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Journal of Cleaner Production 87 (2015) 39e49

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Journal of Cleaner Production


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

Review

Toxic hazards of leather industry and technologies to combat threat:


a review
Sumita Dixit, Ashish Yadav, Premendra D. Dwivedi, Mukul Das*
Food, Drug & Chemical Toxicology Group, CSIR-Indian Institute of Toxicology Research, Mahatma Gandhi Marg, P. O. Box 80, Lucknow 226001, U.P., India

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

Article history: Leather industry has significant economic influence; however, it suffers from the negative impact due to
Received 25 February 2014 environmental pollution caused by tannery wastes produced during leather processing processes. The
Received in revised form tanning processes contribute significantly to chemical oxygen demand (COD), total dissolved solids
24 September 2014
(TDS), chlorides, sulfates and heavy metal pollution. The chemicals discharged into aquatic systems end
Accepted 6 October 2014
Available online 16 October 2014
up in highly polluted sediments and salinisation of rivers. European Chemical Agency (ECHA) has
prioritized some of the hazardous chemicals used in leather under Substances of Very High Concern
(SVHC) and substances for Authorization. The situation has highlighted the need for greener technolo-
Keywords:
Bating
gies. Out of the two broad categories of technical methods, the first group involves the introduction of
Clean technology processing technologies by decreasing the effluent pollution load, avoiding the use of harmful chemicals
Finishing operations and producing solid wastes that can be used as by-products. The other category is related to the treat-
Pre tanning operations ment of wastewater, handling and processing of solid waste in an environment-friendly manner. Both
Post tanning operations methods have been applied to prevent negative impact on the environment during leather production.
Water management The methods have been reviewed for their technical suitability and commercial feasibility and it was felt
that combination of both is essential. The technologies can have up-front additional costs but have to be
balanced against multiple benefits in terms of environmental cleanup, improved labour productivity,
material quality consistency and better international image. By using the best available technologies and
optimized systems the leather industry can evolve as an environment friendly technology.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction upon various tanning processes are vegetable tanned leather


(Madhan et al., 2001a), chrome-tanned leather (Heidemann, 1993;
Leather industry, an age old enterprise provide a wide range of Chagne et al., 1996), aldehyde-tanned leather (Serra et al., 1991;
consumer goods such as shoes, garments, bags etc by turning the Wojdasiewicz et al., 1992), synthetic-tanned leather (Dasgupta,
food industry's waste product into a desirable, useful and sustain- 1980), alum-tawed leather (Montgomery, 1987; Takenouchi et al.,
able range of end products (Aloy et al., 1976). It has been estimated 1997) and rawhide (Bosnic et al., 2000). Cattle skin is generally
that about 1.67  109 m2 of leather is being made annually in the used for leather manufacturing, however, for soft leather items skin
world (FAO, 2001). The annual global trade in leather sector is of other animals like lamb, deer, goats, etc is also used (Heidemann,
estimated as seventy billion dollars (ITC, 1999). 1993).
Different manufacturing processes, ranging from cottage in-
dustry to heavy industry are involved for the durable and flexible 2. Leather production processes
leather material by the tanning of putrescible animal rawhide and
skin (Heidemann, 1993). The different forms of leather depending The manufacturing process for leather preparation can be
divided into three basic sub-processes: preparatory stage/beam
house stage, tanning stage and crusting stage (Suresh et al., 2001;
Abbreviations: AOP, Advanced oxidation process; BBP, Benzyl butyl phthalate; Sivakumar et al., 2010). Surface coating may be an additional step
BOD, Biological oxygen demand; COD, Chemical oxygen demand; CETPs, Common into the leather process.
effluent treatment plants; DBP, Di butyl phthalate; DBT, Di butyl tin; DEHP, Diethyl Preparatory stage or the beam house operation stage is car-
hexyl phthalate; NMP, N-methyl pyrrolidine; OPP, Ortho phenyl phenol; TDS, Total
dissolved solids; TBT, Tri butyl tin; VOC, Volatile organic compounds.
ried out when the hide/skin is prepared for tanning. This stage
* Corresponding author. Fax: þ91 522 2628227, þ91 522 2611547. includes preservation, soaking, liming, unhairing, fleshing, split-
E-mail addresses: mditrc@rediffmail.com, mditrc@hotmail.com (M. Das). ting, reliming, deliming, bating, degreasing, bleaching, pickling and

http://dx.doi.org/10.1016/j.jclepro.2014.10.017
0959-6526/© 2014 Elsevier Ltd. All rights reserved.
40 S. Dixit et al. / Journal of Cleaner Production 87 (2015) 39e49

