Recent Trends in Leather Making: Processes, Problems, and Pathways

Critical Reviews in Environmental Science and
Technology
ISSN: 1064-3389 (Print) 1547-6537 (Online) Journal homepage: http://www.tandfonline.com/loi/best20
Recent Trends in Leather Making: Processes,

Problems, and Pathways
Palanisamy Thanikaivelan , Jonnalagadda Raghava Rao , Balachandran Unni

Nair & Thirumalachari Ramasami
To cite this article: Palanisamy Thanikaivelan , Jonnalagadda Raghava Rao , Balachandran Unni
Nair & Thirumalachari Ramasami (2005) Recent Trends in Leather Making: Processes, Problems,
and Pathways, Critical Reviews in Environmental Science and Technology, 35:1, 37-79, DOI:
10.1080/10643380590521436
To link to this article: https://doi.org/10.1080/10643380590521436
Published online: 12 Jan 2007.
Submit your article to this journal
Article views: 1166
Citing articles: 50 View citing articles
Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=best20
Critical Reviews in Environmental Science and Technology, 35:37–79, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1064-3389 print / 1547-6537 online
DOI: 10.1080/10643380590521436
Recent Trends in Leather Making: Processes,

Problems, and Pathways
Palanisamy Thanikaivelan
Centre for Leather Apparels and Accessories Development, Adyar, Chennai, India
Jonnalagadda Raghava Rao∗ and Balachandran Unni Nair

Chemical Laboratory, Adyar, Chennai, India
Thirumalachari Ramasami
Central Leather Research Institute, Adyar, Chennai, India
Leather processing has emerged as an important economic activity

in several developing countries. Awareness of environmental prob-
lems has increased considerably and during recent years protecting
environment has become a global issue. Currently the leather pro-
cessing industry is going through a phase change due to global envi-
ronmental regulations. The article summarizes the current leather
processing methods with their rationale and environmental prob-
lems. It has been revealed that pretanning and tanning processes
contribute 80–90% of the total pollution load (BOD, COD, TS, TDS,
Cr, S2− , sludge, etc.). Further, toxic gases like ammonia and hy-
drogen sulfide are also emitted. Volatile organic compounds, heavy
metals, and carcinogenic arylamines from posttanning and finish-
ing operations are also creating severe concern. Apart from this, a
great deal of solid wastes like lime sludge from tannery and chrome
sludge from effluent treatment plants are being generated. Ad-
vanced processing techniques as well as effluent treatment strategies
for combating environmental and human health risks are reviewed
in detail. The leather processing industry in various countries, how-
ever, is facing a serious challenge from the public and government.
This is in spite of the implementation of several advanced process-
ing techniques and treatment systems. Hence, there is a need to
revamp leather processing methods anew for the sustainability of
leather industry. Some of the novel concepts in leather processing
are briefly mentioned and discussed.
∗
Corresponding author. Tel: +91 44 2441 1630; Fax: +91 44 2491 1589. E-mail: clrichem@
mailcity.com
37
38 P. Thanikaivelan et al.
KEY WORDS: chemical oxygen demand, dehairing, effluent treat-

ment, enzyme, fiber opening, leather processing, pollution, sludge,
tanning, total solids
I. INTRODUCTION
A. Leather Industry: A Global Perspective
Leather is a unique commodity that links the rural farmer to the fashion world.
Leather as a natural material offers numerous advantages over synthetics,
namely, aesthetic appeal, feel, texture, and breathability. Major product appli-
cations for leather are leather goods, garments, and footwear. More than 60%
of the leathers produced are being converted to footwear (Taeger, 1996). The
annual global trade in leather sector is estimated as US$70,000,000,000 (ITC,
1999). The United States, Germany, and other European countries remain ma-
jor importers of leather products. Countries such as China, India, Thailand,
and Indonesia dominate leather and leather products exports. The demand
for leather and leather products is on the rise and is independent of supply.
Leather processing has emerged as an important economic activity in
several developing countries that are dependent on agricultural economy. It
has been estimated that about 1.67 × 109 m2 of leather is being made annu-
ally in the world (FAO, 2001). The bulk of the leather production is carried
out in developing economies, partially because of the high labor intensity
of the processes involved in the conversion of hides and skins into leather.
India is a major player in the global leather trade. Leather has assumed im-
portance as an opportunity sector for social development, employment gen-
eration, and export realization. Leather is a thrust area in national planning
for the development of India. The Indian leather industry has evolved over
nearly two centuries. Currently, the overall share of India in the global leather
trade is around 3% (ITC, 1999). There are about 2100 tanneries located in
India, with a processing 0.9 × 106 tons of rawhides and skins (Velappan and
Muralidharan, 2001). Major tannery clusters in India are located in the states
of Tamil Nadu, West Bengal, Uttar Pradesh, and Punjab.
B. Leather and Environment: A Challenging Issue

