treatment, the treated wastewater from CETP is finally discharged into the
water body.
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 121

But, LIs are also one of the major polluters worldwide because these
discharge a large volume of complex wastewater. During leather production,
a variety of chemicals with large volume of water are used to convert raw
hide/skins into leather or leather products and generates a large volumes
of wastewater, which is 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 (Lofrano 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; 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 (Rai
et al., 2005; Kongjao et al., 2008; Durai and Rajasimman, 2011). However,
the major pollutants present in TWW include chromium, tannins or syntans
(STs), phenolics and azo dyes (Lofrano et al., 2013; Dixit et al., 2015).
The high concentration and low biodegradability of pollutants present
in TWW is a major environmental concern and thus, it is imperative to
effectively treat/remediate the TWW before its final disposal into 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 chapter highlighted the problem of environmental
pollution and toxic effects of TWW and its chemicals and a detailed account
of bioremediation approaches for its safe disposal into the environment. The
emerging approaches have been discussed with their merits and demerits
has been also discussed

Steps in 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 process is classified into vegetable or chrome tanning
depending on the type of tanning reagent (tannins or chromium) used
(Mannucci et al., 2010) (Table 1). The steps and overall process of leather
production is presented in Fig. 1. However, the tanning process involves
different steps and chemicals for different end products and the kind and
122 Bioremediation of Industrial Pollutants

amount of waste generated may vary in a wide range of quantity and

nature (Lofrano et al., 2013).
Table 1: Comparison between vegetable tanning and chrome tanning process
Parameters Vegetable tanning Chrome tanning
Tanning agent Vegetable tannins (VTs) Chromium salt
Nature Organic tanning Inorganic (mineral) tanning
Action Slow process Fast process
Cost Costly affairs Cost effective
Time Time consuming Less time consuming
Geographical Used in developed countries Used in developing countries
use and few developing countries
Products Heavy leather like shoe soles, Light weight leathers like shoe
luggage, saddlery and belt etc. uppers, garments and bag etc.
Product Higher thermal stability and Softer and more pliable leather
characteristics water resistant
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
necessary when using animal
skins, such as ship skins
Environmental Does not require prior Generation of chromium
Impact preparation of pickling and containing sludge and
therefore contribution to wastewater is still a major
pollution load from sulfate environmental problem of
salts are lower hence chrome tanning process
ecofriendly, but VTs are hard
to biodegrade. Thus, waste
bearing VTs degrade slowly

During 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 goes 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 disturb the ecological balance on
the other hand (Saravanbahavan et al., 2004; Dixit et al., 2015). Moreover,
the sulphonated oils and synthetic tannins or syntans (STs) (an extended
set of chemicals such as phenol, naphthalene, formaldehyde, melamine and
 Organic Pollutants in Tannery Wastewater & Bioremediation Approaches...

Fig 1: Schematic representation of leather production and type of pollutants released.

123
124 Bioremediation of Industrial Pollutants

acrylic resins) are also used in tanning/retanning process to make the leather
more softer (Lofrano et al., 2008; Lofrano et al., 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
leather products in Europe (Lofrano et al., 2008). In addition, the Directive
(1999/815/EC) has directed the industries to label the products if contain
> 0.5% phthalates (benzyl butyl phthalate, di-butyl phthalate and di-ethyl
hexyl phthalate) due to its reproductive toxic potential (EU, 2003). The use
of o-phenyl phenol is restricted for leather finishing due to its carcinogenic
potential (EPA, 2007) as well as 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 sulphate and lead
chromate (fastening agents) are highly toxic in nature (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).

Wastewater Generation and Characteristics

In 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 generation is lagely depends on the nature of
raw material, finishing product and production processes applied (Lofrano
et al., 2013).
Tannery wastewater (TWW) is a basic, dark brown coloured waste
having high COD, BOD, TDS, chromium (III) and phenolics with high pH
and strong odor (Durai and Rajasimman, 2011; Suganthi et al., 2013; Dixit
et al., 2015). However, the characteristics of TWW may vary from industry
to industry, raw materials and chemicals used, type of final product and
the production processes adopted by LIs (Rameshraja and Suresh, 2011;
Lofrano et al., 2013).
During leather production, the beamhouse and tanning operation are
the highly pollution causing steps because beamhouse operation contribute
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 125

