Journal of Cleaner Production 89 (2015) 1e17

Contents lists available at ScienceDirect

Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Review

Eco-friendly waste management strategies for greener environment

towards sustainable development in leather industry: a
comprehensive review
J. Kanagaraj a, *, T. Senthilvelan a, R.C. Panda b, S. Kavitha a
a
Leather Processing Division, CSIR-CLRI, Adyar, Chennai 20, India
b
Chemical Engineering Division, CSIR-CLRI, Adyar, Chennai 20, India

a r t i c l e i n f o a b s t r a c t

Article history: The leather industry deals with proteinous skin material for the conversion of leather and this generates
Received 9 September 2014 huge amount of solid and liquid wastes giving rise to pollution that needs to be overcome by introducing
Received in revised form sustainable cleaner technologies. This review describes various eco-friendly challenges and major
3 November 2014
achievements for abatement of pollution in leather processing. Different cleaner technological methods
Accepted 4 November 2014
Available online 11 November 2014
in preservation of raw hides/skins, unhairing, tanning and dyeing operations are discussed here. Cleaner-
preservation techniques by using chemicals and biological agents have been developed to reduce
pollution problems of salt up to a great extent in leather processing operations. Process intensified op-
Keywords:
Skin preservation
erations have helped to achieve better uptake and to manage pollution load. Enzymatic dehairing are
Enzymatic dehairing implemented to reduce Bio-chemical-Oxygen-Demand (BOD) at the level of 40%, Chemical-Oxygen-
High exhaust tanning Demand (COD) up to 50%. Improved biological methods for bio-degradation of dyes, azo-dyes and
Improved dyeing their mixtures and to reuse the liquors in the process to reduce the dye pollution load in the effluent
Biodegradation of pollutants streams are reviewed. Nano-Particle polymers and improved retanning materials have been synthesized
for high exhaustion of dyeing and retanning properties. Mathematical models predicting kinetics and
growth for the above processes are also reviewed. It could be concluded by utilization of these tech-
nologies, a possible reduction in pollution loads such as BOD & COD, upto levels of 50% & 40%, could be
achieved in leather processing.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Leather making is a very old traditional process that serves so-
cial needs, employs many skilled/unskilled persons while being one
of the highest contributors of global economy. Leather is unique
material and cannot be compromised with synthetic materials and
can be obtained by the conversion of skin/hide into leather where
the skin/hide undergoes various treatments. It provides a wide
Abbreviations: ETP, effluent treatment plant; ppm, parts per million; TSS, total
suspended solids; DNA, deoxyribonucleic acid nucleic acid; FT-IR, Fourier Trans-
formation-Infrared; Lpm, litre per minute; Min, minute; h, hour; UVevis, Ultra
Violet visible; HPLC, High Pressure Liquid Chromatography; U/ml, Units/micro-litre;
M-ESI, Mass-Electrospray Ionization; GCeMS, Gas ChromatographyeMass-
Spectrometry.
* Corresponding author. Leather Processing Division, CSIR-Central Leather
Research Institute, Adyar, Chennai 600020, India. Tel.: þ91 044 24911386, þ91 044
244530630; fax: þ91 044 24911589.
E-mail address: jkraj68@yahoo.co.uk (J. Kanagaraj).
range of consumer goods such as shoes, garments, bags etc. In-spite
of the incipit, leather industry has been categorized as one of the
highly polluting industries having concerns that leather making
activity can have adverse impact on the environment.
Global production of leather is approximately around 4.8 billion
sqft. It is estimated that about 6.5 million tons of wet salted hides
and skins are processed worldwide annually and 3.5 million tons of
various chemicals are used in leather processing (Ramasami et al.,
1999a). Chemicals that are used during the processing are not
fully uptake by the leather leaving huge amount of pollution load
through effluent streams (Fig. 1). The liquid effluent at the level of
45e50 m3 per ton of raw hide is generated during the process.
Nearly 70% of the emission loads of Bio-chemical-Oxygen-Demand
(BOD), Chemical Oxygen Demand (COD), and Total Dissolve Solids
(TDS) are generated in the process (Ludvik, 1996). The leather
making process produces wastes comprising of COD, BOD, Sus-
pended solids, Chromium, dyes, sulphur at the level of 1470 ppm,
619 ppm, 920 ppm, 30 ppm, 50 ppm and 60 ppm respectively

http://dx.doi.org/10.1016/j.jclepro.2014.11.013
0959-6526/© 2014 Elsevier Ltd. All rights reserved.
2 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17

250
Offer
200 Release

g/kg of hide processed

150

100

50

Ammonium…

Reactant Salts
Reactant Products

Mineral Syntans

Fat liquor
Bate

Dyes
Soda Bicarb

Soda Bicarb
Salt

Organic Tannins
Sod. Sulphide
Lime

Cr2O3

Acids
Wet Agent

Sulphuric Acid
Chemicals

Fig. 1. Representation describing the various chemicals used in leather processing operation.