The global environment is degrading due to socioeconomic activities of
mankind. Environmental protection and sustainable development are gaining
public importance. Industries that cause adverse changes to the immediate
environment are being challenged by the society. The global leather industry
is one among them.
Recent Trends in Leather Making: Processes, Problems, and Pathways 39
Leather processing is one of the earliest industrial activities taken up by

humans. The processes used in the manufacture of leather in several devel-
oping countries remain traditional and are often not optimized for chemical
and water usage. Leather making can also be called an activity that helps
in utilizing potential wastes (Germann, 1999; Sykes, 1996). The utilization of
by-products of the meat industry, namely, hides/skins, is achieved by tanning
using basic chromium sulfate (BCS) or vegetable tannins. This, however, is a
simplistic view. A more detailed analysis of environmental consequences of
the tanning industry is critical. The industry has gained a negative image in
the society with respect to pollution. Leather processing activity is therefore
facing a serious challenge and there is public outcry against the industry. This
is in spite of the leather industry having made traceable and visible impacts
in the socioeconomic area through both employment generation and export
earnings.
II. LEATHER PROCESSING: SOURCE OF POLLUTION
Leather processing involves a series of operations, as shown in the flow di-

agram in Figure 1. The operations involved in leather processing may be
classified in three groups: pretanning or beamhouse operations, tanning,
and posttanning as detailed by Ramasami and Prasad (1991). Pretanning
FIGURE 1. Various unit processes and operations in leather processing (Saravanabhavan

et al., 2003).
FIGURE 2. Inflow–outflow diagram for leather processing (Rao et al., 2003).
operations aim at cleaning hides/skins, tanning stabilizes the skin/hide ma-

trix permanently, and aesthetic values are added during post tanning and
finishing operations.
The various chemical inputs into leather processing are given in Figure 2
(Rao and Ramasami, 1997). Water is the main medium of transport for the
chemicals in leather processing. The leather industry uses about 35–40 L of
water/kg of hide processed (Ramasami and Prasad, 1991). With the present
annual processing capacity of 0.9 × 109 kg of hides and skins in India, it is
estimated that nearly 30 to 40 × 109 L of liquid effluent is generated annually.
This gives rise to two major problems for the leather industry: the availability
of good quality water, and the need for treatment of such large quantities of
effluent. The extent of pollution load emanating from the leather processing
using conventional methods can be assessed from the emission factors for
various operations as indicated in Table 1 (Ramasami et al., 1998). Nearly
70% of the emission loads of biochemical oxygen demand (BOD), chemical
oxygen demand (COD), and total dissolved solids (TDS) emanates from the
pretanning operations (Ramasami et al., 1999a, 1999b). Almost the entire
TABLE 1. Typical Range of Emission Factors for Conventional Leather Processing

Composite
Vegetable Chrome Dyeing and (includes
Parameters Soaking Liming Deliming Pickling tanning tanning fatliquoring washing)
Volume of 6–9 3–4 1–2 0.5–1.0 0.5–2 1–2 1–2 30–40

effluent
BOD 6–24 15–40 1–6 0.2–0.7 3–18 0.3–1.6 1–4 30–120
COD 18–60 30–100 2.5–14 0.5–3 7.5–40 1–5 2–14 75–320
Total solids 200–500 90–200 4–20 17–70 12–60 30–120 4–20 450–1000
Dissolved solids 190–400 70–120 2.5–10 17–70 10–50 30–100 3–15 300–800
Suspended solids 15–60 15–80 1.5–8 0.5–3 2–10 1–5 0.6–2 60–160
Chloride as Cl− 90–250 10–30 1–4 10–30 0.5–2.5 15–50 0.5–2 150–350
Total chromium — — — — — 2–10 0.04–0.2 3–10
as Cr
Note. All values expressed in kg/ton of hide or skin processed; These were obtained from the formula
(concentration × volume of effluent)/ton of leather processed (Thanikaivelan et al., 2004, unpublished).
quantity of sulfide discharge is from the dehairing operations (Steven, 1983).