depickling (IL&FS, 2010). At the onset, the hides are trimmed and 3.1. Waste water
soaked not only to restore the lost moisture during curing but to get
rid of salt and other solids. Subsequently, the hides are fleshed to Enormous amount of water and pollutants are discharged dur-
remove excess tissue, muscles or fat adhering to the hide so that ing the entire tanning process (Kaul et al., 2001). The details of
uniform thickness may be obtained. Dehairing is performed mostly water consumption for several steps and the characteristic
by liming process using a series of drums containing lime liquors pollutant loads for each operation are presented in Table 1. Con-
(calcium hydroxide) and sharpening agents, however thermal, ventional pre-tanning and tanning processes accounts for nearly
oxidative, and chemical methods may also be applied. The softness 90% of the total pollution from a tannery (Aloy et al., 1976). Pre-
and flexibility to the leather may be obtained by bating and tanning process results in variations in pH and causes increase in
deliming, which is performed by keeping the hides in a solution of chemical oxygen demand (COD), total dissolved solids (TDS),
ammonium salt dissolved in water along with proteolytic enzymes chlorides, sulphates in tannery wastewaters (Thanikaivelan et al.,
at 27e32  C (Bienkiewicz, 1983; EPA, 1982). Pickling is required as 2000a). The conventional dehairing process with sodium sul-
the next step to adjust the acidity with the use of a brine solution phide and lime accounts to 84% of biochemical oxygen demand
and sulphuric acid. (BOD), 75% of COD and 92% of suspended solids (SS) from a tannery
Tanning converts the raw hide or skin into a stable material that (Marsal et al., 1999). The use of sodium sulphide not only gives rise
dries out to a flexible form without putrefying and becomes suit- to unfavourable consequences on environment but also affects the
able for a wide variety of end applications (Krishnamoorthy et al., efficacy of effluent treatment plants (Bailey et al., 1982). The poor
2012). In general, depending upon the end application of the uptake of 50e70% chromium during commercial chrome tanning
leather, two tanning methods is used; vegetable tanning or chrome method results in material wastage on one hand and creates
tanning. ecological imbalances on the other (Rao et al., 1997). The post-
The process of vegetable tanning usually requires 3 weeks so tanning processalso results in modifications in TDS, COD, and
that the dye penetrates to the hide. Further, the hides are dipped in heavy metal pollution significantly (Simoncini and Sammarco,
sodium bicarbonate or sulphuric acid drums for bleaching and for 1995).
the removal of tannins bound to the surface. Before set out to dry, Highly polluted sediments resulting from discharge of chem-
lignosulfate, corn sugar and oils may be added to the leather and icals adversely affect the ecological functioning of rivers (Schilling
then it undergoes further finishing steps. et al., 2012). High concentration of heavy metals has been found
Chrome tanning is done by the reaction between the hide and in sediments of the river Ganga and its tributaries (Singh et al.,
trivalent chromium salt, most commonly basic chromium sulphate. 2003; Tare et al., 2003). Increase salinisation of rivers and
At pH 3 the tanning materials are introduced and the pH is raised. groundwater has led to the loss of agricultural production and
The soaking, fleshing, liming/dehairing, deliming, bating, and reduced the quality of drinking water in Tamil Nadu, India (Money,
pickling and the drying/finishing steps are essentially the same as 2008). It has been estimated that over 55,000 ha of land have been
in the case of vegetable tanning except that an additional processes contaminated by tannery wastes and around 5 million people are
of retanning, dyeing, and fat liquoring to produce usable leathers. affected by low quality of social environment and drinking water
Many a times oil is applied on the skin before leather drying to (CSIRO, 2001; Sahasranaman and Jackson, 2005).
replace the natural oil lost during beam house and tanyard pro-
cesses; this step is called fat liquoring. The leather is thereafter
wrung, set out, dried, and finished. The pH of chrome tanned 3.2. Solid wastes
leather finish between 3.8 and 4.2 (Heidemann, 1993).
Chrome-tanned leather is more superior to vegetable tanned A great deal of sludge generated from the tannery plants
leather due to its softness, high thermal and water stability and less (Ramasami and Prasad, 1991) render the solid waste management
time consuming. Almost all leather made from the skin of sheep, system highly inactive due to non-biodegradability of the tanned
lambs, goats, pigs is chrome tanned. leather (Dhayalan et al., 2007; Lofrano et al., 2007). Leather itself is
Crusting takes place after the thinning, re-tanning and lubri- slow biodegradable and treatment of different chemicals during
cating of the hide. Sometimes dye is also added in this process. tanning process makes it resistant towards chemical, thermal, and
During crusting, the chemicals added have to be fixed followed by microbiological degradation (Hagerman, 1980; Han et al., 2001).
drying and softening process. Crusting involves several steps like
wetting back, sammying, splitting, shaving, re-chroming, neutrali-
Table 1
zation, re-tanning, dyeing, fat liquoring, filling, stuffing, stripping,
Quantity of wastewater generated and pollution load of each step during processing
whitening, fixating, setting, drying, conditioning, milling, staking, 1 tonne of skin/hide.
and buffing (Bienkiewicz, 1983).
Pollution load Processing operations load kg/tonne hide
Finishing process consists of surface coating that include: oil-
ing, brushing, padding, impregnation, buffing, spraying, roller Soaking Unhairing/ Deliming Chrome Post Finishing
liming and tanning tanning
coating, curtain coating, polishing, plating, embossing, ironing,
bating
combing (for hair-on), glazing and tumbling (Heidemann, 1993).
Waste water 9.0e12.0 4.0e6.0 1.5e2.0 1.0e2.0 1.0e1.5 1.0e2.0
generated
(m3 or Kilolitre)
3. Environmental impacts of leather industry Suspended solids 11e17 53e97 8e12 5e10 6e11 0e2
COD 22e33 79e122 13e20 7e11 24e40 0e5
Environmental impact of tannery wastes containing waste- BOD 7e11 28e45 5e9 2e4 8e15 0e2
Chromium 2e5 1e2
water; hazardous chemicals such as chromium, synthetic tannins, e e e e
Sulphides e 3.9e8.7 0.1e0.3 e e e
oils, resins, biocides, detergents; careless disposal of solid wastes NH3eN 0.1e0.2 0.4e0.5 2.6e3.9 0.6e0.9 0.3e0.5 e
and gaseous emissions creates a negative image of leather industry, Total Kjeldahl 1e2 6e8 3e5 0.6e0.9 1e2 e
although it has significant economic influence (Suresh et al., 2001; nitrogen
Nazer et al., 2006; Jerry, 2011; Sequeira et al., 2011; Shakir et al., Chlorides 85e113 5e15 2e4 40e60 5e10 e
Sulphates 1e2 1e2 10e26 30e55 10e25 e
2012; Islam et al., 2014).
S. Dixit et al. / Journal of Cleaner Production 87 (2015) 39e49 41