high organic and sulfide content whereas tanning operation contribute high
salts (of chloride, ammonium, chromium and sulfate) concentration 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 Rajasimman, 2011). The retanning and
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 contribute low fraction of salt in TWW that is predominantly
originated from the hide/skins in the soak liquor (USEPA, 1986; Lofrano
et al., 2013). The physico-chemical characteristics of TWW are presented
in Table 2.
Table 2: Physico-chemical characteristics of treated tannery wastewater
Parameters Wastewatera Permissible limit
pH 8.85 6.0–8.0
Conductivity (moles cm ) −1
11,000 850
Total solids (TS; mg l ) −1
2,477 2,200
Alkalinity (mg l ) −1
729 500
Total dissolved solids (TDS; mg l ) −1
2,219 2,100
Total suspended solids (TSS; mg l ) −1
258 100
DO (mg l−1) 2.8 4.0–6.0
BOD (mg l−1) 267 30
COD (mg l ) −1
458 250
Sulfate (mg l ) −1
2,400 1,000
Chloride (mg l ) −1
354 600
Magnesium (mg l ) −1
234 200
Phosphate (mg l ) −1
5.5 5.0
Nitrate (mg l ) −1
12.08 10
Total nitrogen (mg l 1) −1
229.04 780
Fluoride (mg l−1) 3.5 2.0l
Phenol (mg l−1) 10.5 1.0
Total chromium (mg l ) −1
19.57 2.0
Oil and grease 17 10
Cr 6+
(mg l )
−1
3.5 0.1
Cu (mg l )
2+ −1
1.9 3.0
126 Bioremediation of Industrial Pollutants

Parameters Wastewatera Permissible limit

Mn (mg l )
2+ −1
1.6 2.0
Zn (mg l )
2+ −1
3.8 5.0
As3+ (mg l−1) 0.30 0.2
Pb2+ (mg l−1) 0.08 0.1
Cd (mg l )
2+ −1
ND b
2.0
Ni (mg l )
2+ −1
3.2 2.5
Co (mg l )
2+ −1
0.22 1.5
Fe (mg l )
2+ −1
3.5 3.0

a
Average of triplicate samples; bNot detected; Adapted from Verma et al. (2015), Saxena
and Bharagava (2015)

Organic Pollutants Present in Tannery Wastewater

In case of leather tanning industry, there has been an increasing
environmental concern regarding the release of various organic pollutants
(OPs) in TWW, which do not degrade much during the secondary treatment
process in industries and goes in the environment. The treatment of TWW
is very complex due to the presence of a variety of chemical compounds,
which are used during the tanning process (Schrank et al., 2004). It has been
shown that biological treatment processes involving microbes are known as
the most environmental friendly and cost-effective but inefficient for effective
removal of OPs from TWW, which goes into the environment causing serious
threats to soil and water ecosystem as well as to humans and animal
life. However, the various types of OPs are reported by few researchers
(Table 3), which were detected and identified by gas chromatography-mass
spectroscopy (GC-MS) analysis of TWW extracted with different solvent
systems. But, there is no much information available about OPs that remain
in TWW after secondary treatment and their biodegradation as well as
their toxicological effects in the environment.

Environmental Pollution and Toxicological Effects of Tannery Wastewater

TWW is ranked as one of the major environmental pollutant among all
the industrial wastewaters (Verma et al., 2008; Gupta et al., 2012). The presence
of a variety of hazardous chemicals such as chromium, chlorophenols,
formaldehydes, STs, oils, resins, biocides, detergents 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 4. The wastewater generated from Common Effluent Treatment Plant
(CETP) contains high BOD, COD, TDS and a variety of toxic heavy metals
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 127