Chrome tanning activity is associated with large discharge of chromium and
sulfate ions (Rao et al., 1983).
A. Pretanning
1. SOAKING
The starting material for leather processing, in most cases, is rawhide or
skin, which had been preserved temporarily by the addition of common
salt. Soaking aims at reversal of cured hides and skins to near the status of
the freshly flayed condition, in terms of dimension and composition. Large
amounts of water and small amounts of preservatives/wetting agents are
used at this stage. The common salt, when removed from the skin during
soaking, constitutes a major source of pollution from tanneries (Ludvik and
Orlita, 1986). Because the dissolved sodium chloride is not easily treated and
removed from wastewater, the discharge of tannery wastewater onto land
leads to significant addition of salinity to the soil (Daniels, 1997). The soak
liquor is characterized by high TDS and chloride content (Ramasami et al.,
1999b). Currently, the problem is tackled by the segregation of soak liquors
for salt recovery through solar evaporation pans. Soak liquor also contains
salt soluble proteins and other organic materials, which contribute marginally
to the BOD and COD load. Through judicious choice of methods, however,
it may be possible to minimize the BOD and COD loads. Obnoxious smell
and ammoniacal odor emanating from degraded protein are also associated
with spent soak liquor.
2. LIMING
One of the most important pretanning operations is liming. The main objec-
tive of liming is removal of hair, flesh, and splitting up of fiber bundles by
chemical and physical means (Ramasami and Prasad, 1991). Hair can be ei-
ther digested (using lime and sodium sulfide) or mechanically removed after
loosening by chemical means. Flesh, being a loose, unstructured, and non-
compact material, has to be separated from leather-making material, corium
(middle layer of skin made up of a protein, collagen, in naturally woven fiber
bundles form), by the action of hydrostatic pressure and then is removed us-
ing a fleshing machine or knife. In this operation, lime and sodium sulfide are
used along with substantial quantities of water (Money, 1996). Lime increases
the pelt pH to 12–13 and also causes osmotic swelling due to ionic imbal-
ances built up in the matrix (Bienkiewicz, 1983). Swelling causes changes in
dimension and charge characteristics of the skin/hide. The skin/hide matrix
essentially becomes anionic, in other words, a cation exchanger. The hydro-
static pressure built up enhances the splitting up of fiber bundles, separation
of unwanted interfibrillary materials, and easy removal of flesh (Ramasami
et al., 1999a). Moreover, the combined action of S−2 and OH− ions helps
to degrade hair protein by nucleophilic displacement reaction at disulfide
bonds, as reported by Windus and Showell (1968).
Significant amounts of chemicals are used during pretanning. Optimum
amounts of chemicals need to be used to reduce the TDS, BOD, and COD
loads. Liming operations lead to not only wastewater containing significant
amounts of BOD, TDS and S2− but also substantial quantities of solid wastes
containing lime sludge, fleshing and hair (Ramasami and Prasad, 1991).
Sodium sulfide, a good reducing agent, interferes in the oxidation of organic
wastes and contributes significantly to the BOD and COD concentrations in
wastewater (Steven, 1983). The extensive use of sulfide yields unfavorable
consequences on environment and the efficacy of effuent treatment plants
(ETPs) (Bailey et al., 1982).
3. DELIMING
The pH of the limed pelt is highly alkaline. The reduction of pH or alkalin-

ity needs to be gradual due to several reasons as given by Ramasami et al.
(1999a), including: (a) The heat of neutralization of alkali and rate of heat
dissipation should be very low, taking into account the heat sensitivity of the
pelt; (b) the presence of sulfides in the pelt limits the pH conditions for the
safe removal of lime, if the formation of hydrogen sulfide is to be avoided;
and (c) the control of pH for optimum activity of bating enzymes used sub-
sequently. Deliming agents based on weakly acidic salts like ammonium
chloride and ammonium sulfate are used to neutralize lime after the hair and
flesh have been removed from the skin (Ramasami and Prasad, 1991). It is
now recognized that the use of nitrogen-bearing salts could affect the N:P:K
ratios of soil (Dix, 2000; Ramasami, 1993). Nitrogen-based deliming agents
are considered a long-term environmental threat (Huber and Satyendra,
1990). The resultant salts of this operation would in turn increase the amounts
of COD and TDS (Ramasami et al., 1994).
4. BATING
The complete removal of unwanted interfibrillary materials and short