(Ludvik, 1996). In order to combat this pollution load suitable part of the fibrous proteins such as hair, fleshing wastes are also
cleaner technologies are needed to create a green environment in contributed to solid wastes. In addition to these wastes, i.e., raw
the said industry. hide/skin trimmings, chrome shavings, buffing dust, chrome trim-
Leather processing follows pretanning, tanning and post tan- mings, leather strips and cuttings, lime and chrome sludge, sludge
ning operations. Prior to pretanning, the raw animal skin and hides from ETP (primary & secondary sludge) are also generated during
are preserved by application of salt that restrains microbial attack. manufacture of leather. The major amount of solid wastes emanate
This process of preserving skins is called as “Curing”. The pre- from beam house operation (80%), tanning operation (19%) and
tanning processes consist of soaking, liming, deliming, bating, finishing operation (1%).
degreasing, and pickling unit operations. During soaking skins/ Literature reveals that per one thousand kg of raw skin/hide
hides are rehydrated to open up the contracted fibre structure. yield 150 kg of leather and remaining 850 kg contributes to solid
Similarly the main objective of liming is to remove hair, deliming is wastes out of which 450 kg is collagen waste and 400 kg is fleshing
to remove lime, bating is to split the fibre into fibril, degreasing is to wastes with 30 m3 of effluent (Ludvik, 1996). The waste accumu-
remove the fat and pickling is to reduce the pH of the skin from 8 to lation leads to sludge problem and chocking of treatment pipes
2.8e5.0. Tanning renders permanent stability to the skin/hide. The which results in reduction of efficiency of treatment plant.
post tanning operations are retanning, dyeing and fat liquoring Disposing of solid waste is an economic burden to tanners as many
mainly to give color and to enhance physic-chemical properties of tanneries are closing down for above problem. Circular economy
leather. Pre-tanning and tanning operations contribute about 57% (CE) model has been tested as a new way of raw materials, water
of the water consumption in leather processing and the washings and energy consumption reduction in the leather industry. This
about 35%. Rao et al. (2002) reported that pretanning and tanning model was suggested for reducing, reusing, recycling and recov-
need about 57% while washing needs about 35% of total water in ering of the tannery effluents in leather processing to the different
leather processing. They provided viable solution (minimized operation processes (Hu et al., 2010). The main aim of this review is
amount of liquid effluent) to pollution problem by reducing to study liquid, solid waste that is generated through different
amount of water through recycling and optimization in leather processes to suggest suitable technology for cleaner production to
processing, particularly in pretanning and tanning (Gutterres et al., overcome the problems in leather industry. The present paper re-
2010). views various cleaner technology options developed that include:
Raw skins/hides, initial material for the leather industry, is Cleaner preservation skin/hide using various eco-friendly chem-
subjected to a wide range of chemical, mechanical, biological and icals, bacteriocin solutions, sustainable method for dehairing of
pH alterations requiring huge amount of water. The unspent quanta skin/hide, high exhaust chrome tanning using different synthesized
of chemicals as generated from the processes are discharged in the additives, high exhaust vegetable tanning during tanning opera-
stream that causes problems to environment. There is an enormous tions; and eco-friendly and improved dyeing process. Modeling of
pressure from the various pollution control bodies to regulate and dye uptake rates in post tanning process has been developed and
minimize the amount of pollution generated from the leather some of them are in practice. Merits and demerits of these above
processing (Ramasami et al., 1999). From a medium sized tannery, mentioned cleaner technologies will be discussed in this review.
over 300 million cubic meters of waste liquor containing thousands
of tons chemicals and solid waste are discharged daily by the 2. Methods
leather industry. They are to be treated adequately and disposed
scientifically complying with the statutory requirements The method of preparing silica gel is carried out by mixing so-
(Mariappan, 1997). Besides liquid waste, leather industry is facing dium meta silicate and hydro chloric acid with pH of 5.5. Boric acid
another problem from disposal of solid wastes. The reason being, and SMB are used in powder form for the preservation of skins.
skin itself is a proteinous material and part of which is loosened Protease for dehairing was obtained from Bacillus sp. The FH and
during different unit operations resulting huge solid wastes. The Biotannin were prepared from fleshing wastes by systematic hy-
non-fibrous proteins such as albumin, globulin and mucoids and drolysis followed by chemical treatment. The fibrin hydrolysate was
 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
obtained from alkaline hydrolysis of animal blood collected from
slaughter house. Dyes for improved dyeing method was prepared
by keratin waste by enzymatic hydrolysis followed by co-
polymerization of amino acid derivative and an acrylate ester in
dispersed condition. Azo dyes were collected from Sigma Aldrich
for Biodegradation using Bacillus cereus sp, Laccase enzyme ob-
tained from Micrococcus luteus and azo reductase enzyme.
Biodegradation of phenol was carried out by using mixed culture of
Pseudomonas putida Tan-1 and Staphylococcus aureus Tan-2. Math-
ematical modeling for understanding kinetics and growth of mi-
crobes was carried out using experimental data and Matlab Ver 12.1
software.
3. Preservation of raw skin/hide
Conventional method for preservation is carried out using salt
(sodium chloride). Availability of common salts is plenty in nature.
Prior to leather processing the skin/hide is preserved by using salt.
Besides having antibacterial and antifungal activities, the dual
functions of common salt, such as dehydrating power and bacte-
riostatic property, are being exploited in the preservation of skin/
hide. Preservation of skin by using salt is one of the popular curing
methods followed world wide. During the salt-curing method the
moisture content of skin is reduced from 70% to 30% making the
condition of skin/hide non conducive for bacterial growth. The salt
curing method is cost effective and easy to practice but suffers
heavily from an environmental perspective (Dalton, 2012;
Muthsubramanian and Mitra, 2006). The salt is discharged not
only from pickling, and chrome tanning operation but also from
curing stage in major amount. The leather industry is contributing
40% of TDS and 55% of chlorides (Cl) in the effluents generated from
curing operation (Musa et al., 2011). Sodium chloride is very diffi-
cult to remove and also cause problems to the effluent treatment.
According to pollution control board norms the TDS must be
2100 mg/L in the treated leather waste water (Bienkiewiez, 1983).
Hence, suitable cleaner technologies in the preservation methods
are envisaged to abate this problem.
3.1. Cleaner preservation of skin/hide using silica gel
The cleaner preservation technique using silica gel method has
been proposed over conventional salt curing method. This sug-
gested preservation method is cost effective, easy to adopt and is an
environmental friendly approach. A better preservation system can
be established using inert compound silica gel. This novel method
uses silica gel which is prepared by mixing sodium meta-silicate
and hydrochloric acid at pH of 5.5 and followed by spray drying.
The resulting powder is used for the preservation purpose. The
recommended method for preservation uses optimum amount of
silica gel powder at 15% with or without 0.1% PCMC (Para Chloro
Meta Cresol). The less-salt method of using silica gel at the level of
5% with salt 5% has also been developed. The efficacy of preserva-
tion using this new method was accessed by various parameters
such as moisture content using Nuclear Magnetic Resonance (NMR)
micro-imaging technique, total extractable nitrogen using nitrogen
analyzer and bacterial count by standard agar plate technique, the
fibre structures were analyzed using scanning electron microscope
(SEM). The results indicate that the new cleaner preservation
technique was as effective as salt curing and did not cause any
problem during soaking and leather manufacturing processes. This
new preservation method was found to be a feasible alternative to
reduce pollution load in treated skins and to combat the problem of
Cl and TDS issues (Cuadros et al., 2012; Thanikaivelan et al., 2001).
The reduction in pollution load of TDS was by 3 fold in soaking
process by less salt preservation technique was achieved. The
3
pollution load was reduced at the maximum level upto 70e75% for
TDS and 80e85% for Cl. The leather properties obtained were
comparable to salt cured leather. The results reveal that this
method was as efficient as conventional salt curing with no ill ef-
fects in the leather processing. The problems of chloride and TDS
can be solved using an effective alternative salt curing method.
The skin that was preserved using silica gel did not show any
structural modification/degradation. The results of microscopic and
moisture analysis data shows no evident of harmful effect on the
leather making which indicates that there is less probability for the
bacterial population to manifest deterioration (Fig. 2). The newly
developed method has environmental advantageous over the
conventional method associated with BOD, COD, TDS and Cl. The
method is economically viable, practically feasible with 10e15% of
cost reduction and preferable replacement for the salt curing
method (Kanagaraj et al., 2001).
3.2. Preservation of skin/hide using boric acid method
Salt free and less-salt preservation systems based on boric acid
have been investigated and evaluated at ambient temperature of
30e35  C as alternative preservation method. New preservation
technique over the conventional one using either boric acid at the
level of 5% for salt-free method or a mixture of boric acid (2%) and
common salt (5%) for less-salt method has been devised. Both of the
methods resulted in more than 80% reduction in Cl and TDS in the
effluents. The proposed method based on boric acid have been
found to be efficient and cleaner in preserving the skin by both salt-
less and less-salt methods as demonstrated by the preservation
parameters and leather properties. The application methodology of
the curing agent has been maintained the same as that of the
conventional system. Boric acid does not pose any serious health or
safety problems on usage. Also, the new technique does not need
any extra set-up or infrastructure for practical implementation of
the method. This method is one of the suitable techniques that
emerge as viable alternatives for the conventional salt preservation
system.
3.3. SMB method
New preservation system by using SMB has been developed. Salt
free preservation system using SMB at 1% and less salt preservation
system by using SMB (0.5%) with salt 5% are able to preserve the
skin very effectively.
The results observed from the preserved skin indicated that
generation of the nitrogen content and also the bacterial count is
comparatively lower than in the salt cured skin which reveals that
skins are preserved in a better manner compared to the salt cured
skin. The observed count of bacterial population with the salt-less
curing process is not enough to manifest deterioration and there-
fore, did not seem to affect the collagenous network of the skin as
seen from the data of the mechanical properties of cured skin. The
pollution profile of the preserved skin indicated the reduction of
TDS and Cl levels by about 15e20 times over the conventional salt-
cured skin (Kanagaraj et al., 2005).
3.4. Phytochemical preservation of skin/hide
The phytochemical preservations were carried out by using
deoiled and oiled neem cake. These cakes at various levels showed/
gave satisfactory results in preserving the raw skins. These methods
reduce pollution load of TDS and Cl upto 60%. Another new
phytochemical preservation technique using powdered tamarind
leaves as preservative chemical is reported to produce satisfactory
preservation. These extracts were obtained by using methanol and
4 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
Fig. 2. NMR imaging of skin preserved by Silica Gel Method. (B1-Experimental skin showing more white spots indicating presence of more water content and S1-Control sample
preserved by salt curing showing less white spots indicating less water content in the skin sample).
concentrated under vacuum till crude extract. These methods also
reduce pollution load of TDS and Cl up to more than 50% (Tamil
Selvi et al., 2011; Font et al., 2011).
3.5. Preservation of skin/hide using bacteriocin solutions
The present work is focusing on using bacteriocin as an
effective bio-preservative to preserve the skin without any
harmful effect to living beings. Bacteriocin is antimicrobial and
antifungal peptide which is ribosomally synthesized from Lactic
Acid Bacteria. The principle behind the work is to inhibit various
micro organisms present in the skin/hide by using the bacte-
riocin. The goat skin was preserved with 15% bacteriocin solution
and stored for seven days at room temperature, which showed
the complete inhibition of microbial growth even after seven
days of storage. Then the goat skin was further processed into
crust leather and then was analyzed by SEM and physical testing
data. The results revealed no significant changes in the fiber
structure of the skin due to preservation by bacteriocin. It was
noted from further experiments that TDS was reduced at the
level of 94.4% and Cl were minimized to 95.6% during leather
processing. It was concluded that bacterocin can be used as very
potential curing agent for preservation of skins/hides (Kanagaraj
et al., 2014). Use of other chemicals for the preservation was also
advocated by several researchers with optimized parameters of
curing efficacy. The literature (Chandra Babu et al., 2012) reveals
that the role of chilling temperature on the preservation efficacy
was suggested as 4  C and optimum temperature for 7 days
storage. However, the chilling profiles inform that a blast chiller
and hooking arrangements might be necessary for bringing down
the temperature to 4  C in less than 2 h to avoid bacterial
damage.
4. Pretanning process
Pretanning step includes soaking, dehairing operations that
generate huge amount of liquid wastes which are discussed below.
4.1. Enzymatic soaking process
Soaking is the first unit operation in pretanning process where
salted skins/hides are washed with water for the removal of salts,
and to partially solublize and to remove the denatured protein
(Detimer et al., 2012, 2013; Puvanakrishnan et al., 1981). Enzymes
during soaking accelerate the process of removing hyaluronic acid
and improve quality through, more effective rehydration of the
skin, fat degradation dispersion, better removal of carbohydrates or
protein components (Cavello and Cavallitto, 2013; Detimer et al.,
2012; Nazer et al., 2006). Both proteases and lipases aid soaking
processing. They are particularly helpful when processing fatty raw
materials. Very dry raw materials, fresh hides without salt, where
the removal of non structural proteins and carbohydrates is very
difficult (Ramasami et al., 1999; Fennen et al., 2013; George et al.,
2014).
Ma et al. (2014) demonstrated soaking process by using three
enzymes, TanG, LimeG and FP50 which were optimized. Optimal
process parameters (temperature and pH) along with optimal
enzyme formulation yielded good leather. Protein and hydroxy-
proline absorbance of soaking bath showed degree of enzymatic
hydrolysis to protein and collagen of skin indicating combined
synergistic effect of TanG and LimeG. The formulation had high
enzyme activity at alkaline pH. Pollution reduction in terms of
reduction in turbidity, suspended solids (SS), BOD and COD were
achieved and reported. Use of eco-friendly enzyme brought BOD/
COD ratio to 0.89 indicating the waste can be biodegradable. Morera
 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
et al. (2013) explained soaking of bovine and ovine skins using ul-
trasound and recommended for less water and process time.
4.2. Eco-friendly method for dehairing of skin/hide
Dehairing is one of the important operations in pretanning
process where hair is removed by using suitable chemicals. Tradi-
tional method of liming is based on application of lime (10e20%)
and sodium sulfide (2e5%) that generates lot of pollution problem.
Liming method generates nearly 50% of COD and 40% of BOD that
contributes to 60e70% of the total pollution load in leather pro-
cessing (Senthilvelan et al., 2012). Global concerns on the envi-
ronmental impact of leather industry have led tanners to reduce
the elements of toxicity in the effluents (Senthilvelan et al., 2012).
However, sodium sulfide is a toxic chemical that bears unfavorable
consequences on environment and the efficacy of effluent treat-
ment plants. As a remedy, alternate viable methods are proposed by
using protease to replace the lime and sodium sulfide for eco-
friendly processing of leather (Oppong et al., 2006; Aravindhan
et al., 2007).
Senthilvelan et al. (2012) developed enzymatic unhairing by
using protease enzyme to replace sulphide. This enzyme was ob-
tained from Bacillus sp. The optimum activity of the enzyme was
found to be at pH 11.0, at temperature at 45  C and duration 16 h.
From the results it was found that complete dehairing was achieved
by using alkaline protease at 2% for duration of 16 h. The method
provided sustainable technology where BOD, COD, TSS, and TDS
were reduced at the level of 62.8, 79.0, 88.2, and 82.5% respectively
in comparison with the control sample. The leather produced by
this method was subjected to SEM studies. The SEM analyses
revealed similar fiber orientation and compactness compared with
control sample. In addition to that, the color matching studies of
the enzymatically dehaired leather showed better color properties
than control sample.
Dayanadan et al. (2003), proposed a method for dehairing of
goat skins using proteolytic enzyme isolated from Aspergillus tam-
arii obtained by solid state fermentation (SSF) by using wheat bran.
The stability of the enzyme for dehairing was optimized at different
parameters such as pH 9e11 and temperatures 30e37  C with
enzyme concentration of 1% w/v and incubation periods of
18e24 h. The production was carried out aseptically at 26  C on
100 g substrate containing 60% moisture with 10% inoculums and
107 spores per ml in an incubator for 72 h. The substrate was
extracted using 20 mM Tris HCl buffer, pH 8.0 for 30 min and su-
pernatant was obtained by prechilled acetone extraction to get 80%
(v/v) saturation. The precipitate was collected and dialyzed with
20 mM Tris buffer, pH 8.0, containing 2 mM CaCl2, which was
lyophilized and stored at 4  C.
The stability of the enzyme for dehairing was optimized at
different parameters such as pH 9e11 and temperatures 30e37  C
with enzyme concentration of 1% w/v and incubation periods of
18e24 h. The dehairing experiment carried out with an enzyme
concentration of 1% (w/w) yielded complete dehairing with 18 h.
The dehaired leather produced good quality of leather with
pollution reduction of BOD (50%), COD (40%), TDS (60%) and TSS
(20%). In addition to that the leather produced by this method also
showed comparable strength properties. By using this method it is
possible to produce eco-friendly leather and also to replace sulfide
completely by this process. Enzyme (protease and lipase) based
beam house operations of leather were demonstrated (Saurabh
et al., 2013) to achieve 100% dehairing & degreasing whereby
natural skin color was preserved with a reduction in BOD and COD
of effluent. The protease is subtilisin-like serine protease with low
collagenase activity that gives enzymatically feasible and envi-
ronmentally benign leather. Alkaline proteases were developed to
5
degrade hair for the application of the proteases in dehairing cow
hides that indicated positive results. The resultant dehairing pro-
cess gave environmentally friendly enzymatic process yielding
comparable leather qualities (Abraham et al., 2014). A crude bac-
terial protease isolated from Pseudomonas fluorescens demon-
strated better dehairing activity on goat skins. The results
confirmed that the enzymatic dehaired leathers exhibited com-
parable leather qualities with an eco-friendly approach to cleaner
leather (Kandasamy et al., 2012). By using this method it is
possible to produce eco-friendly leather and also to replace sul-
phide completely by this process (Arunachalam and Saritha, 2009;
Verma et al., 2011; Dettmer et al., 2013; Subbarao et al., 2009).
Alkaline protease (George et al., 2014) obtained from vibrio
metschnikovii NG155, at pH 10, temperature 65  C effectively
dehairs the skins. In addition to that better physiochemical
properties of dyed crust and lesser pollution load in dehairing
process were achieved in leather processing. Dettmer et al. (2013,
2012) reviewed use of enzymes in leather processing to improve
and optimize process and to produce good quality of leather.
Combination of 4% hydrogen peroxide with enzyme at the level of
100e300 U g/l is a viable method of unhairing process to replace
lime and sulphide from the conventional process for the produc-
tion of better quality leather. This oxidative enzymatic unhairing
could be an eco-friendly method (Andrioli and Gutteres, 2014).
Kinetics leading to enzymatic unhairing was carried out by other
researchers that described linearity between release of total pro-
tein and square root of time at the initial stage that suggests that
enzymatic unhairing by protease was a diffusion controlled pro-
cess at the initial stage. The results showed that release of total
protein further confirms that it is a hydrolysis of core protein by
protease that leads to the degradation of proteoglycans and
release of protein and saccharides (Song et al., 2011; Wang et al.,
2009). It has been found from literature that several commercial
enzyme formulations were available in combination with hydro-
sulfide and peroxides for better results. These experiments indi-
cate that activity of enzyme is stabilized by the addition of
hydrosulfide through activity measurements; peroxide has some
activation effect. Effluent outlets (Nazer et al., 2006) from
dehairing-liming of hides were recycled to reduce needed amount
of chemicals in the modified liming process thereby increasing
economic benefits and reducing pollution load of COD to 50% and
environmental impact by 24%. Valeika et al. (2009) introduced an
unhairing method using enzymes, sodium hydroxide, sodium
sulphide and disodium hydrophosphate to produce high quality
pelt that decreased pollution created by sodium sulphide and
other calcium compounds. Kinetics of enzymatic unhairing by
protease was presented by Song et al. (2011). The linearity of graph
revealed that enzymatic unhairing by protease is a diffusion-
controlled process at the initial stage indicating degradation of
proteoglycans and the release of protein and saccharides in the
process. The authors suggested control of time of reaction to
protect the collagen layer. Jegannathan and Nielsen (2013) dis-
cussed soaking followed by liming for animal hides where hair is
digested by the action of sulphides. They suggested using protease
and lipase as supplement for reducing process time, amount of
chemical, tensides and soda. Li et al. (2009) presented methods
avoiding production of sulphide by enzymatic process that
reduced waste water by not converting hair to organic matter to
come out with waste water stream. Saravanan et al. (2014) sug-
gested use of sans lime and sodium sulfide to replace costly en-
zymes. They found that release of proteo-glycans and
carbohydrates are more in the case of enzyme based systems
(takes 5 h for complete removal of hair) compared to limeesulfide
system. The micrographs of histological staining revealed that hair
loosening is due to breaking down of proteo-glycans present in
6 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17