especially chromium, which makes it potentially toxic for humans and other
living beings (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).
Table 3: Organic pollutants (OPs) identified in tannery wastewater using different
extraction solvents through GC-MS analysis.
Extraction Persistent Organic Pollutants References
solvent
Dichloromethane 2, 4-bis(1, 1-dimethyl) phenol Alam et al. (2009)
(DCM)
10-Methylnonadecane
Docosane
bis(2-ethylhexyl)phthalate
2,6,10-Dodecatrien-1-ol- 3, 7, 11-trimethyl
acetate
Methanol 1, 3-Hexadien-5-yn Alam et al. (2009)
1, 2-Benzenedicarboxylic acid, diisooctyl
ester
Actonitrile + 2,2,3-Trimethyl oxepane Alam et al. (2009)
acetone
Benzene
3-Nitropthalic acid
Chloroform + 2-(2-hydroxy)-2 propyl cyclohexanol Alam et al. (2010)
hexane
Dibutyl phthalate
Tetratetracontane
bis (2-methoxyethyl)phthalate
Hexatriacontane
Heneicosane
Docosane
Tricosane
1,2-Benzenedicarboxylic acid, diisooctyl
ester
(diisooctyl phthalate)
Dichloromethane Phenyl N-methylcarbamate Alam et al. (2010)
(DCM)
Caprolactam
Octacosane
2,6,10,15-tetramethylheptadecane
128 Bioremediation of Industrial Pollutants

Extraction Persistent Organic Pollutants References

solvent
Nonadecane
2,6,10,14-tetramethylhexadecane
Triacontane
Heptadecane
Tetracosane
Eicosane
9-methylnonadecane
Heptadecane
1,2-benzenedicarboxylic acid, diisooctyl
ester
(diisooctyl phthalate)
Dotriaconatn
Ethyl acetate L-(+)-Lactic acid Chandra et al.
(2011)
Acetic acid
Benzene
2-hydroxy-3-methyl-butanoic acid

Adapted from Saxena and Bharagava (2015).

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 oxygenation 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 eutrophication of polluted water bodies
and thus adversely affecting the ecological functioning of aquatic resources
(Rai et al., 2005; Durai and Rajasimman, 2011; Schilling et al., 2012; Dixit et
al., 2015). The high concentration of heavy metals in sediments of Ganga
river and its tributaries has been reported (Singh et al., 2003; Tare et al.,
2003). 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 5 million peoples are affected by
low quality of drinking water and social environment (CSIRO, 2001). 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) (Fig. 2).
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 129

Table 4: Applications, toxicity and LD50 for chemicals used during leather
production in leather industry
Chemicals Applications LD50 in Target organs
rats (oral
mg/kg)
Pentachlorophenol Applied as a biocide 2000 Eyes, nose, skin,
(PCP) (carcinogen) in preservative for respiratory tract, blood,
raw hides/skins kidney, liver, immune
system and reproductive
system
Di-butyl phthalate Applied as a 7499 Eyes, lungs,
(DBP) plasticizer in artificial gastrointestinal (GI) tract
leather manufacturing and testes
Benzyl butyl Applied in 2330 Eyes, lungs, liver and
phthalate (BBP) preparation of micro- reproductive system
porous artificial
leather coating/water
vapour-permeable
sheet materials
Bis(2-ethylhexyl) Applied as a 30.000 Liver and testes
phthalate (DEHP) plasticizer in artificial
leather manufacturing
Short chain, Additive for leather 3090 Liver, kidney and thyroid
chlorinated treatment (gives
paraffin’s smoothness), leather
clothing and belts
and as oiling agent
Anthracene (a Additive during 16,000 Kidneys and liver
carcinogen) tanning
Nonyl phenol (less Applied during 1475 Blood. Lungs, eyes, skin,
biodegradable) finishing central nervous system
(CNS) and kidneys
N-methyl Applied as a 3914 Eyes, kidneys, lymphatic
pyrrolidone coalescene, system, liver, lung and
plasticizers and testes
wetting agents
Methyl Applied as biocide 1800 Skin and eyes
isothiazolinone
(carcinogen)
Organotin Applied as a catalyst 175 GI tract and liver
compounds (Dibutyl
tin) (a carcinogen)
Chemicals Applications LD50 in Target organs
rats (oral
mg/kg)
130 Bioremediation of Industrial Pollutants