hairs through the use of enzymatic applications is the objective of bating
(Ramasami and Prasad, 1991). The majority of the commercial preparations
of the enzymes used in bating are generally more effective in the pH range of
8.2 to 8.8 or 3.5 to 4.5. The liquid wastes from this operation contain usually
small quantities of proteineous matter and other debris, which contribute to
BOD and COD significantly. These loads could be minimized through careful
choice of bating formulation (D’Souza and Vedarajan, 1997; Dederle et al.,
1984).
5. PICKLING
Pickling is a process in which the partially anionic matrix is temporarily con-

verted into a cationic matrix in order to prepare the stock for the subsequent
chrome tanning operation (Bienkiewicz, 1983). It uses substantial quantities
of sulfuric acid and sodium chloride. In this operation, the pH is adjusted to
2.5–2.8. In order to suppress osmotic swelling caused by acid addition, the
concentration of sodium chloride is maintained at the required ionic strength
(O’Flaherty et al., 1978). Excessive use of common salt and sulfuric acid, as
carried out commonly during pickling operation, leads to significant COD as
well as TDS loads (Ludvik, 1997; Prasad et al., 1981). In the case of vegetable
tanning, the need for extensive pickling does not arise. It has now been es-
tablished that sulfate ions in wastewater not only contribute to the TDS but
also reduce the efficacies of ETPs (Rajamani, 1997; Ramasami et al., 1999a).
B. Tanning
Tanning is a process in which the leather-making protein is permanently sta-
bilized against heat, enzymatic biodegradation, and thermomechanical stress
(Ramasami, 2001). In commercial practice, vegetable and chrome tanning
methods are widely used. The vegetable tanning method does not need the
prior preparation stage of pickling and therefore the contributions to pollu-
tion load from sulfate salts are lower. Vegetable tannins, however, are known
to be hard to biodegrade (Healy and Young, 1978), and hence wastes bearing
vegetable tannins degrade slowly.
Among the various tanning systems, chrome tanning is the most com-
monly used tanning system in commercial practice due to its ability to pro-
duce softer, weightless, bright-shade leathers with high wet heat resistance
in a shorter time frame. More than 90% of the leathers processed globally
contain chromium (Covington, 1997a; Germann, 1995, 1999). In chrome tan-