hair follicle. They also suggested means of reducing amount of
enzymes to be used. Thanikaivelan et al. (2002) presented zero
discharged tanning through different steps using conventional and
enzymatic processes. They compared enzymatic systems (using
alpha amylase) with conventional process and suggested to skip
deliming and reliming steps.
5. Tanning process
exhaustion of chromium in liquor and SEM studies gave comparable
results as of control. Due to improved uptake of chromium pollution
load such as BOD, COD, TDS, TSS were reduced to the level of 60, 43, 1
and 3% respectively in the experimental tanning process. Economic
and environmental benefits to chrome tanning were obtained by
adopting closed loop aluminiumechrome combination tanning and
two-stage tanning (Sundar et al., 2002). It provides high exhaust
chrome tanning.

Tanning is one of the important unit operations in leather

making where skins are treated with tanning agents to convert the 5.2. High exhaust chrome tanning systems using biotannin
putrescible skin into imputrescible leather. Chrome and vegetable
tanning methods are popular tanning methods out of which former Biotanin is a protein based tanning agent prepared from similar
is well known and is practiced worldwide (90%). Chrome tanning fleshing wastes as described in above section. In order to prepare
process is carried out with the help of Basic Chromium Sulfate (BCS) the biotanin, fleshing waste were hydrolyzed by using proteolytic
at the level of 8e10% in the tanning process (Nashy et al., 2011; enzyme and further breaking down the peptide into amino acid
Vedaraman and Muralidharan, 2011). However the BCS used in level. Subsequently these products were treated with sodium
tanning process is not absorbed up by the skin fully and gets dis- borohydride and dimethyl sulphate (to evaporate methane) fol-
charged along with the effluent. This leads to serious pollution lowed by addition of pyridinium cholorochromate to give aldehyde
problem. BCS, in the form of chromium (III) has been used in tan- which is the main functional group in Biotannin that provides
ning that is converted into chromium (VI) which is said to be tanning action to skins (Kanagaraj et al., 2003; Gupta, 2004). The
carcinogen. According to the international standard, the prescribed Biotanin has been applied to the pelt and tanning property was
discharge limit is 3 ppm and above this level is prone to damage studied. The results of the tanning experiments showed that there
DNA, affects skin, liver and kidneys in human being. In addition to was an improvement in the exhaustion of chrome tannins from 67
that, chromium at higher concentration level affects the soil, fresh to 92% by the application of Biotannin at the level of 2% in chrome
water, fish and aquatic organism. Inspite of these limitations, it has tanning. COD reduction of 58% was achieved in this method. An
become necessary to produce leather using BCS to get superior improvement in shrinkage temperature, dyeing property and
quality of leather. However, environmental norms restrict to physical strength properties were obtained in the experimental
maintain the discharge norms of the chemical that are present in processes in comparison with control processes (Table 1). The
treated water. Some measures have been made compulsory to organoleptic properties of the leather obtained after treatment
reuse the chrome present in the tanning effluent. with Biotannin in post tanning process were better than the control
Dixit et al. (2015) presented a review article on hazardous/toxic process. Hence, the developed product can be used as a tanning
pollution from leather industry and suggested two categories of agent that helps for the improved exhaustion in the chrome tan-
green technologies (i) introduction of processing technologies by ning process. Chromium salts were replaced by highly masked and
decreasing the effluent pollution load, avoiding the use of harmful basified salts during tanning where basified tanning float can be
chemicals and producing solid wastes that can be used as by- recycled depending on quality of grain of leather. They suggested a
products (ii) treatment of wastewater, handling and processing of saving of 18 L of water per kilogram of tanned leather accounting
solid waste in an environment-friendly manner. saving of 90% of water (Morera et al., 2011).
Present review also discusses various technologies for reducing
chromium in the effluent (by raising the uptake) that have been
developed by the leather processing department of CLRI to mitigate 5.3. High exhaust chrome tanning using novel copolymer
the pollution problem of chromium tanning salts. High exhaust
chrome tanning systems such as use of Fleshing-Acrylate com- Kanagaraj et al. (2007) proposed another method for high
posite, modified protein based Biotannin from fleshing wastes, exhaustion in chrome tanning using novel NPD which was pre-
Nano Particle Dispersion (NPD) and Nano Particle Polymer (NPP) pared by polymerizing two monomers namely, an acrylic ester and
and fibrin hydrolysate have been developed. The details of these an amino acid derivative, by micro emulsion polymerization
cleaner technologies will be briefed in the following section. methods. The NPD showed characteristics of particle size at 40 nm,
low relative viscosity (hr) of 1.08 at 25  C, zeta potential of NPD at
5.1. High exhaust chrome tanning using FH 32.9 mv showing anionic nature of copolymer particle. The NPD
was used in chrome tanning which showed improved exhaustion of
This method discusses about use of FH, composite in chrome tanning. NPD used at the level of 4% resulted in exhaustion of 94% in
tanning for high exhaustion of chromium in the tanning bath. In chrome tanning process (Table 2). The produced leather exhibited
order to prepare FH, the fleshing wastes from the tannery were comparable organoleptic and physical strength properties and
collected and hydrolyzed by alkali digestion method. The FH at the offered an eco-friendly way of leather making (Kanagaraj et al.,
level of 4% used in tanning bath gave chrome exhaustion of 91.2% in 2008).
the tanning process (Vesela et al., 2002). This is very high exhaustion
as compared to the 65% in the conventional chrome tanning
method. The main reason for the improved uptake of chromium by Table 1
High exhaust chrome tanning using biotannin.
the use of FH can be explained by the fact that FH could easily form
complexes with collagen and also with chromium by forming a Experiments Chemicals used Grain Middle Flesh %
bridge between 2 chromium complexes. Hence, binding of collagen Exhaustion
become stronger and it makes better leather compared to conven- Tanning BCS 8% þ BT 1% 2.15 ± 0.02 1.63 ± 0.04 2.20 ± 0.05 89 ± 1.4
tional methods (Nashy et al., 2011; Braganca et al., 2013). The Tanning BCS 8% þ BT 2% 2.20 ± 0.02 1.74 ± 0.06 2.26 ± 0.04 92 ± 1.5
chrome liquor, treated and untreated FH leathers were assessed for Tanning BCS 8% þ BT 3% 2.28 ± 0.06 1.76 ± 0.04 2.30 ± 0.08 94 ± 1.6
Control BCS 8% 1.57 ± 0.06 1.34 ± 0.03 1.60 ± 0.05 67 ± 1.0
various parameters. The shrinkage temperature, strength,
 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17 7

Table 2
Distribution of chrome and % exhaustion of chrome using NPD.

Experiment Chemicals used Grain layer (%Cr2O3) Middle layer (%Cr2O3) Flesh layer (%Cr2O3) Total chromium (%Cr2O3) % Exhaustion

Tanning 1 BCS 8% þ NPD 1% 4.52 ± 0.03 4.40 ± 0.06 4.46 ± 0.02 4.50 ± 0.04 89
Tanning 2 BCS 8% þ NPD 2% 4.68 ± 0.03 4.52 ± 0.03 4.63 ± 0.03 4.62 ± 0.02 91
Tanning 3 BCS 8% þ NPD 3% 4.70 ± 0.04 4.57 ± 0.04 4.62 ± 0.02 4.71 ± 0.05 93
Tanning 4 BCS 8% þ NPD 4% 4.76 ± 0.06 4.63 ± 0.02 4.72 ± 0.04 4.76 ± 0.04 94
Control (without NPD) BCS 8%þ 3.74 ± 0.04 3.68 ± 0.03 3.70 ± 0.04 3.70 ± 0.03 74

5.4. Fibrin hydrolysate as a chrome exhaust aid in the leather 5.6. Improved chromium management for environmental
production sustainability