Azo dyes (Orange Applied as a dyeing 3418 Blood, liver and testes
II) (carcinogen) agent
Hexachlorobenzene Applied for raw hide/ 10,000 Reproductive system
(carcinogen) skins preservation
Chromium (a Applied as a tanning 3250 Kidneys, CNS and
carcinogen) agent hematopoietic system
Formaldehyde (a Applied in finishing 100 Eyes and lungs
carcinogen) of leather
Arsenic (a Applied in finishing 763 Liver, kidneys, skin, lungs
carcinogen) of leather and lymphatic system
Sodium dichromate Applied in Not Blood, kidneys, heart,
preparation of available lungs and eyes
chrome-tanning salts
Cobalt dichloride Applied in dyeing 80 Skin, lungs, liver, kidney
and finishing and heart
Cadmium sulphate Applied as fastening 280 Lungs, liver, tissues and
(Pigment) agents and used reproductive system
in marking and
surfacing of material.
Lead chromate Applied as fastening 1000 Lungs, liver, tissues and
(pigment) agents and used reproductive system
in marking and
surfacing of material.

Adapted from Dixit et al. (2015).

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 micronucleus test and
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 developmental 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 level of 1 mgLî1.
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
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 131

fish Tilapia mossambica and fresh water fish, Labeo rohita (Hamilton) has also
been recently studied (Sounderraj et al., 2012; Praveena et al., 2013).

Fig
Fig 2:
2: A h
huge
ug
ge fo
foam
foaming
a in
am ng pr
prob
problem
oble
ob
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lem ca
c
caused
us
sed bby
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ttannery
nner
nner
nn ery
y wawast
wastewater
stew
ewat
ater
er
on
on s
surface
urrfa
face
ce w
waters
a er
at ers
rs (Original
(O
Ori
r gi
g na
n l ph
p
photograph)
otog
ot ogra
og ra
aph
ph))

Further, the TWW 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 treatment process (Verma et al., 2008; Ramteke et al., 2010;
Bharagava et al., 2014).
Generally, LIs discharges their wastewater into nearby canals/rivers,
which is directly/indirectly is being used by farmers for the irrigation of
agricultural crop (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 and ultimately reached into the human/animals body
and cause toxicity (Sinha et al., 2008). However, the chromium toxicity is
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 (Matsumoto et al., 2006; Raj et al., 2014).
Thus, the use of Cr loaded TWW for the irrigation of agricultural crops
132 Bioremediation of Industrial Pollutants

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
(Akini and Akini, 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 provide
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 Rajasimman, 2011; Asfaw et al., 2012). 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 the
significant level of soil pollution as well as acidification because of high
salt load in wastewater (Alvarez-Bernal et al., 2006; Mwinyihija, 2010; Raj
et al., 2014). High sulphide 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
reduced their growth and finally retarding the bioremediation process and
if it enters in 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 particularly pentachlorophenol
(PCP), which is highly carcinogenic, teratogenic and mutagenic in nature and
causes toxicity to living beings by inhibiting the oxidative phosphorylation,
inactivating the respiratory enzymes and damage the mitochondrial structure
(Jain et al., 2005; Verma and Maurya, 2013). 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 (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).
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 133

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, 4-aminobiphenyl, hexachlorobenzene and
benzidine in TWW collected from northern region of India and tested
their toxicity on reproductive system of male rats. However, the presence
of phthalates (EDCs) such as bis(2-ethylhexyl)phthalate, Dibutyl phthalate,
bis(2-methoxyethyl)phthalate in TWW has been also reported (Alam et al.,
2009; 2010). Therefore, the adequate treatment/remediation of TWW prior
to its final disposal into the environment is required.

Bioremediation Approaches for Tannery Wastewater and its Chemicals

TWW is a major source of soil and water pollution and it is therefore
essential to adequately remediate/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. However, the physico-
chemical approaches used for the treatment of tannery wastewater are
highly expensive and environmentally destructive as these consume a large
quantity of chemicals to treat the wastewater and also generate a large
quantity of sludge in the environment and thereby these approaches are
not environmental friendly. To overcome these problems, bioremediation id
an eco-friendly tool for the treatment of tannery wastewater. Bioremediation
utilize microbes for the effective treatment of tannery wastewater without
any adverse effects on the environment.

Bioremediation Approaches
TWW is a high strength wastewater, which is characterized by very
high BOD, COD and TDS and contains a variety of organic and inorganic
pollutants such as chromium and sulphide with its low biodegradability
that is of serious environmental concern. The physico-chemical treatment
methods are not efficient and ecofriendly because these methods use a large
amount of hazardous chemicals and generate a large quantity of chromium
contaminated sludge in the environment. Therefore, the bioremediation is
134 Bioremediation of Industrial Pollutants

eco-friendly way to reduce the pollutants load from TWW prior to its safe
disposal into the environment.
Bioremediation is the eco-friendly method 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 remediation of TWW are
the Activated sludge process (ASP) and Upflow Anaerobic Sludge Blanket
(UASB) process (Durai and Rajasimman, 2011).