Table 2
Uses, Structures, LD 50 and toxicity of chemicals used in leather industry.

Name Uses Structure LD50 in rats, oral (mg/kg) Target organs

Benzyl butyl phthalate Used in process for the production of 2330 Eyes, lungs, liver,
a micro porous artificial leather reproductive system
coating/water vapour-permeable
sheet materials.

Bis(2-ethylhexyl) Used as plasticizers in a processing 30,000 Liver and testes


phthalate (DEHP) of shoes soles, and artificial leather
manufacturing

Di butyl phthalate (DBP) Used as a Phthalate plasticizer in 7499 Eyes, lungs, gastrointestinal
the artificial leather industry tract, testes

Anthracene Used as a tanning agent 16,000 Kidney, liver, fat and


(for leather) carcinogen

short chain chlorinated Additive for the leather treatment 3090 Liver, kidney, thyroid and
paraffin's (PBT) (renders smoothness to leather), carcinogen
leather clothing and belts and as
a leather oiling agent.
Sodium dichromate Principal raw material used in the Not available Blood, kidneys, heart,
production of chrome tanning lungs, eyes and
materials for the leather industry carcinogen
like Chrome-tanning salts

Cobalt dichloride Used in leather dyeing and 80 Lungs, liver, kidney,


finishing as well found in heart, skin
tanned leather

Nonyl phenol Used in finishing 1475 Blood, lungs, eyes,


skin, CNS, kidneys and
low biodegradability

Methyl isothiazolinone Biocide,microbiological protection 1800 Skin, eyes and carcinogen

N-Methyl pyrrolidone Coalescence, plasticizers, wetting 3914 Eyes, kidney, lymphatic


agent system, liver, lung, testes

Formaldehyde Leather finishing HCHO 100 Eyes, lungs and carcinogen


Heavy metalsArsenic As 763 Liver, kidneys, skin, lungs,
lymphatic system and
carcinogen
Chromium used for dyeing Cr 3250 Kidney, CNS,
haematopoietic system
Organotin compounds As a catalyst 175 Gastrointestinal tract,
(Dibutyl tin) liver and carcinogen

Azo dyes (Orange II) Used for Dyeing 3418 Blood, liver, testes
and carcinogen
42 S. Dixit et al. / Journal of Cleaner Production 87 (2015) 39e49