In a separate attempt, fibrin hydrolysate, a different product of
animal slaughter house-discharges was used as a chrome exhaust
aid for the improvement of exhaustion of chrome tanning of skins/
hides. The said aid, crude fibrin hydrolysate was prepared by
alkaline hydrolysis and was used at the level of 1, 2, 3% as an
exhaust aid. An amount of 3% fibrin hydrolysate was found suitable
to increase the exhaustion from 70% to 91%. It also reduced BOD at
level of 50.8%, COD of 54.3%, TDS of 17.8% and TSS of 17.9% in the
tanning process. Improvement in dye uptake, organoleptic (soft-
ness, grain) and physical strength properties were also observed
(Kanagaraj et al., 2007; Yuanlong et al., 2012).
Efficient removal of solid wastes reported by other researchers
that the solid waste was reduced by 18% by this cleaner method.
Ultra sound (Song et al., 2008) was used to improve conversion
efficiency from 57.6% to 84.1% during proteolyticeenzymatic hy-
drolysis where the pore diffusion gets enhanced. They reported that
the solid waste was reduced by 18% by this cleaner method.
Aravindhan et al. (2007) presented an integrated chemo-enzymatic
methodology to reduce COD, TDS, Chloride, Sulphate to eradate
unsafe chemicals to provide clean environment during dehairing
and chrome tanning. They reported that the modified process re-
sults in decrease in COD and TS (total solids) loads by 67 and 78%,
respectively, as compared with control process.
A novel technique to remove chromium from effluent stream
was developed. The neutralized wattle extract was added to the
effluent to react with chromium that resulted in the precipitation of
chromate-flavanoid type of polymers in the bath. The resultant
sludge/precipitate were separated and the supernatant was reused
for fresh tanning (as recycled stream) for tanning process (Parti
et al., 2013). Experiments carried-out with the recycled liquor
resulted in almost complete utilization of chromium up to a level of
87% uptake compared to 76% in the control sample. The organo-
leptic, physical strength and color properties of leather were
comparable with the conventionally produced leather (Karthikeyan
et al., 2011).
Tannery solid wastes containing sludge, shaving and buffing
dusts was used to make compost for effective utilization of energy
to get a maximum oxygen flow of 3.0 g/min. Electron Paramagnetic
Resonance (EPR) and FTIR studies showed that there was no con-
version of Cr(III) to Cr(VI). The calcined waste was made into blocks
for testing for unconfined compressive strength (120e180 kg/cm2)
and heavy metal leaching. They found the percentage of metal
fixation was 99.1 and dissolved organic concentration in the
leachate was 55e66 mg/l (Sekaran et al., 2007).
5.7. Vegetable tanning

5.5. Biosorption of chromium in waste water
Even after adopting cleaner technological options for high
exhaustion of chrome during tanning, it has been found that waste
water/effluent from tannery contains chromium which needs to be
removed (Shanthi et al., 2013). Biosorption of chromium is a viable
and cleaner option in which chromium is absorbed by Bacillus
pumilus from tanning effluent that reduces chromium concentra-
tion with acceptable limit. It was confirmed from experiments that
reduction of chromium was achieved by 99.5% by adopting this
technique (Table 3). The presence of chromium metal-B. pumilus-
collagen crosslinkage was confirmed by FT-IR and SEM (Fig. 3).
Reduction in the environmental pollution load such as COD, TOC,
TDS, & TSS to the level of 92%, 92%, 90%, and 93% respectively were
found out in the experimental samples. The results concluded that
this method can be very eco-friendly, cleaner and sustainable
which were in close agreement with other researchers (Guo et al.,
2006; Hintermeyer and Tavani, 2013; Liu et al., 2001; Sovsky
et al., 2011).
It has already been stated that most of the leather tanning is of
chrome-tanning type, however, improved cleaner tanning options
have been practiced in case of vegetable tanned leather which are
discussed below: Vegetable tanning which is one of the traditional
tanning systems uses natural plant materials such as leaves, barks,
nuts and fruits to extract tannins (polyphenols) for tanning of the
skin/hides. Kanth et al. (2009) discussed cleaner production op-
tions using natural products during leather processing to reduce
COD and TDS. They suggested using enzymes for vegetable tanning
process.
Use of wattle extract at the level of 10e40% for vegetable tan-
ning generates pollution load with significant BOD, COD and
organic TDS content. Though these do not pose any hazard but their
accumulation gives rise to foul smell due to oxidative degradation
and needs alternate eco-friendly and cleaner methods. Some of
these methods widely practiced are (i) use of Biotanin (ii) use of FH.
Biotannin at the level of 3% yielded high exhaustion of vegetable
tannin to the level of 95% and also 2% of fibrin hydrolysate yielded
more than 90% of exhaustion in the vegetable tanning process. Both

Table 3
Reduction of chromium by using different biomass concentration (Bacillus pumilus).

S. No Concentration of chromium (ppm) Concentration of culture (ml) Chromium present in supernatant (ppm) Chromium present in biomass (ppm) % of Reduction

1 40 5 16 24 60
2 40 10 8.0 32 80.5
3 40 15 5.0 35 88
4 40 20 2.0 38 95.5
5 40 25 1.0 39 99.5
8 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
Fig. 3. SEM-EDX images of a) chromium loaded biomass sample, b) bacterial biomass and c) biomass and chromium at the initial hour. d) EDX spectrometer of chromium loaded
biomass.
these methods resulted in good leather having satisfactory organ-
oleptic, physical strength and color properties.
5.8. Combined biodegradation and ozonation for management of
tannins
In the present approach (Kanagaraj and Mandal, 2012; Ocak
et al., 2011), biodegradation is combined with ozonation for the
removal of tannins and dyes from effluent. Vegetable (Wattle
Extract) and chrome tannins and also dyes were targeted for their
removal by this technique. Biodegradation (280 h) was carried out
initially using culture of Aspergillus niger, Penicillium sp. and fol-
lowed by subsequent ozonation (4 h) to have better degradation
rate. Ozonation was done by ozonizer with a preset flow rate of
2 lpm with concentration of 8 g/30 min. The experimental results
showed degradation efficiency of 92e95%, 94e95% and 85e87%
for reduction of Vegetable tannin, Dyes and Chrome tannin
respectively (Table 4). Other analytical tests e.g., UVevis and FT-IR
etc., revealed that the functional groups in the vegetable tannin
molecules namely flavanoid compounds were derivatized into
smaller components while the dye that belonged to azo category
with double bond of N]N was converted into biomass. Chrome
tannins were converted into chromic oxide by these combined
effects. This is one of the cleaner methods to reduce the pollution
load of COD, TOC, TDS and TSS in the effluent containing above
compounds. The mechanism of degradation is clearly explained
in Fig. 4.
6. Post tanning process
Post tanning process includes dyeing, retanning operations that
are discussed below.
6.1. Dyeing process
Post tanning operation is carried out mainly to add color,
strength and organoleptic properties of the leather. Dyeing and
retaining processes are important operations carried out in post
tanning process. In this operation, acidic, basic, direct and metal
complex dyes are used in dyeing that provides suitable color and
light fastness properties to the leather (Lee et al., 2012). Due to
limitations on reactions and diffusions chemical dyes do not show
complete exhaustion in the process. Remaining amount of dyes gets
discharged in the effluent causing major pollution problem. Espe-
cially azo dyes that exert unique properties to the substrate, at the
same time it is categorized as carcinogenic due to the presence of
aryl amine radicals. To solve/minimize the above problems suitable
technologies are needed for complete degradation of dyes in the
effluent (Asad et al., 2007; Fang et al., 2004; Elisangela et al., 2009).
In the present review, suitable technologies were developed for
improved exhaustion of dyes in dyeing bath and consequently bio-
degradation of these dyes from effluent is discussed. Another
important operation in the post tanning process is retanning where
retanning-agents are used which are synthetically prepared from
phenol/formaldehyde sources that are useful in providing above
 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
Table 4
Reduction of pollution loads by biodegradation and chemical methods.
Samples Chemical methods
Various methods
Wattle extract Barium chloride
Chrome tannin Magnesium oxide
Dye Zinc oxide
Mixture of the components Barium chloride þ magnesium oxide þ zinc oxide
said properties. These agents contain many non-tannins that are
not fully taken-up by the leather during processing and generates
as pollutants in the effluent (Zhang et al., 2011).
6.2. Improved dyeing process by using NPP
In this approach NPP is used in dyeing for the improved
exhaustion of dyes. NPP is prepared by using copolymer consists of
a new monomer derived from an amino acid derivative and an
acrylate ester in dispersed condition with microemulsion poly-
merization reaction (Kanagaraj and Panda, 2011). Resultant NPP
showed naro particle size distribution with particle size of 60 nm,
low relative viscosity (hr) of 1.02 at 25  C and zeta potential of NPP
at 30.2 mV with anionic property. The application of NPP (2%) in
the dyeing process resulted in the improvement of uptake of dye up
to 99.10%. It has been observed from PM6 semi empirical quantum
mechanical level; the interaction of NPP with dye showed four
reactive sites. The results further indicated geometries of the
reactive sites that showed that binding energies of site 2 and 3 were
higher in comparison with 1 and 4. The binding energies calculated
for the sites showed increased binding energies for the site 2 and 3
Fig. 4. Mechanism of biodegradation e ozone treatment for wattle extracts, chromium
and dye samples. The wattle extract is biodegraded into derivatives of flavnoids. Basic
Chromium Sulphate is biodegraded into Chromium Oxide Sulphuric acid. Azo dye is
biodegraded into Sodium 4-Amimno-5-hydroxy-3,6-Dinitrosonapthalene-2,7-
Disulfonate.
9
Aspergillus niger Penicilium sp
(% reduction) (% reduction)
Initial and final loads (ppm) % Reduction
3540e420 89.2 92.4 95.2
1280e60 95.4 85.5 87.6
2370e830 65.1 94.1 95.1
3610e1080 70.1 90.8 95.1
with the values of 73.71 and 60.54 kcal/mol against 5.80 and
8.85 kcal/mol for the sites 1 and 4 respectively (Fig. 5a, b). The ki-
netics and color measurement study showed that dye uptake was
enhanced by using NPP. In addition to that the results obtained
from FT-IR spectra indicated the role of NPP taking part in hydrogen
bonding between different element of secondary structure helps in
the additional stability for dye uptake. This study was proved by
kinetic model for enhanced uptake of dye in experiment. The pre-
sent method is suitable for reducing pollution load arising out of
the presence of dyes in the dyeing process. Literature reports that
Ershad-Langroudi and Mirmontahai (2013) used nano particles and
polyethylene glycol to treat goat skin to retain viscoelastic, plastic
deformation etc mechanical properties of finished leather to avoid
unwanted erosion due to natural aging and other hydrostatic,
handling frictions (Ershad-Langroudi and Mirmontahai, 2013;
Gong et al., 2011). Nanocomposites were applied in tanning and
retanning process during making of suede leather and the effects
on the leather were observed for shrinkage temperature, me-
chanical properties, softness, biodegradability of the leather sam-
ples. The results showed that the application of nanocomposites to
the leather gave high hydrothermal stability, biodegradability and
softness. Investigation through SEM studies indicated that the
nanocomposites treated leather showed well-dispersed fibrils and
uniform fluffiness in the experimental sample (Ma et al., 2014a).
7. Biological management of chemical auxiliaries
The excess chemicals used in leather processing operations
comes out with effluent causes major pollution load which needs to
be reduced by means of following methods.
7.1. Biodegradation of azo-dyes
Among various dyes used in leather processing, azo dyes play
important role because of its strong binding affinity towards the
collagen fibres and imparting superior color properties to leather.
According to international norms, azo-dyes are banned substances
because of carcinogenicity associated with it (Husseiny, 2008). Azo
dyes, which are aromatic compounds having eN]Ne groups, are
the most important and largest class of synthetic dyes used in
commercial applications (Vandevivere et al., 1998; Hassan et al.,
2013; Viral and Kunjal, 2012). They are considered as the xenobi-
otic compounds that are very recalcitrant to biodegradation process
(Stolz, 2001). However, some of the dyes possessing azo-groups
have to be degraded by cleaner biodegradation methods (Palma
et al., 1999; Nigam et al., 2000; Dalmases et al., 2012). The other
approaches for the reduction of pollution problem arising out of
dyes are end of pipe treatments where dye can be biodegraded
completely to other forms or other intermediate metabolites.
Among these, biodegradation of dye by biological means is the eco-
friendly one and has the advantages over other systems. These
methods are environmentally friendly and cost comparative alter-
native to chemical decomposition process (Whiteley, 2007; Khalid
et al., 2011; Ozdemir et al., 2008; Olukanni et al., 2006).
10 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
Fig. 5. (a). Interaction sites present in Nano Particle Polymer (NPP). The dye acid black dye binds to these sites. (b). Optimized geometries of NPP by PM6 semi-empirical quantum
mathematical level. Calculated Binding energies of optimized geometries at PM6 level of theory showing: Site (1) 5.80; Site (2) 73.71; Site (3) 60.54; Site (4) 8.85 kcal/mol
respectively.
7.2. Biological method for decolourization of an azo dye
In the present approach, azo-dye has been bio degraded by
bacterium identified as B. cereus that showed optimum activity at
pH 7.3, temperature 37  C and duration of 4 days. The azo dye,
named, Acid Black was considered for biodegradation study
(Kanagaraj et al., 2012). The biodegradation experiment carried
out with 10 ppm of azo dye with the help of the bacterium
showed reduction of 80 and 96% in agitated and static conditions.
Further to that the results like UVevis spectra analysis showed
the disappearance of peak in the visible region of treated sample
(Nikhil et al., 2012). The other investigations such as FT-IR
analysis exhibited the transformation of azo linkages, mass
spectra analysis showed new intermediate metabolites such as p-
nitroaniline, 2,8diamino, 3,6 dithio 1- napthanol and 2,8 dia-
mino-1-napthalol with molecular weight 139, 240 and 174
respectively were formed. Pollution reduction values such as COD
and TOC in treated sample was noticed to be 85 and 87%. The
results revealed that the B. cereus is an efficient organism that
could degrade the dye effectively and reduce the pollution
thereof with this better alternative (Leelakriangsak and Borisut,
2012).
Literature reveals that three bacterial species such as M. luteus,
Listeria denitrificians and Nocordia atlantica exhibits strong decol-
ourizing activity. Among these N. atlantica showed almost complete
decolourization as compared to at least 80% of the other isolates
(Hassan et al., 2013). Ali et al. (2014) developed suitable technology
using a strain, namely, sphingomonas sp., isolated from petroleum
sludge that was capable of efficient aerobic degradation of at least 7
diverse azo dyes of more than 70% in 24 h. HPLC analyses of the
metabolites of three different azo dyes showed that depending on
the availability of oxygen during the dye degradation process, and
different sets of metabolites could be produced from these dyes (Ali
et al., 2014).
7.3. Biodegradation of an azo dye by using azoreductase enzyme
In this approach, azo-dye (C.I. Acid Blue 113) is degraded by
enzymatic treatment, namely, azoreductase enzyme. It was ob-
tained from bacterium Shigella boydii. Biodegradation experiments
carried out with the help of azoreductase enzyme showed
maximum rate of dye degradation of 96 and 92% for 100 and
200 mg/L of dye concentrations (maximum enzyme activity as
0.0014 U/ml). The other pollution parameters such as TOC and COD
values were reduced up to 87 and 88% (Senthilvelan et al., 2013).
The FT-IR results showed transformation of azo linkage, the pres-
ence of aromatic amine indicate the presence of azoreductase
enzyme, mass spectrum data showed the conversion of dye into
new intermediate metabolite like aniline, naphthalene 1,4-
diamine, 3-aminobenzenesulfonic acid, naphthalene-1-sulfonic
acid, 8-aminonaphthaalene-1-sulfonic acid, 5,8-diaminonap
hthalene-1-sulfonic acid. Biodegraded dye sample was further
reused in leather dyeing process which gave better color properties
that of conventional one. The present method is an eco-benign
method for biodegradation of azo dyes in dye effluents.
7.4. Biodegradation of an azo dye by using laccase enzyme
In this work, laccase enzyme obtained from M. luteus was used
for the biodegradation of azo dyes. The enzyme showed optimum
growth conditions at pH 7.0, temperature at 37  C and incubation
duration of 72 h. The enzyme was applied on the suitable dyes
namely CI Acid Black 52 and CI Acid Blue 113 for the degradation
and results were noted. These dyes (CI Acid Black 52 and CI Acid
Blue 113) resulted in the biodegradation rate of 92.2% and 94.5%
respectively (Table 5). The UVeVisible spectral analysis indicated
the absence of peaks in the visible region of the experimental
samples showing the complete biodegradation of dye samples. FT-
IR spectroscopy results showed the transformation of N]N into
N2 or NH3 and then into biomass (Fig. 6). The metabolites formed
in the biodegraded dye sample were analyzed by Mass-
Electrospray Ionization (M-ESI) spectra. C.I. Acid Blue 113 de-
grades to aniline (with mass 93.13), 5,8-diaminonapthalene 1-
sulfonic acid (with mass of 238.26), 8-amino naphthalene-1-
sulfonic acid (with mass of 223.25) and 5-aminonapthalene-1-
sulfonic acid (with mass of 223.25). The other dye, C.I. Acid
Black 52 results in intermediates such as 7-amino-4-hyrazinyl
naphthalene-1-thiol, 4,7-diamino naphthalene-1-thiol, naphtha-
lene-1,6-diamine and naphthalene-2-ol with the respective mo-
lecular weights of 205.28, 190.26, 158.20 and 144.17. It is
confirmed from the mass analyses report that all the above dyes in
presence of laccase undergo degradation phenomenon and results
in various intermediate metabolites as above. Apart from these,
the experimental samples showed pollution reduction of BOD and
COD values to the level of 93.2and 92.0 respectively for the above
dyes.
 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17 11