ning, the cationic matrix (pickled pelt) is treated with BCS. Diffusion of
chromium(III) salts into the skin matrix at pH < 3.0 initially leads to ionic in-
teractions (Rao et al., 1997). Over longer durations of tanning, readjustments
in pH of the medium around 3.8–4.0 lead to irreversible binding of Cr(III) salts
to the protein through coordinate covalent bonding (Shuttleworth, 1950).
The addition of an alkali, sodium bicarbonate, not only increases the pH
to the pK a value of carboxy amino acids but also increases the basicity
(Schorlemmer basicity, defined as the percentage of number of hydroxyl
groups combined with one atom of chromium [Sharphouse, 1983]) of Cr(III)
species (Venkatachalapathi et al., 1982). The interaction of chromium(III) salts
with the protein matrix involves a complex array of chemical processes. At
least two kinetic stages have been identified in the chrome tanning operation
(Rao, 1991). The binding of chromium at the molecular level provides inter-
and intrachain crosslinks along the triple helices, penta fibril, and fibrillar as-
semblies up to higher organizations of collagen (Covington, 1997a). Thus, the
molecular mass of collagen may increase from 300,000 to (300,000)n daltons
where n is the number of collagen molecules interlocked through coordinate
covalent interaction with chromium complexes. This increase in long-range
order of the matrix would essentially result in increase in thermomechanical
stress and to further desolvation due to the reduction in the interaction of
water clusters around the protein functional groups (Gayatri et al., 1999).
BCS is a mixture of many molecular species such as octaaqua-
µ-dihydroxochromium(III), octaaqua-µ-dioxochromium(III), hexaaqua-µ-
dihydroxo-µ-sulfatochromium(III), and tetraaquahydroxosulfatochromium-
(III) (Rao et al., 1997). High kinetic lability and poor thermodynamic affinity
of some of the species lead to poor uptake of chromium during chrome tan-
ning. Depending on the manufacturing conditions, the uptake of BCS may
vary (Chandrasekaran et al., 1999). When the uptake levels are low, higher
amounts of chromium along with neutral salts are discharged, which increase
the COD, TDS, and SO2− 4 content in the spent chrome liquor (Chandrasekaran
et al., 1989). Although the oxidation state of chromium in the tanning salt is
only trivalent, discharge norms do not often specify the redox states, because
of the concerns of possible conversion of the trivalent state to the more toxic
hexavalent form (Fathima et al., 2001; Bartlett and James, 1979). The spent
chrome tanning solutions are sources of both TDS and chromium pollution,
which need to be addressed.
C. Posttanning
Posttanning operations, in general, attempt the addition of aesthetic val-
ues and improvement of intrinsic properties of leather (Ramasami et al.,
1999c). Rechroming, neutralization, retanning, dyeing, and fatliquoring form
the major steps of posttanning operations (Ramasami and Prasad, 1991). Post-
tanning operations are carried out in a narrow pH range of 4.0–6.0 using a
wide variety of proprietary formulated chemicals. It is now realized that post-
tanning processes contribute to neutral salts, COD, and heavy metal pollution
(Simoncini and Sammarco, 1995). Wastewater from posttanning processes
contains COD, TDS, and Cr in the range of 8.25, 10.7, and 0.12 kg/ton of
leather processed, respectively (Ramasami et al., 1998). Additionally, azo dyes
and biocides add to the toxic load of wastewater streams (BASF, 1998). The
contributions to BOD, COD, and TDS loads in wastewater are significantly
lower from the posttanning operations in comparison to the total discharge.
It, however, is necessary to carry out treatability studies on the proprietary
formulations so that nondegradable substances may be avoided.
D. Finishing
The pollution load and the volume of the effluent generated in finishing oper-
ations are not significant. This waste stream is characterized by the presence
of polymeric binders, heavy-metal-based pigments, solvents, nitrocellulose,
and other topcoat materials, as described by Greif (1990). The volume of
effluent from these operations including washing is about 1–2 m3 /ton of
rawhide processed (Langerwerf and Chandrababu, 1999). The air pollution
related to use of formaldehyde, unreacted acrylic monomers, toxic-metal-
based pigment formulations, and solvent-based top coats causes concern,
as the bulk of the gaseous wastes is produced in this set of unit operations
(Swarna et al., 1999; Corning et al., 1991; Deselinicu et al., 1997).
E. Solid Wastes
Apart from liquid and gaseous wastes, large quantities of solid wastes are
also generated during leather processing and subsequently during effluent
treatment (Germann, 1999). Although some of the wastes find limited applica-
tions, the safe disposal of the bulk of the solid wastes has posed serious prob-
lems. The types of solid wastes generated in a tannery processing 1 ton of raw
skins/hides have been quantified in Table 2 (Kaul and Ravindranath, 1999).
III. COMBATTING ENVIRONMENTAL CHALLENGES:

TECHNOLOGICAL MEASURES
Environmental challenges from leather processing arise from both the na-
ture and the quantity of wastes discharged. In combatting the environmental
challenges in the leather processing industry in general and in developing
countries in particular, there has been an attempt to emphasize the role of
effluent treatment plants (ETPs) (Rao et al., 1999). Conventional tannery ETPs
TABLE 2. Nature and Quantity of Solid Wastes Produced from Processing

1 Ton of Raw Skins/Hides
Nature of solid waste Quantity (kg)
Salt from handshaking 80

Salt from solar pans (not realized) 220
Hair (pasting ovine) 100
Raw trimmings 40
Lime sludge (mostly bovine) 60
Fleshing 120
Wet blue trimmings (grain splits) 30
Chrome splitting (bovine) 65
Chrome shaving (mostly bovine) 95
Buffing dust (including shaving bovine after crust) 65
Dyed trimmings 35
Dry sludge from ETP 125
Note. From Rao et al. (2004).
offer physicochemical treatment followed by biological and tertiary treatment

to meet the standards (Rao et al., 1999). Significant technological advance-
ments are being made in the end-of-pipe treatment methods to achieve higher
efficiency in meeting the standards in a cost-effective manner. The anaer-
obic treatment of tanning wastewaters in different locations in India has
included the application of technologies based on lagoons, contact filter, up-
flow anaerobic sludge blanket (UASB) reactor, and high-rate biomethanation
(van Groenestijn et al., 1995; Rajamani et al., 1995; Ramasami and Sahasrana-
man, 2000). Technologies based on biomethanation attempt to convert the
organic wastes into methane. UASB technology for the treatment of tannery
wastewaters is indeed relevant by virtue of the advantage of lower energy
and area requirements. Although anaerobic treatment of tannery wastewa-
ter is efficient to reduce the BOD and COD loads by 50–60%, posttreatment
using aeration methodologies is essential to achieve 30 ppm and 250 ppm
BOD and COD norms (Buljan, 1996), respectively, in India and many other
countries. Such posttreatment methodologies for tannery wastewaters from
anaerobic biodigestion have included the use of aerators with and with-
out the aid of aerobic microorganisms. A new method based on wet air
oxidation at ambient pressure and temperature conditions has been devel-
oped and successfully commissioned in individual ETPs in India (Sekaran
et al., 1999). A new posttreatment technology, chemoautotrophic activated
carbon oxidation, developed and adopted for treating tannery wastewaters
after anaerobic treatment and filtration, enables reduction of COD, sulfates,
and color. Activated carbon filters, reed bed and root zone techniques, and
reverse osmosis methods are being investigated for providing tertiary treat-
ment of tannery wastewater (Rajagopalan and Thimmapuram, 1997; Daniels,
1995). The high-rate transpiration system has emerged as a possible method
for treating salt-bearing tannery wastewaters (Rao et al., 2001). Recently, an
accelerated evaporation and crystallization of saline streams using flat-plate