This in turn affects the agro based activities and degrades produce carcinogenic and allergenic aromatic amines. The EU Azo
groundwater system (Mwinyihija et al., 2012). These wastes are a Colorants Directive (2002) has given a list of azo dyes that should
threat to ecology and aquatic system in vicinity of tannery plants not be used in leather articles as they may release one or more
(Mwinyihija et al., 2010). Adding of pesticides for hide conservation prohibited aromatic amines in detectable concentration above
during transport also add to the problem (Pollution Prevention and 30 ppm in the finished articles or in the dyed components. Orga-
Abatement Handbook, 1998). notin compounds like dibutyl tin (DBT) used in leather finishing as
a catalyst may contain tributyl tin as an impurity which is highly
3.3. Volatile organic compounds toxic and has hormone like activity (Omura et al., 2001). No re-
striction has been set yet for synthetic tannins although there have
Pollutants such as ammonia, hydrogen sulphide, volatile hy- been extensive impact assessment and treatment applications for
drocarbons, amines and aldehydes are emitted to the atmosphere individual chemicals such as cresols, phenols (Hohreiter and Rigg,
from tannery plants as effluents (Fela et al., 2010). Ammonia 2001; Wang et al., 2002).
emissions may occur during deliming, unhairing, or drying pro-
cesses, while, emissions of sulphides may be the result of liming/ 4. Legislation scenario for leather industries
unhairing and subsequent processes. Hydrogen sulphide is released
in tannery wastewater from alkaline sulphides if the pH is less than The discharge limit parameters are different from one country to
8.0. Particulate emissions contain chromium, which may occur other. Some legislative authorities have a check on the quality of
(EPA, 1982; Streicher, 1987) due to reduction of chromate or treated effluents; while others on the quality of the recipient water
through handling of basic chromic sulphate powder or from the bodies; some define the permissible levels of impurities to be dis-
buffing process (EPA, 1982; Streicher, 1987; Telecon, 1996). Thus charged per day into the recipient water body, whereas in some
substantial amount of volatile organic compounds (VOC) are cases specifications are linked to the total amount of waste water
emitted during different tanning processes which may pose threat discharged (Bosnic et al., 2000).
to the atmosphere if not controlled properly. In many countries, tannery effluents are subjected under overall
legislation of industrial waste discharge rather than specific limits
3.4. Toxicity of chemicals used in leather industry (Bosnic et al., 2000). During 1990's several tanneries in India were
ordered to close the units as they could not meet the standards of
A wide variety of chemicals are used in order to bring the leather pollution control systems, while many of them had to pay huge
in the usable form in the preparation of a variety of products. compensation for the damage caused by salinisation of ground-
Table 2 describes the uses, structures, LD50 and toxicity of chemicals water (CSIRO, 2001). Government has encouraged the tanneries to
used in leather industry. The regulatory bodies have put restriction built Common Effluent Treatment Plants (CETPs) to treat the toxic
on the use of these chemicals in leather industry. Phthalates like wastewater from tanneries by giving subsidies. Despite this initia-
benzyl butyl phthalate (BBP), di-ethyl hexyl phthalate (DEHP) and tive, many of the pollution problems are still unresolved due to the
di-butyl phthalate (DBP) are used as plasticizers in micro porous higher cost associated to the treatment of effluents thereby causing
artificial leather coating. Due to the reproductive toxic potential of illegal dumping (Beg and Ali, 2008). It was noticed that one of the
these phthalates, EU (2003 a) has directed the companies to label if Uganda's main leather producing company directly dumped its
the products contain more than 0.5% of these phthalates. Nonyl waste water in a wetland adjacent to Lake Victoria (The Monitor,
phenol, used in finishing of leather, should not be more than 0.1% in 2009). In Crotia the proper pollution abatement cost exceeded
finished products as prescribed by EU (2003 b). The decision was the compensation cost against irresponsible behaviour (EcoLinks,
taken due to high persistence of these chemicals in the environ- 2001).
ment because of its low bio-degradability. Additionally, nonyl Some countries have made regulations related to production,
phenol shows oestrogens like activity. Biocides are used for the import and sale of leather products with regard to hazardous
microbiological protection of mainly water based finishing chem- substances. Table 3 describes the maximum permissible limits of
icals. Some biocides like methyl isothiazolinone (MIT) and chlor- chemicals used in leather and leather products prescribed by some
isothiazolinone (CIT) when used in combination act as an irritant of the countries. Furthermore, in order to restrict the use of these
(EPA, 1998). chemicals, European Chemical Agency (ECHA) has prioritized few
The use of o–phenyl phenol (OPP) is restricted for leather fin- chemicals under Substances of Very High Concern (SVHC) which
ishing chemicals due its carcinogenic activity (EPA, 2007). N- are considered to be hazardous not only to the environment but
Methyl pyrrolidone works as coalescence, plasticizer, levelling also to humans (UK REACH, 2009). It has been observed that out of
agent, wetting agent and as a swelling material thus giving high these 30 SVHC substance list provided by ECHA, almost all of the
performance in finished leather. This compound has been classified chemicals are used in the leather industry (ECHA, 2010).
as a reproductive toxin (OEHHA, 2001). The use of formaldehyde is
inevitable in the manufacture of various types of leathers due to its 5. Technological options to combat the threat posed by
action as cross linker for casein top coats (Ram Mohan et al., 2008). leather industry
Due to the carcinogenic property of formaldehyde, its use is
restricted (EU, 1998). Inorganic pigments such as lead chromate, Environmental concerns over leather industries have been
cadmium sulphate are used due to their fastness and brilliant growing for the past two decades. High industrial and human
colour but these are toxic heavy metals (ATSDR, 2008; IARC, 2004; population density and the use of old technologies all cause
Louis et al., 2003). It has been shown that chromium (III) under increased levels of pollutant in the atmosphere (Maia, 1998). This
certain ligand environments leads to apoptosis by causing struc- situation has highlighted the need for greener technologies (Gupta
tural modifications in proteins (Shrivastava and Nair, 2001; and Babu, 2009; Sundarapandiyan et al., 2010, 2011;
Balamurugan et al., 2002). Krishnamoorthy et al., 2012). The protection of the environment
Azo dyes, the synthetic dyestuffs based on nitrogen are used in has become a global issue throughout the world.
leather industry for dyeing the leather articles. The toxicity of For reducing the negative environmental impact of hide pro-
several azo dyes has been mentioned earlier (Khanna and Das, cessing, there are two broad methods. The first method is generally
1991; Ramchandani et al., 1994). Many azo dyes on cleavage termed as low-waste or cleaner technologies that avoid the use of
S. Dixit et al. / Journal of Cleaner Production 87 (2015) 39e49 43