Aerobic Approach
In aerobic process, the waste decomposition rate is fast and also not
characterized by unpleasant odours, but a large amount of sludge is
generated. The findings of several studies on the aerobic treatment of TWW
using ASP are summarized in Table 5.
TWW is highly saline in nature 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), and 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 0.5-2% w/v) cause cell disruption even with the
acclimatized cultures and finally leads 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 well reported to inhibit the growth
of heterotrophs as well as nitrifying/denitrifying bacteria (Stasinakis et al.,
2002; Farabegoli et al., 2004). The Sequencing Batch Reactor (SBR), a type of
ASP effectively used for the biological treatment and nitrogen removal from
TWW in presence of inhibitors because of its low cost, flexible operation,
selection and enrichment of a particular microbial species (Farabegoli et al.,
2004; Durai and Rajasimman, 2011; Rameshraja and Suresh, 2011; Lofrano
et al., 2013).
Moreover, the fluctuation in temperature range also has adverse
effects on the nitrification process. The fluctuation in temperature range
significantly affects the removal of organic carbon and nitrogen from TWW
whereas have 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 nitrification process through increased aeration and total
nitrogen removal efficiency (up to 60%) at a temperature range between
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 135

21-35 ĈC during an intermittent aeration type of operation has been reported

(Insel et al., 2009).
Table 5: Microorganisms reported in the degradation of tannery wastewater
References Microorganisms COD BOD Cr
removal removal removal
(%) (%) (%)
Kim et al. (2014) Brachymonas denitrificans 98.3 - 88.5
Noorjahan (2014) E. coli 90 90 63.8
Bacillus sp. 95.4 95.4 73.5
Elmagd and Mixed culture 98.3 98.4 98.3
Mahmoud (2014)
Sharma and Fusarium chlamydosporium 71.80 - -
Malviya (2014) SPFS2-g
Yusuf et al. (2013) B. subtilis 87.6 - -
P. fragi 85.2
El-Bestawy et al. Providencia vermicola W9B- 79.16 94.14 93.66
(2013) 11, Escherichia coli O7:K1
CE10, Bacillus sp. 58,
Bacillus amyloliquefaciens
T004, Pseudomonas stutzeri
M15-10-3, Bacillus sp. PL47
Mandal et al. Thiobacillus ferrooxidans 69 72 5
(2010)
Nanda et al. Nostoc sp. 37.8 48.6 -
(2010)
Ramteke et al. E. coli 98.46 90 -
(2010) Vibrio sp. 87.5
Pseudomonas sp. 96.15
Sivaprakasam et P. aeruginosa, B. flexus, E. 80 - -
al. (2008) homiense, S. aureus
Vankar and Bajpai Trichoderma sp. - - 97.93
(2008)
Onyancha et al. S. condensate - - >75
(2008) R. hieroglyphicum
Srivastava et al. Acenetobacter sp. - - 90
(2007)
Rajasimman et al. Mixed culture 46-85 65-93 -
(2007)
Wang et al. (2007) Thiooxidans - - 99.7
Srivastava and Aspergillus sp. - - -
Thakur (2006) Hirsutella sp. 70
136 Bioremediation of Industrial Pollutants

References Microorganisms COD BOD Cr

removal removal removal
(%) (%) (%)
Lefebvre et al. Halophiles 95 - -
(2005)
Thanigavel (2004) Mixed culture 89.5 - -
Shakoori et al. Bacterial strain - - 87
(2000)