Table 5
Degradation of dyes by Laccase.

Different dyes Time duration (h) % of Degradation

0h 12 h 24 h 36 h 48 h 60 h 72 h 84 h 96 h

C.I. Acid Black 52 (mg) 20 19.3 17.2 11.9 9.1 6.6 4.3 3.1 1.56 92.2
C.I. Acid blue 113 (mg) 20 19 16.8 11.5 8.7 5.5 3.9 2.7 1.1 94.5
Control dye (mg) 20 19.7 18.3 16.4 14.1 12.4 9.1 6.5 4.3 78.5

7.5. Biodegradation of phenol 7.6. Improved uptake of retanning agents

Besides biodegradation of dyes, phenol also poses many envi-
ronmental challenges due to complex nature of phenol. Phenol
biodegradation is highly prioritized due to its hazardous nature on
the environment. P. putida Tan-1 and Staphylococcus aureus Tan-2
were used to biodegrade phenol. Experiments carried out by using
above species showed the rate of degradation of 94.2 and 88.1% for
phenol concentration of 600 and 800 mg/L respectively (Stoilova
et al., 2008; Sudipta and Somnath, 2010). The GCeMS spectral
investigation showed no phenol peak in the treated sample indi-
cating transformation of phenol into other intermediates like
catechol, succinate, cisecismuconate, ketoadipateenol lactone and
b-Ketoadipate (Fig. 7). FT-IR spectra confirmed the disappearance of
band at 3045 cm1 and a shift from aromatic to aliphatic region in
the experiment. The pollution loads such as COD was reduced to
91.3% for mixed culture (Senthilvelan et al., 2014a,b; Yamaga et al.,
2010).
A method has been designed for improved uptake of the
retanning agents in post tanning process. A retanning agent syn-
thesized by water based anionic Sulfonated Melamine-
Formaldehyde Condensate (SMFC) with very low free formalde-
hyde content was employed for retanning. 1e3% of SMFC was used
to treat leather that resulted in about 98% exhaustion of dye. The
organoleptic, color and physical strength properties were also
improved drastically in this method. Moreover, it was found that
the end product-leather attributed a very low content (<10 ppm) of
free formaldehyde (Jaisankar et al., 2010).
8. Mathematical modeling
As mathematical modeling can help to carryout scale-up or
down studies without repeating experiments, uptake of dye by

Fig. 6. FT-IR spectrum of the degraded dye samples (a e control sample C.I. Acid black
52 at zeroth hour; b e control sample C.I. Acid black 52 after 96 h and c e experimental
dye C.I. Acid blue 113 after 96 h).
Fig. 7. GCeMS investigation of the phenol degraded sample a. Control sample indi-
cating the biodegradation of phenol sample in absence of Pseudomonas putida Tan-1
and Staphylococcus aureus Tan-2 strains b. Experiment sample indicating the biodeg-
radation of phenol sample in presence of Pseudomonas putida Tan-1 and Staphylococcus
aureus Tan-2 strains.
12 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17

leather, degradation of dye and phenols in effluent etc were Parameters and surface properties of hair and flesh sides do not
mathematically modeled to describe the phenomena for optimi- change in this dyeing process. Adsorbed amount of dye can be
zation of process parameters (duration of exposure, temperature expressed as.
and pH).
t 1 1
¼ þ t (1)
8.1. Improved dyeing process q k2 q2e qe

Modeling of adsorption isotherms and kinetics for uptake of dye
by leather had been explained to provide uptake profile with time
and values of equilibrium (qe) concentration of dye-uptake
(adsorbed amount, q mg/l at time t h). A continuous surface reac-
tion with pore diffusion model is synthesized to describe adsorp-
tion of dye from bath to leather through a non-stationery
concentration field. It is assumed that monolayer of flesh side of
fluid will act as faster reactive spots and the chemicals will diffuse
slowly through the inner side of (across the thickness) leather.
where k2 is kinetic adsorption constant (pseudo 2nd order kinetics).
Dyeing process takes two stages to complete. During the initial
stage of the process the uptake rate is faster due to reaction of
active sites of dyes and the layers of leather (flesh side); later on,
as the dye penetrates through pores and micropores structures of
leather, the diffusion controlled process become slower and dye
uptake rate becomes sluggish (Fig. 8aec). Fig. 8a shows plot of dye
uptake against time where t/q (as per Eq. (1)) has been plotted
against time whereas q is plotted against time in Fig. 8b. Fig. 8a