Table 3
Mandatory requirements in leather products of some countries.

Mandatory residual substances limits (RSLs) EU Germany Austria Denmark France Netherlands Switzerland

Pentachlorophenol 30 ppm 5 ppm 30 ppm 30 ppm 30 ppm 30 ppm


Azo dyes* 30 ppm
Chromium VI 3 ppm 10 ppm
Lead 90 ppm
Cadmium 100 ppm 75 ppm 100 ppm 100 ppm
Arsenic Absent
Organotin Compounds Absent
Specific Flame Retardants <0.1%
Phthalates 0.1% 0.1% 0.05%
PCBs and PCTs Not to be used
Biocides** 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 10 ppm
Formaldehyde >1500 ppm >1500 ppm 200-400 ppm 120 ppm

Source: http://ec.europa.eu/enterprise/chemicals/legislation/markrestr/index_en.html.
Azo dyes or the following aromatic amines on cleavage*: Biphenyl-4-ylamine; 4-aminobiphenyl xenylamine; Benzidine; 4-Chloro-o-toluidine; 2-Naphthylamine; o-ami-
noazotoluene; 4-amino-20 ,3-dimethylazobenzene; 4-o-tolylazo-o-toluidine; 5-Nitro-o-toluidine; 4-chloroaniline; 4-methoxy-m-phenylenediamine; 4,40 -methylenediani-
line; 3,30 -dichlorobenzidine; 3,30 -dimethoxybenzidine o-dianisidine; 3,30 -dimethylbenzidine 4,4-bi-o-toluidine; 4,40 -methylenedi-o-toluidine; 6-methoxy-m-toluidine; p-
cresidine; 4,40 -methylene-bis-(2-chloroaniline); 4,40 -oxydianiline; 4,40 - thiodianiline; o-toluidine; 2-aminotoluene; 4-methyl-m-phenylenediamine; 2,4,5-trimethylaniline;
o-anisidine 2-methoxyaniline; 4-amino azobenzene.
Biocides**(23 approved): Human hygiene biocidal products; Private area and public health area disinfectants and other biocidal products; Veterinary hygiene biocidal
products; Food and feed area disinfectants; Drinking water disinfectants; Preservatives; In-can preservatives; Film preservatives; Wood preservatives; Fibre, leather, rubber
and polymerised materials preservatives; Masonry preservatives; Preservatives for liquid-cooling and processing systems; Slimicides; Metalworking-fluid preservatives; Pest
control; Rodenticides; Avicides; Molluscicides; Piscicides; Insecticides, acaricides and products to control other arthropods; Repellents and attractants; Other biocidal
products; Preservatives for food or feedstocks; Antifouling products; Embalming and taxidermist fluids; Control of other vertebrates.
PCBs: Polychlorinated biphenyls PCTs: Polychlorinated terphenyl.