Bioremediation applies living microorganisms to degrade

environmental pollutants or to prevent pollution or it is a technology for
removing pollutants from the environment thus, restoring the original
natural surroundings and preventing further pollution. Microorganisms
(bacteria, fungi and actinomycetes) play a significant and vital role
in the bioremediation of chromium contaminated soil and industrial
wastewaters.
Megharaj et al. (2003) isolated chromium resistant bacterial strain Bacillus
cereus S-6 from effluents of tannery, which was used for the reduction
of toxic hexavalent chromium into less toxic trivalent chromium. At an
initial hexavalent chromium concentration of 100 øg/ml, the cytosol and
membrane preparation of the strain were able to reduce almost 67 and
43% of hexavalent chromium within 24 hrs incubation period while the
heat killed cytosol and membrane preparation reduced 24 and 18% within
the same time period. They reported that tannery effluent may change the
characteristics of soil and interfere with the intake of water by plants. The
presence of sulphide and chromium in tannery effluent affects plant life
and soil productivity.
Several reports have indicated biological reduction of hexavalent
chromium by microorganism both aerobes and anaerobes. Biological
reduction of hexavalent chromium usually occurs at a neutral pH range
and generates an insignificant quantity of chemical sludge as well as offers
potential cost-effective remediation strategy (Donati et al., 2003). Subsequent
studies have shown that the capacity for hexavalent chromium reduction is
widespread and is shown in organisms such as Bacillus subtilis, Pseudomonas
aeruginosa, Achromobacter, Eurydice, Micrococcus roseus and Escherichia coli
(Flores and Perez, 1999) as well as Pseudomonas ambigua (Gunha et al.,
2001), Pseudomonas fluorescens (Jonnalagadda et al.. 2007), Enterobacter cloacae
(Komori et al., 1990), Streptomyces sp. (Romanenko and Korenkov, 1977),
Pseudomonas putida (Schulin, 2007), D. desulfuricans and D. vulgaris (Lovely
and Phillips, 1994) and Pseudomonas liquefaciens (Sultan and Hasnain,
2005).
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 137

Srinath et al. (2002) studied that the Bacillus circulans and Bacillus
megaterium are able to bioaccumulate 34.5 and 32.0 mg chromium/g dry
weight, respectively and brought the residual concentration of hexavalent
chromium to the permissible limit in 24 hrs when the initial concentration
was 50 mg hexavalent chromium/L. They stated that biosorption of
hexavalent chromium was shown by Bacillus megaterium and another strain,
Bacillus coagulans. Living and dead cells of Bacillus coagulans biosorbed 23.8
and 39.9 mg chromium/g dry weight, respectively, whereas, 15.7 and 30.7
mg chromium/g dry weight was biosorbed by living and dead cells of
Bacillus megaterium, respectively.
Muhammed Faisal and Shahida Hasnain (2004) demonstrated that the
ability of Brevibacterium cells to accumulate toxic hexavalent chromium at
different chromate concentrations (100, 500 and 1000 øg/ml) in different time
intervals (15 min, 2 hours and 4 hours). They showed that the Arthrobacter
oxydans does a complete uptake of hexavalent chromium concentration (35
mg/ml) in about 10 days.
Igwe and Abia (2006) found that the chromium was bioremoved from
tannery wastewater by Aspergillus oryzae. Aspergillus oryzae can grow in
different concentration of chromium 120-1080 mg/L. They observed that
maximum biomass growth and chromium removal rate at pH, 3.3, trivalent
chromium concentration equal to 240 mg/L and inoculum size equal to
0.12% (dry weight) were 0.25 (dry weight ) and 94.2%, respectively. They
stated that bacterial strains were isolated and enriched from the contaminated
site of Tamil Nadu Chromates and Chemicals Limited (TCCL) premises,
Ranipet, Tamil Nadu, India. It was found that a bacterial concentration of
15+/-1.0 mg/g of soil (wet weight) 50 mg of molasses/g of soil as carbon
source were required for the maximum hexavalent chromium reduction.
The bioreactor operated at these conditions could reduce entire hexavalent
chromium (5.6 mg /g of soil) in 20 days.
Shaili Srivastava and Indu Shekhar Thakur (2006) studied the
relationship between the hexavalent chromium resistance of culturable
microbial community and hexavalent chromium resistance and reducing
ability strains of each population. Shaili Srivastava and Indu Shekhar Thakur
(2007) isolated chromium resistant bacterial strain Bacillus cereus S-6 from
effluents of tannery was used for the reduction of toxic hexavalent chromium
into less toxic trivalent chromium. At an initial hexavalent chromium
concentration of 100 øg/mL, the cytosol and membrane preparation of
the strain were able to reduce almost 67 and 43% of hexavalent chromium
within 24 hrs incubation period while the heat killed cytosol and membrane
preparation reduced 24 and 18% within the same time period.
138 Bioremediation of Industrial Pollutants