Fig. 8. a. Growth of microbial culture. (i) Substrate concentration is plotted against microbial concentration (ii) specific growth rate of bacterial cells with time at different initial
concentrations of dye. b. Kinetics of dyeing by mathematical modeling. (i) shows plot of dye uptake against time with Langmuir isotherm (experimental and predicted values). (ii)
Shows plot of dye uptake against time with Langmuir isotherm (experimental and predicted values) [Expt e stands for experimental; Model e stands for predicted]. c. Effects of
parameters on dye uptake rate (without Nano Particle Polymer). Dye up [take increases with increase in temperature, time or pH].
 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
shows a very good agreement between experiment and model
values with a R2 ¼ 0.9983. Fig. 8b yields a R2 ¼ 0.9680. Fig. 8c
shows effect of model parameters on dye uptake without NPP
(nano-particle polymer). It was found (Kanagaraj and Panda,
2011) that dye adsorption by leather is better represented by
Langmuir isotherm confirming involvement of a single layered
adsorbate.
8.2. Biodegradation of phenol
Phenol and its derivatives, though toxic in nature, are widely
found in most of the industrial wastes causing pollution. These
hazardous chemicals make it mandatory to treat the effluent
properly. These compounds are not completely eliminated in
conventional treatment or they are formed due to many inter-
mediate reactions during effluent treatment. Thus, biological
treatments are necessary to eliminate these compounds or
degrade these chemicals to lower molecular end products without
producing further toxic residues. Haldane model has been fitted
(Senthilvelan et al., 2012) for the growth of mixed culture. It is
assumed that with course of time the growth rate increases while
some of the cells starts dyeing that increases with time and ulti-
mately comes to stable value when the culture starts surviving
giving a balance between growth and death rates. The model can
be described as:
Fig. 9. Modeling of phenol degradation. a). Plot of substrate concentration with time. b). Plot of [log(cell growth)/time] with [log(substrate)/time]. c). Plot of progress of parameters
with time. d). Model validation: Comparison of experimental values (substrate concentration) with that of theoretical model (Haldane kinetics).
13
ðs  s0 Þ2 lnðx=x0 Þ
Ks lnðs=s0 Þ þ ðs  s0 Þ þ ¼ (2)
2Ki t  t0
and the cell growth dynamics
lnðx=x0 Þ lnðs=s0 Þ
¼  kd (3)
t t
where Ks is half saturation constant (mg/l) and s (mg/l) is substrate
concentration, s0 is initial substrate concentration (mg/l), x is of cell
mass (mg), t is time in min, kd is the death rate (mg/l) and Ki is
substrate inhibition constant (mg/l).
Fig. 9a shows the time course profile of the phenol biodegra-
dation by the mixed culture. It can be seen that the mixed culture is
able to degrade completely up to 40 mg/l in a time of 80 min. It is
evident from the experiment that the time taken by the mixed
culture to degrade phenol is dependent on its initial concentration
and bio-degradation rate is dependent on initial concentration of
phenol. Fig. 9b shows a declined growth profile due to rise in death
rate of the culture. This graph helps in finding out the death rate kd.
The intercept in y axis is 0.0355 and using Eq. (3) it can be found
that kd ¼ 0.0355. With depletion of substrate concentration cell
growth increases which is shown in Fig. 9c. Profile of growth rate is
plotted against time in Fig. 9d where the maximum growth rate is
found to be 0.35 l min1. Initially, the growth rate is very high and
then due to starting of death rate, the actual growth and survival
14 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
rates decrease and reach to steady value. Haldane equation was
used to find Ks (saturated substrate conc.) and Ki (inhibition con-
stant) parameters using nonlinear least square. In order to under-
stand the mechanism of degradation and kinetics of the treatment
process, it is necessary to formulate a mathematical model for
further studying the system and for finding optimization and safe
operability conditions for the specific problem (Senthilvelan et al.,
2012). Due to presence of higher concentration of substrates (s),
Haldane kinetics was found suitable for degradation with inhibi-
tion. The growth rate is given by
mm s
m¼ 2
(4)
Ks þ s þ Ks i
where Ki is substrate inhibition constant (mg/l), Ks is half velocity
concentration (mg/l) and mm be maximum growth rate (h1). It was
assumed that cell growth enters to lag phase, exponential and
stationery phases. Some of the cells die in the system. Nonlinear
regression of experimental growth rate data yielded Ks ¼ 35 mg/l
and Ki ¼ 779 mg/l and residual norm was found to be 0.0195
indicating that the time taken by the mixed culture to degrade
phenol is depended on its initial concentration and bio-degradation
rate is dependent on initial concentration of phenol.
8.3. Biodegradation of azo dyes e modeling
Textile and leather industries use different types of azo dyes and
release toxic and carcinogenic effluents containing these dyes
Fig. 10. a. Plot of 1/q against c/q for the adsorption of dye by biological means showing
validation of Langmuir isotherm. b. Plot of 1/q against c/q: Comparison between
experimental and theoretical model for the dye degradation process.
which needs to be treated using laccase enzyme for complete
degradation before releasing to the environment. Experiments
were conducted (Senthilvelan et al., 2014a,b) where complex dye
molecule degrades into intermediates and then finally to non-toxic
end product, to formulate mathematical model for the degradation.
With the assumption that the system is well mixed where V be the
volume of the liquor (l), W be weight (mg) of dye and S0 be its
concentration (mg/lit) at time t ¼ 0 of mixing, a model was made to
explain the microbes assisted enzymatic degradation kinetics. The
parent dye degrades through formation of intermediates and finally
to end product helping in the growth of biomass. This degradation
process using laccase produced by the microbial species is of
pseudo first order type. It is also assumed that the phenomenon is
dominated by reaction and not by diffusion or adsorption. As soon
as the enzyme comes out of the cell, it helps to degrade the sub-
strate dye. Growth of biomass is proportional to amount of degra-
dation of dye. After mixing the microbial cells, the concentration of
dye in the effluent is monitored/analysed by withdrawing samples
at relevant hours. Growth rates of biomass are calculated from
experimentally observed values of dye degradation. With these
values, parameters of the model structures of Haldane growth Eq.
(4) are estimated using nonlinear least square algorithm. Ks and Ki
can be found out from nonlinear regression of growth rate data
(Fig. 10a, b). Ks ¼ 17.98 mg/l, Ki ¼ 41.34 mg/l and Kd ¼ 0.0011 mg/l
where Kd is death rate, and residual norm was found to be 0.0314
for CI Acid Blue 113. Fig. 10a shows % degradation of dye with time.
It can be found from the figure that at 96 h, the % degradation is
about 92%. Fig. 10b shows plot of specific growth rate of cells with
respect to time of observation/degradation. It can be observed from
the figure that at about 12 h, the growth rate of cells becomes
maximum. Growth of biomass is proportional to amount of
degradation of dye. From the experiments it can be said that the
particular microbe follows Haldane kinetics of growth in degrading
the selected dye.
As most of the leather industries use chromium (though at a
higher concentration, this heavy metal is toxic and carcinogenic), it
is needed to be removed from effluent water of these industries. A
mathematical model was developed explaining the bisorption ki-
netics using Langmuir isotherm. The model assumes that the
adsorbent particles (microbes) constitute homogeneous medium
while adsorbate molecules gets adhered to the surface of adsorbent
particles. Adsorbate slowly enters through diffusion and is also
transferred through the adsorbent particles by “Creeping” from one
adsorption site to another on the solid surface. This transport can be
explained by initial diffusion (Fick's 2nd law) and flowed by
attaining equilibrium between the solid phase and liquid phase
concentration (C) at the surface of adsorbent particles (radius, R).
Let q be adsorbed concentration (mg/l) in the pores of matrix, r be
any point along radius (m), t be time (h) and Ds be diffusivity
(m2s1). A material balance equation (pore diffusion) with
following boundary condition was established.
 