harmful chemicals and produce solid wastes which can be used as The recycling and reuse of spent liquor after the removal of the
by-products (EC, 1997a). The second method is related to the pollutants in leather processing provides better water management
treatment of wastewater and the environment-friendly handling (Parthasarathy, 1995). It has been suggested that ideally zero or
and processing of solid waste (EC, 1997b; c). The methods applied in near-zero discharge of waste liquors should be encouraged (Sykes,
both groups can be used to prevent leather production with less 1997). Common salt or sodium chloride emerges largely from the
negative impact on the environment. curing, pickling, and chrome tanning practices. Salt less or less-salt
curing may be an alternative to wet salting (Kanagaraj, 2005). Solar
5.1. Low waste or cleaner technologies drying, freeze drying or microwave/dielectric drying should be
considered (Komanowsky, 2000). Chemicals like potassium chlo-
The cleaner processing options need to be cost-effective in order ride, boraxephenol, boric acid, zinc chloride, silica gel and metal
to be economically viable and the success of these technologies oxinates can be used in place of sodium chloride (Bailey, 1995a;
depends on: (a) reduction of pollution in terms of quantity and Kanagaraj et al., 2000, 2005). Processing green hides and skins,
quality, (b) leather quality improvement and/or cost reduction, (c) use of gamma and electron beam irradiation techniques and
reproducibility of the process, (d) cost effectiveness to be transportation in refrigerated condition are some other options for
economically viable, and (e) wide market opportunities. A report by a better cleaner processing (Bailey, 1995b, 1999; Bailey et al., 2001).
Ludvik (2000) shows some possible options of reduction of pollu- Soaking requires 25% of the total water consumption in con-
tion load during processing of bovine hides into chrome tanned ventional leather processing. But the chloride load is a hurdle in
leathers by introducing advanced technologies based on low-waste recycling process as salt is not eliminated during physical, chemical
processing methods (Fig. 1). and biological treatment of waste water. The industrially proven

Fig. 1. Advanced technological options for leather processing.