Saranraj et al. (2010) isolated a bacterial strain from tannery effluent and
identified it as Enterococcus casseliflavus. It showed a high level resistance of
800 øg/ml chromium. The minimal inhibitory concentration of chromium
was found to be 512 øg/ml of potassium dichromate in Nutrient broth
medium. The chromium adsorption was more significant by the live
cells than killed cells at different time intervals. It was observed that the
inoculation of Enterococcus casseliflavus reduced the BOD and COD values
of tannery effluent. The maximum adsorption of chromium was at a
temperature of 35 to 45ĈC and at a pH of 7.0 to 7.5.

Anaerobic Approach
The use of anaerobic approach to treat TWW is an interesting option
as compared to aerobic approach because of low energy consumption and
sludge production however its full scale applications 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 hydrolysis 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 is 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 (Lofrano et al., 2013). 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 Rajasimman,
2011; Mannucci et al., 2014). In these countries, the spread of new and large
industrial area 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.
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 139

Phytoremediation of Tannery Wastewater and Chemicals

Phytoremediation is an eco-sustainable technology used for the
remediation of industrial wastewaters or contaminated soil and using plants
comprised of two components, one by the root colonizing microbes and
other by plant themselves, which accumulates metabolites and convert the
toxic compounds into non-toxic products. Phytoremediation is an emerging
green technology used to clean up the contaminated sites, which combines
the disciplines of plant physiology, soil chemistry and soil microbiology. It
is cost effective and has aesthetic advantages and long term applicability.
It is best applied at sites with shallow contamination of organic, nutrient
or metal pollutants that are amenable to one of the five applications:
phytotransformation, rhizoremediation, phytostabilization, phytoextraction
and rhizofiltration. After sufficient plant growth and metal accumulation,
the above ground parts of plant are harvested and removed, resulting in
permanent removal of metals from the contaminated site. Currently, the
use of constructed wetlands and treatment ponds are increasing due to its
eco-friendly technology for wastewater treatment and management.
The constructed wetlands (CWs) are the man-engineered, eco-friendly
systems designed to remove the pollutants from highly polluted industrial
and municipal wastewater. 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 operational 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 pollutants from TWW (Mant et al., 2004;
Calheiros et al., 2007; 2008; 2012), selecting the suitable supporting media/
substrate for proper growth and development 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/transformation of pollutants
and subsequently to 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 affect 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. Culture-dependent techniques are
known to be insufficient to study the microbial community structure because
numerous microorganisms are unculturable in lab conditions (Ward et al.,
1990). Hence, molecular techniques such as random amplified polymorphic
140 Bioremediation of Industrial Pollutants

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;
Calheiros et al., 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 mgCrdm-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 cmd-1 has been
studied and found that only P. australis and T. latifolia were able to establish
successfully (Calheiros et al., 2008). Further, they 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 mgL-1 and for BOD5 inlet: 16-220 mgL-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.

Emerging Approaches for the Remediation of Tannery Wastewater

The TWW discharged even after the conventional treatment process is
still contains many refractory and recalcitrant organic pollutants (ROPs)
and thus, require further removal for environmental safety. Therefore,
in order to overcome this problem, the use of emerging approaches is
increasing in the current years. Emerging approaches includes membrane
technologies, membrane bioreactors, anammox technology and advanced
oxidation processes.
Advanced oxidation processes (AOPs) refers to the set of chemical
treatment processes that uses strong oxidizing agents (O3, H2O2) and/or
catalysts (Fe, Mn, TiO2) and sometimes also uses the high-energy radiation,
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 141