vq 1 v vq
¼ 2 Ds r 2 for 0  r  R and t  0 (5)
vt r vr vr
with initial condition as q ¼ 0, 0  r R and t  0 and boundary
conditions as vq/vr ¼ 0 for r ¼ 0
qe kL Ce
¼ for r ¼ R (6)
qm 1 þ kL Ce
where q be the dimensionless normalized concentration of adsor-
bate inside the adsorbent (with e for equilibrium and m for
maximum) and KL be associated mass transfer in liquid phase. The
observed qm values (concentration of maximum adsorbed)
 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
conclude that the maximum adsorption corresponds to a saturated
monolayer of adsorbate molecules on adsorbent surface with
constant energy and no transmission of adsorbate in the plane of
the adsorbent surface. The observed KL values shows that the
adsorbent prefers to bind acidic ions and that speciation pre-
dominates on sorbent characteristics, when ion exchange is the
predominant mechanism takes place in the adsorption of chro-
mium ion. Langmuir constant (kL) is a measure of the amount of
chromium adsorbed per unit weight of adsorbent, when saturation
is attained, was found to be 10.98. Also it was found that the
adsorption with a monolayer reaches saturation after 120 h. A
separation factor of RL ¼ 0.9 suggests that (0 < RL < 1) the
adsorption is favorable with monolayer.
9. Future directions for eco-friendly sustainable leather
processing
This study reviews various eco-friendly means of producing
leather starting from curing to post tanning operations for cleaner
production. Keeping in the mind of cleaner and green waste man-
agement, the viable unit operations have been reviewed. Now-a-
days, it is mandatory to adopt and practice various cleaner pro-
duction strategies in the industry for the greener environment. Use
of cleaner preservation techniques using boric acid method, enzy-
matic soaking and dehairing by protease, improved high exhaust
chrome tanning with the help of FH, improved dyeing by NPP,
improved retanning by using SMFC have been suggested. By
adopting these technologies, it is possible to abate the ways for
reduction in pollution load such as BOD, COD, TDS and TSS up to
levels of 50%, 40%, 50% and 20% respectively. Mathematical models
can show the way to predict kinetics and diffusive mechanism that
will help in up scaling the process for commercial exploitation. The
said technologies help the tanner to get rid of the pollution prob-
lems. These technologies are very helpful for minimization of major
proteinous wastes such as Fleshing, Keratin wastes and major
chemical wastes such as salt, chrome tannin, vegetable tannin, dye
compound in the leather industry.
10. Conclusions
From the above study, it is understood that various cleaner
technological options adopted in leather processing have been
discussed in detail. Eco-friendly methods of curing by using silica
gel, boric acid, SMB can be used for cleaner preservations as they
reduce TDS and Cl to a minimum level of 80%. Phytochemical
preservation using neem cake and tamarind leaves has also re-
ported. Use of bacteriocin not only helps in preservation but also
reduces TDS upto 94.4% and Cl 96.5%. Enzymatic unhairing has
replaced use of sulfide by eco-friendly proteolytic enzymes which
not only improve results on dehairing step but also reduces the
BOD, COD at the level of 40% and 50% respectively. The solid
(fleshing) waste can be used to generate valuable end products
such as modified FH, Biotannin (used for improved chrome tan-
ning). The chromium pollution arising in tanning can be minimized
by using the FH composite and fibrin hydrolysate. The pollution
load arising out of chrome, vegetable tannin and dye can be mini-
mized by using biodegradation and ozonation techniques. Use of
NPP in dyeing helps in cleaner production while SMFC yields
improved re-tanning of leather. Biodegradation of azo dyes and
phenols can reduce toxicity of effluent. Suggested methods of
biodegradation of azo-dyes using suitable bacterial strain such as
Bacillus cereus and Azoreductase enzyme can effectively reduce
pollution hazards. In all the cleaner techniques reviewed in this
article, the properties of the leather were found comparable or
improved over the conventional/traditional techniques. This review
15
gives state of art of available cleaner leather processing methods
and their benefits.
References
Abraham, J., Gea, T., Sa
nchez, A., 2014. Substitution of chemical dehairing by pro-
teases from solid-state fermentation of hair wastes. J. Clean. Prod. 74, 191e198.
Ali, L., Alhassani, H., Karuvantevida, N., Rauf, M.A., Ashraf, S.S., 2014. Efficient aer-
obic degradation of various azo dyes by a Shingomonas sp. isolated from pe-
troleum sludge. J. Biorem. Biodeg. 5 (3), 1e10.
Andrioli, E., Gutteres, M., 2014. Associated use of enzymes and hydrogen peroxide
for cowhide hair removal. J. Am. Leather Chem. Assoc. 109 (2), 35e69.
Aravindhan, R., Saravanabhavan, S., Thanikaivelan, P., Rao, J.R., Nair, B.U., 2007.
A Chemo e enzymatic pathway leads towards zero discharge tanning. J. Clean.
Prod. 15, 1217e1227.
Arunachalam, C., Saritha, K., 2009. Protease enzyme an eco-friendly alternative for
leather industry. Ind. J. Sci. Technol. 2 (12), 29e32.
Asad, S., Amoozegar, M.A., Pourbabaee, A.A., Sarbolouki, M.N., Dastgheib, S.M., 2007.
Decolorization of textile azo dyes by new isolated halophilic and halotolerant
bacteria. Bioresour. Technol. 98, 2082e2088.
Bienkiewiez, K., 1983. Physical Chemistry of Leather Manufacture. RE Krieger
Publishing Company, Florida, USA.
Braganca, I., Nouws, H., Crispin, A., 2013. Adding value [valorization] to tannery
fleshings: Part-II effect of protein hydrolysates on leather dyeing. JSLTC 97,
111e120.
Cavello, I., Cavallitto, S., 2013. Optimization of keratinolytic protease production by
Pupureocillium LPS#876 as a sustainable management of tannery hair. J. Am.
Leather Chem. Assoc. 108 (8), 300e310.
Chandra Babu, N.K., Karthikeyan, R., Swarna kumara, B., Ramesh, R., Shanthi, C.,
Sadulla, S., 2012. A systematic study on the role of chilling temperature on the
curing efficiency of hides and skins. J. Am. Leather Chem. Assoc. 107, 362e370.
Cuadros, S., Manresa, M.A., Font, J., Bautista, M.E., Puig, R., Marsal, A., 2012. Alter-
native fungicides for the leather industry: application in various processes.
JSLTC 96, 225e233.
Dalmases, B. Anna, Jorba, Montse, Valles, F. Joaquim, Shendrik, Alexander, Olle
Otero, Lluís, 2012. Biodegradation of leather tanned with inorganic salts. JSLTC
95, 63e67.
Dalton, D., 2012. New generation fungicide for the leather industry. J. Am. Leather
Chem. Assoc. 107 (1), 1e32.
Dayanadan, A., Kanagaraj, J., Sunderraj, L., Govindaraju, R., Suseela Rajakumar, G.,
2003. Application of alkaline protease in leather processing e an eco-friendly
approach. J. Clean. Prod. 11, 533e536.
Detimer, A., Coelho, C.J., Cavalli, E., Misturini, R.D., Gusatti, C., Ayub, M.H.Z.,
Gutterres, M., 2012. Optimization of the biotechnological process for hide
unhairing in substitution of toxic sulphide. Chem. Eng. Technol 35, 803e810.
Dettmer, A., Anjos, P.S.D., Gutterres, M., 2013. Special review paper: enzymes in the
leather industry. J. Am. Leather Chem. Assoc. 108 (4), 146e158.
Dixit, S., Yadav, A., Dwivedi, P.D., Das, M., 2015. Toxic hazards of leather industry and
technologies to combat threat: a review. J. Clean. Prod. 87, 39e49. http://
dx.doi.org/10.1016/j.jclepro.2014.10.017.
Elisangela, F., Andrea, Z., Fabio, D.G., Cristiano, R.M., Regina, D.L., Artur, C.P., 2009.
Biodegradation of textile azo dyes by a facultative staphylococcus arlettae strain
VN-11 using a sequential microaerophilic/aerobic process. Int. Biodeter. Bio-
degrad. 63, 280e288.
Ershad-Langroudi, A., Mirmontahai, A., 2013. Hydroxyapatite nanoparticles and
polyethylene glycol treatment of historical leatheremechanical properties.
J. Am. Leather Chem. Assoc. 108, 449e456.
Fang, H., Wenrong, H., Yuezhong, L., 2004. Biodegradation mechanisms and kinetics
of azo dye 4BS by a microbial consortium. Chemosphere 57, 293e301.
Fennen, J., Herta, D., Pelckmans, J.-T., Christner, J.T.F.L., Ledertechnik, A.G.,
November/December 2013. The sulphide challenge: improved leather quality
using less sulphide. Leather Int. 25e27.
Font, J., Reyes, M., Cuadros, S., Bacardit, A., Marsal, A., 2011. Determination of TCMTB
and other fungicides in leather. J. Am. Leather Chem. Assoc. 106 (11), 316e352.
George, N., Chauhan, P.S., Kumar, V., Puri, N., Gupta, N., 2014. Approach to eco-friendly
leather: characteristics and application of an alkaline protease for chemical free
dehairing of skins and hides at pilot scale. J. Clean. Prod. 79, 249e257.
Gong, Y., Cheng, K., Zhang, T., Chen, W., 2011. Automated clean leather dyeing
assisted by Whikal, U.S. and microwave. J. Am. Leather Chem. Assoc. 106 (4),
127e132.
Guo, Z.-R., Zhang, G., Fang, J., Dou, X., 2006. Enhanced chromium recovery from
tanning waste water. J. Clean. Prod. 14, 75e79.
Gupta, S.D., 2004. Modified the blue chrome tanning for lambskins: low residual
chrome tannage. JSLTC 88, 116.
Gutterres, M., Aquim, P.M., Passos, J.B., Trierweiler, J.O., 2010. Water reuse in tannery
beamhouse process. J. Clean. Prod. 18, 1545e1552.
Hassan, M.M., Alam, M.Z., Anwar, M.N., 2013. Biodegradation of Azo dyes by bacteria
isolated from dyeing Industry effluent. Int. Res. J. Biol. Sci. 2 (8), 27e31.
Hintermeyer, B.H., Tavani, E.L., 2013. Absorbtion, bioabsorption and bio-
accumulation used to remove chromium (III) from tanning waste waters: a
critical Review. JSLTC 97, 231e237.
Hu, J., Xiao, Z., Zhou, R., Deng, W., Wang, M., Ma, S., 2010. Ecological utilization of
leather tannery waste with circular economy model. J. Clean. Prod. 18, 221e228.
16 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
Husseiny, S.M., 2008. Biodegradation of the reactive and direct dyes using egyptian
isolates. J. Appl. Sci. Res. 4 (6), 599e606.
Jaisankar, S.N., Gupta, S., Lakshminarayana, Y., Kanagaraj, J., Mandal, A.B., 2010. Water-
based anionic sulfonated melamine formaldehyde condensate oligomer as
retanning agent for leather processing. J. Am. Leather Chem. Assoc.105, 289e296.
Jegannathan, K.R., Nielsen, P.H., 2013. Environmental assessment of enzyme use in
industrial production e a literature review. J. Clean. Prod. 42, 228e240.
Kanagaraj, J., Chandra Babu, N.K., Sadulla, S., Suseela Rajakumar, G., Chandra
Kumar, N., 2001. Cleaner techniques for the preservation of raw goat skin.
J. Clean. Prod. 9, 261e268.
Kanagaraj, J., Gupta, S., Basker, G., Reddy, B.S.R., 2008. High exhaust chrome tanning
using novel copolymer for eco-friendly leather processing. J. Am. Leather Chem.
Assoc. 103, 36e42.
Kanagaraj, J., Mandal, A.B., 2012. Combined biodegradation and ozonation for
removal of tannins and dyes for the reduction of pollution loads. Environ. Sci.
Pollut. Res. 19, 42e52.
Kanagaraj, J., Panda, R.C., 2011. Modeling of dye uptake rates, related interactions,
and binding energy estimation in leather matrix using protein based nano-
particle polymer. Ind. Eng. Chem. Res. 50, 12400e12408.
Kanagaraj, J., Sadulla, S., Jawahar, M., Victor Babu, K., 2003. Interaction of aldehyde
developed from amino acids of tannery waste in a lower- chrome tannage: an
eco-friendly approach. J. Soc. Leather Tech. Chem. 89, 18e27.
Kanagaraj, J., Sastry, P., Rose, C., 2005. Effective preservation of raw goat skin for the
reduction of total dissolved solids. J. Clean. Prod. 13, 959e964.
Kanagaraj, J., Senthilvelan, T., Mandal, A.B., 2012. Biological method for decolour-
isation of an azo dye: clean technology to reduce pollution load in dye waste
water. Clean. Technol. Environ. Policy 14, 565e572.
Kanagaraj, J., Shanmugaiah, V., Sekar, S., Sastry, T.P., 2007. Fibrin hydrolysate as a
chrome exhaust aid and retaning agent in the leather production: an approach