44 S. Dixit et al. / Journal of Cleaner Production 87 (2015) 39e49

methods for reducing chloride load have been recommended by and aluminiumetannic acidesilica- based tanning agents have
shaking the liquor in special drums (EC, 1997a); using wheel type been developed (Thanikaivelan et al., 2000b; Madhan et al., 2001b,
de-salting machines (Rao et al., 2001) and counter-current soaking 2002, 2003; Fathima et al., 2003, 2004; Sunderarajan et al., 2003;
technique (Rao et al., 2003). Addition of environmentally accept- Krishnamoorthy et al., 2012) for reducing the chromium emis-
able antiseptics or commercial chemical bactericides such as ethyl sion. The controlled incineration of tannery wastes in a starved air
dithiocarbamate and isothiazolin (Buljan, 1995; EC, 1997a), use of thermal incinerator and solidifying the calcined waste resulting in
sodium sulphate (Vankar and Dwivedi, 2009), processing green 99.1% metal ion fixation is another alternative to reduce the chro-
hides (Frendrup, 1995; EC, 1997a) have also been suggested to mium burden on the environment (Sekaran et al., 2007). The tan-
decrease the salt load. The recycling of spent floats in liming and nery wastes then can be used as fuel or nitrogenous source for
unhairing processes showed substantial decrease in sulphide (70%), leguminous plants (Famielec and Wieczorek-Ciurowa, 2011; Lima
Ca(OH)2 (90%), BOD (7%) and COD (26%) load (Frendrup, 1995; EC, et al., 2010).
1997a).
Sulphide-lime based unhairing and liming achieves a significant 5.2. Solid waste treatment and management
decrease in both total solids and dissolved solids (Frendrup, 1995;
EC, 1997a). Enzymatic unhairing is an option for a clean beam The conventional disposal methods are not practicable for the
house process (Frendrup, 1995; Thanikaivelan et al., 2000a; Valeika disposal of tanned leather wastes due to leaching of Cr3þ from the
et al., 2012). Enzyme-assisted unhairing followed by reliming with tanned leather wastes to groundwater and conversion of Cr3þ to
once used relimed liquor ensures complete reduction of water Cr6þ; emissions of nitrogen oxide (NOx); generation of hydrogen
(Thanikaivelan et al., 2000b; Shrewsbury, 2002). An economically cyanide (HCN); Cr3þ and NH3 during incineration (Rai et al., 1989).
viable option based on enzymatic dehairing and pickle-less chrome Less toxic soluble Cr6þ can be produced at low incineration tem-
tanning can lead to 67% and 78% decrease in COD and total solids peratures (300e600  C) (Rai et al., 1989). More promising results
(Aravindhan et al., 2007). Lime splitted hides save chromium and can be achieved by integrating the active microflora to degrade the
other chemicals and the waste can be easily utilized as a by-product low molecular weight compounds and further degradation of the
(Frendrup, 1995; EC, 1997a). Ultrasound not only decrease the metabolites by anaerobic species (Beccari et al., 2002).
waste but also yield better leather quality (Valeika et al., 2009; Anaerobic digestion of solid waste produce biogas nutrient
Dettmer et al., 2013; Sivakumar et al., 2009). enriched effluents for agricultural purposes (Gnanamani and
A 97% decrease in ammonia load in effluents may be obtained by Kasturi Bai, 1992; Dhayalan et al., 2007). During leather process-
using ammonia-free deliming and bating with commercial prod- ing, 850 kg of solid waste is produced per tonne raw hide and
ucts such as acids, esters of carboxylic acids, non-swelling aromatic 150 kg is converted into leather, the remaining waste can be
acids (Frendrup, 1995; IUE, 2008). Carbon dioxide deliming in place recycled and utilized as a useful by product and raw materials
of ammonia decrease the pollution load of effluents to a significant (Colak et al., 2005; Ahmad and Ansari, 2013). Hydrolysate of keratin
extent (Palon and Marsal, 2002; IUE, 2008; Manfred et al., 2012; has been employed in chrome tanning, retanning and exhaustion
Gallego-Molina et al., 2013). Furthermore, it has been established without altering the physical strength of leather (Chakraborty and
that deliming and bating can be effectively carried out as a floatless Sarkar, 1998). Fleshings have been explored for the possible utili-
operation without impairing any physical/chemical or grain char- zation into useful end products such as soap, bio diesel and fat li-
acteristics (John et al., 2001). quor (Colak et al., 2005; Ravindranath and Gopalakrishnan, 2010).
The spent pickle liquor contains high concentrations of neutral Modified fleshing hydrolysate not only has better uptake capacity
salts (8e10%) and has an acidic pH (Chandrasekaran et al., 1989). of chromium in chrome tanning and rechroming (Kanagaraj et al.,
The options of salt less pickling pickle less chrome tanning and 2001a) but also, leather obtained has better physical and organo-
pickle recycle are some solutions to overcome the problem (Pojer leptic properties than conventionally produced method
and Huynh, 1999; Burrows, 2001). These recycle methods reduce (Kanagaraj et al., 2001b). Fleshings hydrolysed by pancreatic en-
TDS of the effluent discharged from the identified stream zymes could be used as a feed formulation by mixing with other
(Sundarapandiyan, 2010). feed ingredients (Kumaraguru et al., 1998).
Conventional chrome tanning processes use only 40e70% of the Glue, gelatine, reconstituted collagen, adhesives, films and
material (Warrier et al., 1995a, 1995b) and the disposal of the chrome cake can be obtained from chrome tanned leather, splits,
remaining wastes is a cause of concern (Ramasami, 1996; Fela et al., buffing dusts and trimmings (Brown et al., 1996; Cot et al., 2003;
2010). Intrinsically modified chrome tanning salts (Suresh et al., Cantera et al., 2000; Cantera, 2003; Taylor et al., 2002, 2003). A
2001; Thanikaivelan et al., 2002), use of chromium syntan or oxa- new parchment-like material from chrome shavings has been
zolidine (Gupta and Babu, 2009; Morera et al., 2006; found to be useful in the manufacture of home furnishing products
Sundarapandivan, 2011), high exhaustion tanning process (Sastry et al., 2005). The wet blue shavings completely digested by
(Frendrup, 1995; Covington, 1995; EC, 1997a), recycling/reuse alkali protease have been used for casein formulation in leather
techniques ((Rao et al., 1999a, 2002) would invariably help in finishing (Crispim and Mota, 2003). Chrome collagen residues have
increasing the chrome utilisation and decreases the chrome been used for the production of regenerated leather and various
discharge. The reuse of pickle liquor for the subsequent batches as articles (Cot et al., 1986, 2003). Utilization of tannery waste as feed,
well as resorting to pickle free alumechrome combination for fertilizer or cosmetic additive is a step for zero solid waste
tanning result in reduction of significant levels of TDS (Rao et al., (Castilhos et al., 2002; Daudt et al., 2007; Gish, 2000; Konrad and
2004; Burrows, 2001; Sivakumar et al., 2005). Use of Sargassum Castilhos, 2002; Lima et al., 2010). Utilising tannery waste as a
seaweeds to remove chromium from tannery effluent and make use protein source for poultry feed is a step for zero solid waste (Paul
of this seaweed in the manufacture of basic chromium salt as a et al., 2013).
reductant is another option (Aravindhan et al., 2004). A combina-
tion between the chemical precipitation and the biological removal 5.3. Treatment of waste water
of chromium from tanning wastewater may render the tanning
process eco-sustainable and environment friendly (Abdullah et al., Conventional tannery effluent treatment plants (ETPs) offer
2010). Chromiumesilica-, chromium iron, aluminiumezinc-, physicochemical treatment followed by biological and tertiary
chromiumezinc-, chromiumezincesilica-, zirconium oxychloride treatment to meet the standards (Rao et al., 1999b). Significant
S. Dixit et al. / Journal of Cleaner Production 87 (2015) 39e49 45