e.g., UV light (Lofrano et al., 2013). AOPs are based on the production
and utilization of hydroxyl radicals, which are strong oxidizing agents and
quickly and non-selectively oxidize a broad range of organic pollutants
in less time (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 stable inorganic compounds such as H2O, CO2 and salts, i.e. they
undergo mineralization (Rameshraja and Suresh, 2011). The treatment
efficiency of AOPs is mostly evaluated in terms of COD removal however
TOC is also a more suitable parameter to study the state of mineralization.
There are various types of AOPs such as fenton oxidation, photo-oxidation,
photo-fenton oxidation, ozonation, photocatalysis and electrochemical
treatment processes 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.
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 (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 (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 electrochemical 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, its high oxidative capability
and efficiency make AOPs popular techniques for the tertiary treatment
of recalcitrant organic and inorganic pollutants. However, the increasing
interest in wastewater reuse and more stringent regulations regarding
the water pollution prevention and control are currently accelerating the
implementation of AOPs at large scale.
Membrane technologies (MTs) are used for the mechanical separation/
purification of industrial wastewater with the help of permeable membranes.
The MTs offers many economic benefits to leather industry, especially the
142 Bioremediation of Industrial Pollutants

recovery of chromium from TWW and are used for purification/reuse of

wastewater and chemicals of deliming/bating liquor, reduction of pollution
load due to unhairing and degreasing, removal of salts as well as in the
biological treatment of TWW for its reuse (Lofrano et al., 2013). There are
several membrane-based technologies such as cross flow microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO) and supported
liquid membranes (SLMs) are used for the purification of TWW (Lofrano
et al., 2013; Dixit et al., 2015). However, the use of reverse osmosis (RO)
with a plane membrane has been suggested for the removal of refractory
compounds such as chlorides and sulphates and more recovery of water
from wastewater, which can be reused in the industrial process and thus
reducing the groundwater consumption (De Gisi et al., 2009). In addition,
the economical evaluation of membrane filtration technologies has been
discussed in detail by Scholz and Lucas (2003). However, the successful
integration of MTs in a conventional purification process for TWW streams
has been recently reported by Stoller et al. (2013)
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 offers 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 phenomenon that affect the sludge settleability (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 Tamilnadu Pollution
Control Board (TPCB) India has been evaluated (Suganthi et al., 2013).
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%
Organic Pollutants in Tannery Wastewater & Bioremediation Approaches... 143

of operational costs in sludge disposal as compared to the conventional

nitrification/denitrification processes (Anjali and Sabumon, 2014). Therefore,
industries, producing wastewaters having high concentration of ammonia,
are showing increased interest in anammox process. However, the long start-
up time and inhibitive nature in the presence of organic carbon and NH4-N
limits its field applications. Further, the development of mixed microbial
consortium consisting of ammonia oxidizing bacteria, anammox bacteria,
and denitrifying bacteria is expected to treat wastewaters containing both
ammonia and organic carbon.

Challenges in the Degradation and Detoxification of Tannery Wastewater

The major problems with the TWW is its complex nature due to the
persistent pollutants like tannins and other poorly biodegradable compounds
as well as toxic metals that can inhibit the biological treatment. Besides these,
TWW also contains some toxic metals ions like Cd2+, Cr6+, Fe3+, Zn2+ and
Pb2+ etc., also have a high inhibitory and antimicrobial activity reducing the
anaerobic digestion of TWW. Stasinakis et al. (2002) observed a significant
inhibition of heterotrophic growth in the presence of 10 mgLî1 Cr6+. Recently,
the sequential applications of bacteria and wetland plants have been reported
to be very promising for the degradation and detoxification of TWW, but
this has to be optimized yet with the detailed microbiology of wetland
plants, plants rhizosphere and detoxification mechanisms. Moreover, the
nature of TWW and extent of their toxicity need to be investigated in
detail for their complete degradation and detoxification during the treatment
process at CETPs.

Conclusion
Tannery wastewater is a major source of environmental pollution. The
conventional treatment processes applied for the treatment of tannery
wastewater are not efficient as these do not treat the tannery wastewater
properly. Further, the physico-chemical treatment processes are also not
environmental friendly and consume a large amount of chemicals as well
as generate a huge amount of chromium contaminated sludge in the
environment. Therefore, the bioremediation approaches may be the suitable
alternative for the degradation and detoxification of tannery wastewater for
environmental safety. Further, the search for effective microorganisms for
the degradation and detoxification of tannery wastewater is required.

Acknowledgements
Authors are extremely grateful to the „Science and Engineering Research
Board‰ (SERB), Department of Science & Technology (DST), Government of
India (GOI), New Delhi for financial support as „Major Research Project‰
144 Bioremediation of Industrial Pollutants

(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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