towards environmental e friendly leather processing. Leather Age 29, 64e71.
Kanagaraj, J., Tamil Selvi, A., Senthilvelan, T., Chandra Babu, N.K., Chandrasekar, B.,
2014. Evaluation of new bacteriocin as a potential short-term preservative for
goat skin. Am. J. Microb. Res. 2 (3), 86e93.
Kandasamy, N., Velmurugan, P., Sundarvel, A., Raghava, R.J., Bangaru, C.,
Palanisamy, T., 2012. Eco-benign enzymatic dehairing of goatskins utilizing a
protease from a Pseudomonas fluorescens species isolated from fish visceral
waste. J. Clean. Prod. 25, 27e33.
Kanth, S.V., Venba, R., Madhan, B., Chandrababu, N.K., Sadulla, S., 2009. Cleaner
tanning practices for tannery pollution abatement: role of enzymes in eco-
friendly vegetable tanning. J. Clean. Prod. 17 (5), 507e515.
Karthikeyan, R., Chandrababu, N., Mandal, A., Shegal, P., 2011. Keratin-silica matrix-
Anew problem filler from chicken feathers for retanning. J. Am. Leather Chem.
Assoc. 106 (2), 35e75.
Khalid, A., Batool, S., Siddique, M.T., Nazli, Z.H., Mahmood, R.B.S., Arshad, M., 2011.
Decolorization of remazol black-B azo dye in soil by fungi. Soil Environ. 30 (1),
1e6.
Lee, S., Shin, E., Kim, W., Park, S., 2012. Dyeing process for improving properties of
black color using natural dyes and mordant. J. Am. Leather Chem. Assoc. 107 (2),
33e69.
Leelakriangsak, M., Borisut, S., 2012. Characterization of the decolorizing activity of
azo dyes by Bacillus subtilis azoreductase AzoR1. Songklanakarin J. Sci. Technol.
34 (5), 509e516.
Li, K., Chen, H., Wang, Y., Shan, Z., Yang, J., Brutto, P., 2009. A salt free pickling regime
for hides and skins using oxazolidine. J. Clean. Prod. 17 (17), 1603e1606.
Liu, M.-H., Zang, H., Zhang, X.-S., Deng, Y., Liu, W., Zhan, W., 2001. Removal and
recovery of chromium (III) from aqueous solutions by a spherical cellulose
adsorbent. Water Environ. Res. 73, 322e328.
Ludvik, J., 1996. Cleaner Tanning Technologies. UNIDO report, pp. 18e25.
Ma, J., Hou, X., Gao, D., Lv, B., Zhang, J., 2014. Greener approach to efficient leather
soaking process: role of enzymes and their synergistic effect. J. Clean. Prod. 78,
226e232.
Ma, J., Lv, X., Gao, D., Li, Y., Lv, B., Zhang, J., 2014a. Nanocomposite-based green
tanning process of suede leather to enhance chromium uptake. J. Clean. Prod.
72, 120e126.
Mariappan, M., 1997. Environmental protection initiatives in Indian tanneries e a
perspective review. In: Proce. 30th Leather Research Industry Get Together.
CLRI, Chennai, pp. 151e161.
Morera, J.M., Bartolí, E., Chico, R., Sole
, C., Cabeza, L.F., 2011. Minimization of the
environmental impact of chrome tanning: a new process reusing the tanning
floats. J. Clean. Prod. 19 (17e18), 2128e2132.
Morera, J.P., Bartoli, E., Singla, C., 2013. Effect of ultrasound on bovine and ovine
skins soaking. J. Clean. Prod. 59 (11), 79e85.
Musa, A., Selvi, A., Aravindhan, R., Madhan, B., Fathima, A., Rao, J.,
Chandrasekaran, B., 2011. Evaluation of antimicrobial activity of Law-
soniaInermis (Henna) against microbial strains isolated from goat skins/leather.
J. Am. Leather Chem. Assoc. 106 (5), 145e178.
Muthsubramanian, L., Mitra, R.B., 2006. A cleaner production method for the syn-
thesis of bronopol e a bactericide that is useful in leather making. J. Clean. Prod.
14, 536e538.
Nashy, E., Hussein, A., Essa, M., 2011. Novel retanning agent for chrome tanned
leather based on emulsion e nano particles of styrene/Butyl acerylati Co-
polymers. J. Am. Leather Chem. Assoc. 106 (9), 241e248.
Nazer, D.W., Al-Saed, R.M., Siebel, M.A., 2006. Reducing the environment impact of
the unhairing-liming process in the leather tanning industry. J. Clean. Prod. 14
(1), 65e74.
Nigam, P., Armour, G., Banat, I.M., Singh, D., Marchant, R., 2000. Physical removal of
textile dyes from effluents and solid-state fermentation of dye-adsorbed agri-
cultural residues. Bioresour. Technol. 72, 219e226.
Nikhil, B.S., Dimple, R.V., Nishant, S.J., 2012. Decolorization, degradation and azo-
reductase study by bacterial transformation of reactive red HE8b. Int. J. Res.
Biosci. 1 (1), 29e41.
Ocak, B., Aslan, A., Gulumser, G., 2011. Utilization of chromium tanned leather
solid wastes in microencapsulation. J. Am. Leather Chem. Assoc. 106 (7),
232e238.
Olukanni, O.D., Osuntoki, A.A., Gbenle, G.O., 2006. Textile effluent biodegradation
potentials of textile effluent- adapted and non-adapted bacteria. Afr. J. Bio-
technol. 5, 1980e1984.
Oppong, D., Bryant, D.S., Rangarajan, R., Steele, S., 2006. Application of molecular
techniques to identify bacteria isolated from the leather industry. J. Am. Leather
Chem. Assoc. 101, 140e145.
Ozdemir, G., Pazarbasi, B., Kocyigit, A., Omeroglu, E.E., Yasa, I., Karaboz, I., 2008.
Decolorization of acid black 210 by vibrio harveyi TEMS1, a newly isolated
bioluminescent bacterium from Izmir Bay, Turkey. World J. Microbiol. Bio-
technol. 24, 1375e1381.
Palma, C., Moreira, M.T., Mielgo, I., Feijoo, G., Lema, J.M., 1999. Use of a fungal
bioreactor as a pretreatment or post-treatment step for continuous decolor-
isation of dyes. Water Sci. Technol. 40, 131e136.
Parti, A., Chaudhary, R., Subramani, S., 2013. Biochemical method for extraction and
reuse of protein and chromium from chrome leather shavings: a waste wealth
approach, 108 (10), 365e372.
Puvanakrishnan, R., Bose, S.M., Dhar, S.C., 1981. Comparative studies of enzyme
unhairing with immobilized pancreatic enzyme product and enzyme depilatory
“M” in the manufacture of garment leather. Leather Sci. 32e38.
Rao, R.J., Chandrababu, N.K., Muralidharan, C., Unni Nair, B., Rao, P.G., Ramasami, T.,
2002. Recouping the wastewater: a way forward for cleaner leather processing.
J. Clean. Prod. 11, 591e599.
Ramasami, T., Rao, J.R., Chandrababu, N.K., Parthasarathi, K., Rao, P.G., Saravanan, P.,
Gayathri, R., Sreeram, K.J., 1999. Beamhouse and tanning operations: process
chemistry revisited. J. Soc. Leather Tech. Chem. 83, 39e45.
Ramasami, T., Sreeram, K.J., Gayatri, R., 1999a. Emerging Options of Leather Pro-
cessing for Waste Minimization UNIDO Manual on Design, Operational and
Maintenance of Tannery Effluent Treatment Plants. RePo-UNIDO and AISHTMA,
Chennai, pp. 20e31. Unit 1.
Saravanan, P., Shiny Renitha, T., Gowthaman, M.K., Kamini, N.R., 2014. Under-
standing the chemical free enzyme based cleaner unhairing process in leather
manufacturing. J. Clean. Prod. 79 (15), 258e264.
Saurabh, Saran, Mahajan, Richi V., Kaushik, Rekha, Isar, Jasmine, Saxena, Rajendra
K., 2013. Enzyme mediated beam house operations of leather industry: a
needed step towards greener technology. J. Clean. Prod. 54 (1), 315e322.
Sekaran, G., Swarnalatha, S., Srinivasulu, T., 2007. Solid waste management in
leather sector. J. Des. Man. Technol. 1 (1), 47e52.
Senthilvelan, T., Kanagaraj, J., Mandal, A.B., 2012. Application of enzymes for
dehairing of skins: cleaner leather processing. Clean. Technol. Environ. Policy
14, 889e897.
Senthilvelan, T., Kanagaraj, J., Panda, R.C., 2014a. Enzyme-mediated bacterial
biodegradation of an azo dye (C.I. Acid Blue 113): reuse of treated dye waste-
water in post-tanning operations. Appl. Biochem. Biotechnol. 174, 2131e2152.
Senthilvelan, T., Kanagaraj, J., Panda, R.C., Mandal, A.B., 2014b. Biodegradation of
phenol by mixed microbial culture an eco-friendly approach for the pollution
reduction. Clean. Technol. Environ. Policy (16), 113e126.
Senthilvelan, T., Kanagaraj, J., Vinodh Kumar, M., Mandal, A.B., 2013. Biodegradation
of an Azo Dye by using Azoreductase enzyme and its relevance in leather
manufacture. In: XXXII Congress of IULTCS, May2013, Istanbul/Turkey, Leather
Age, pp. 13e19.
Shanthi, C., Banerjee, P., Chandrababu, N., Rajakumar, G., 2013. Recovery and
characterization of protein hydrolysate from chrome shavings by microbial
degradation. J. Am. Leather Chem. Assoc. 108 (6), 231e239.
Song, J., Tao, W., Chen, W., 2008. Ultrasound-accelerated enzymatic hydrolysis of
solid leather waste. J. Clean. Prod. 16 (5), 591e597.
Song, S., Tao, W., Chen, W., 2011. Kinetics of enzymatic unhairing by protease in
leather industry. J. Clean. Prod. 19 (4), 325e331.
Sovsky, J.M., Sedliacihy, J., Jukovic, P., Kopny, J., Duchovic, P., 2011. Dechroming of
chromium shavings without oxidation to hazardous Cr6þ. J. Am. Leather Chem.
Assoc. 106 (1), 8e17.
Stoilova, I., Krastanov, A., Bui, H., 2008. Biodegradation of mixed phenolic com-
pounds by a microbial association of Aspergillus awamori and Thermoascus
aurantiacu. EJEAF Chem. 7, 2625e2633.
Stolz, A., 2001. Basic and applied aspects in the microbial degradation of azo dyes.
Appl. Microbiol. Biotechnol. 56, 69e80.
Subbarao, C.H., Sathish, T., Ravichandra, P., Prakasam, R.S., 2009. Characterization of
thermo and detergent stable serine protease from isolated bacillus circulans and
evaluation of eco-friendly applications. Proc. Biochem. 44, 262e268.
Sudipta, D., Somnath, M., 2010. Performance and kinetic evaluation of phenol
biodegradation by mixed microbial culture in a batch reactor. Int. J. Water
Resour. Environ. Eng 2, 40e49.
Sundar, V.J., Raghava Rao, J., Muralidharan, C., 2002. Cleaner chrome tanning e
emerging options. J. Clean. Prod. 10 (1), 69e74.
Tamil Selvi, A., Shipra, S., Krithiga, G., Chandrasekaran, B., Rose, C., 2011. Antioxidant
and antimicrobial activity of leaves extract (Tamarindus indica) and it's
phytochemical characterization. J. Pharm. Res. 4 (12), 4435e4438.
 J. Kanagaraj et al. / Journal of Cleaner Production 89 (2015) 1e17
Thanikaivelan, P., Raghava Rao, J., Unni Nair, B., Ramasami, T., 2001. Approach to-
wards zero discharge tanning: role of concentration on the development of eco-
friendly liming-reliming processes. In: Poster Paper presented at 26th IULTCS
Congress, Cape Town, South Africa, March 2001.
Thanikaivelan, P., Rao, J.R., Nair, B.U., Ramasami, T., 2002. Zero discharge tanning: a
shift from chemical to biocatalytic leather processing. Environ. Sci. Technol. 36
(19), 4187e4194.
Vandevivere, P.C., Bianchi, R., Verstraete, W., 1998. Treatment and reuse of waste
water from the textile wet-processing industry: review of emerging technolo-
gies. J. Chem. Technol. Biotechnol. 72, 289e302.
Valeika, V., Beleska, K., Valeikiene,
_ V., Kolodzeiskis, V., 2009. An approach to cleaner
production: from hair burning to hair saving using a lime-free unhairing sys-
tem. J. Clean. Prod. 17 (2), 214e221.
Vedaraman, N., Muralidharan, C., 2011. Two stage leather dyeing e a novel approach
to minimize dye discharge in the effluent. J. Am. Leather Chem. Assoc. 106 (5),
184e189.
Verma, A., Pal, H.S., Singh, R., Agarwal, S., 2011. Pottential of Alkaline protease
isolated from thermoactinomyces sp. RM4 as an alternative to conventional
17
chemicals in leather industry dehairing process. Int. J. Agric. Environ. Bio-
technol. 4 (2), 173e178.
Vesela, A., Suchomel, L., Kupee, J., Mladek, M., 2002. Chromium and its exhaustion.
Das Leder 36, 37e43.
Viral, S., Kunjal, P., 2012. Degradation of azo dye Acid blue 158 by soil microbes. Res.
J. Biotechnol. 7 (2), 50e57.
Wang, R., Min, C., Haiming, C., Li, Z., 2009. Enzyme unhairing an eco-friendly
biotechnological process. J. Soc. Leather Tech. Chem. 93, 51e55.
Whiteley, C.G., 2007. Bioremediation of textile dyes. Ind. Bioprocess 29, 7.
Yamaga, F., Washio, K., Morikawa, M., 2010. Sustainable biodegradation of phenol
by acinetobacter calcoaceticus P23 isolated from the Rhizosphere of Duckweed
Lemna aoukikusa. Environ. Sci. Technol. 44, 6470e6474.
Yuanlong, C., Min, C., Xiaoju, C., Wenhua, Z., Xuepin, L., Bi, S., 2012. Enzymatic hy-
drolysis of skin shavings for preparation of collagen hydrolysates with specified
molecular weight distribution. JSLTC 96, 16e20.
Zhang, B., Xu, L., Ding, K., 2011. Dyeing/cross linking property of natural iredoid to
protein fibers. J. Am. Leather Chem. Assoc. 106 (4), 121e126.