technological advancements are being made in the end-of-pipe casein top coats but also as a biocide. Finishing chemicals may
treatment methods to achieve higher efficiency in meeting the contain formaldehyde even when no formaldehyde was used for
standards in a cost-effective manner. The anaerobic treatment of production as many raw materials are preserved in formaldehyde
tanning waste water has included the application of technologies base. To overcome this problem use of formaldehyde scavengers
based on lagoons, contact filter, up flow anaerobic sludge blanket can be adopted as in the case of some Wet End Chemicals (Ram
(UASB) reactor, and high-rate biomethanation (Rajamani et al., Mohan et al., 2008). Inorganic heavy metal pigments like lead
1995; Van Groenestijn et al., 1995; Ramasami and Sahasranaman, chromate, cadmium sulphide and others can be replaced by organic
2000; Lefebvre et al., 2006; El-Sheikh et al., 2011). Post treatment pigments or pigments from rare earth colorants which are free of
methodologies for tannery waste-water from anaerobic bio- carcinogenic aryl amines (Sreram et al., 2009).
digestion have included the use of aerators with and without the
aid of aerobic microorganisms (Farabegoli et al., 2004; Ganesh et al., 6. Conclusion
2006). Membrane technologies such as activated carbon filters,
reed bed, root zone techniques, crossflow microfiltration, ultrafil- A critical review on the conventional leather processes and the
tration and reverse osmosis methods are being utilized for principles behind each step reveals that the bulk of the pollution
providing tertiary treatment of tannery waste water (Daniels, 1995; rests in pre-tanning and tanning processes, though post tanning
Rajagopalan and Thimmapuram, 1997; Labanda et al., 2009; and finishing steps also pollute the environment. The pre-tanning
Gallego-Molina et al., 2013; Wang et al., 2011). Membrane bio- and tanning processes causes increase in COD, BOD, TDS, SS, chlo-
reactors are being used for the treatment of tannery waste water rides and sulphates in tannery effluents. The post-tanning pro-
against conventional activated sludge process (Suganthi et al., cesses result in modifications in TDS, COD and heavy metal
2013). The high-rate transpiration system and an accelerated pollution. The sludge generated from the tannery plants effect the
evaporation with crystallization of saline streams using flat-plate agro based activities and degrade the groundwater in the vicinity.
collectors have emerged as a possible method or treating salt- Substantial amount of volatile organic compounds are emitted
bearing tannery wastewaters (Rao et al., 2001; Buljan et al., during tannery process and cause a threat to environment if not
2001). Studies have shown that respirometry combined with controlled properly. The negative impact of tannery industry has
sequencing batch reactor (SBR) may be an effective way for the call attention to the need for green technology. The emergent green
biodegradation of tannery waste water (Ganesh et al., 2006). technologies have been divided into two broad methods; (i) Low
AOP treatment such as UV light, ozone (O3), photocatalytic waste or cleaner technologies that decrease the effluent pollution
oxidation and their combination (Schrank et al., 2004, 2005; Costa load, avoid the use of harmful chemicals and produce solid wastes
et al., 2008; Monteiro et al., 2009; Hoshyar et al., 2012) and Fenton that can be changed into useful by products (ii) treatment of
reagent (Schrank et al., 2005; Lofrano et al., 2010; Mo denes et al., wastewater and the environment-friendly handling and processing
2012) have been used as pre-oxidation or post-oxidation of tan- of solid waste.
nery wastewater (Di Laconi et al., 2002, 2010). These treatments are
based on the principle of production and utilization of powerful
oxidants in a short time. An improved coagulation process by
Lofrano et al. (2007) gave an effective removal of toxic components
from tannery wastewater. Integrated waste water ponds and con-
structed wetlands (CWs) are other options studied for treatment of
tannery effluents (Tadesse et al., 2004; Calheiros et al., 2008, 2012).
Plants such as Arundo donax and Sarcocornia fruticosa in CWs can
remove up to 51e80% COD and 53e90% BOD from the tannery ef-
fluents (Calheiros et al., 2012). Recently, Dunn et al. (2013) has
showed the use of tannery effluent for growth medium of Artho-
spira (Spirulina) and retaining of chromium in wetlands with the
help of non-specialized media (Dotro et al., 2012).

5.4. Development of some eco-friendly chemicals for leather and


leather products

The consumer consciousness and strict regulations by the


worldwide authorities require leather products with the lowest
possible risk for the environment. The chemical industry has
accepted the challenge with the development of new eco-friendly
products. Phthalates used as nitrocellulose lacquer emulsions, can
be successfully replaced by castor oil which maintains the typical
lacquer emulsion properties like glossy touch, softness and elas-
ticity (Blach, 2004). Enzymes, amino acids or oxazolidine can be
used as an alternative in tanning processes (Kanth, 2009;
Krishnamoorthy et al., 2012; Sundarapandivan et al., 2011).
The ecological useful alternatives for nonyl phenol and nonyl
phenol ethoxylates are fat alcohol ethoxylates especially C12 and
C14, the combination of which can successfully replace nonyl
phenol ethoxylates (Tox-Ecology, 2002). As an alternative for the
solvent N-Methyl pyrrolidone (NMP), high wear top coat acrylics
being free of solvents have been advocated (Blach, 2004). Formal- Fig. 2. Environmental impact of leather industry and technologies to combat the
dehyde in leather finishing is not only used as a cross linker for threat.
46 S. Dixit et al. / Journal of Cleaner Production 87 (2015) 39e49

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2012. Use of constructed wetland systems with Arundo and Sarcocornia for
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