collectors and sprinkler systems has been developed (Buljan et al., 2001).
Some of the technological options for the handling of solid wastes (Kaul
and Ravindranath, 1999; Scheijgrond, 1998) are as follows. Timmings of raw
hides/skins and pelts and fleshings can be utilized for glue manufacture.
Collagen recovered from raw hide/skin and leather trimmings can be advan-
tageously used in the preparation of collagen-based biomaterials for medical
and other applications (Kumar et al., 2002; Sai et al., 1995; Balasubramani
et al., 1997; Huc, 1985; Miller, 1996; Taylor et al., 1997, 1998). The salt ob-
tained from mechanical desalting and solar evaporation can be used for
curing or pickling or be disposed off in a nearby area. Biomethanation of
fleshings and solid sludge from primary and secondary treatments is an eco-
nomically viable option for secured disposal (Aloy et al., 1989). The hair re-
covered from leather processing is conventionally used for the manufacture
of low-priced rugs and carpets. Keratin, a protein of hair, has also been con-
verted into hydrolysate and used as a tanning aid (Ramamurthy et al., 1989).
Sludge from lime pits finds use in land filling as well as in construction of
low-priced houses. The barks and nuts from vegetable tanning can be used as
fuel for boilers and brick kilns and as a soil conditioner (Parks, 1916; Herlihy
and Billings, 1996). The shavings, trimmings, and buffings of vegetable- and
chrome-tanned leather find usage in the manufacture of leather boards (Gish,
2000; Sykes, 1997b; Okamura and Shirai, 1972). It has also been shown that
chrome shavings can be used as a reductant in the manufacture of BCS (Rao
et al., 2002a). A new parchment-like material from chrome shavings has been
developed and is found useful in the manufacture of home furnishing prod-
ucts (Rose et al., 2001).
The cost-effectiveness of waste treatment and management in the leather
processing sector has long remained a most important issue. There is now
an emerging recognition that the environmental issues in the leather process-
ing sector are better managed by a new approach. The approach involves
(a) pollution avoidance through waste minimization, (b) technological up-
grading of waste treatment systems, and (c) safe disposal of treated effluent
and sludge into receiving bodies with adequate precautions to avoid eco-
logical destruction. The role and importance of technological measures to
combat environmental challenges from leather processing activity are now
increasingly recognized.
IV. WASTE MINIMIZATION IN LEATHER PROCESSING:

A STEP FORWARD
The measures for waste minimization in leather processing involve a close au-
dit of the type and quantity of chemicals used, exhaustion levels of chemicals
used, amount of wastes generated, and possible technological and manage-

ment steps needed to reduce wastes and ensure that the wastes discharged
are treatable. Tannery waste management has become a matter of serious
concern in recent years, and noncompliance with environmental regulations
has resulted in closure of tanneries in some parts of India (Sykes, 1997a;
Sahasranaman and Buljan; 2000). The assessment of the extent of pollu-
tion and identification of sources through a process audit has been carried
out in different tanning centers in India to evolve effective and appropriate
strategies for mitigating the pollution-related problems faced by the leather
industry. These are essential if leather processing is to be rendered environ-
mentally sustainable.
In-plant control measures for mitigating tannery pollution generally aim
at the reduction or elimination of toxic wastes through process adjustments
(Ramasami et al., 1994). It is generally believed that lasting solutions to the
problem of tannery pollution rest in cleaner processing. The development
and implementation of cleaner technologies in general require (a) careful au-
diting of the toxicological characteristic of every chemical inputs, (b) avoid-
ing environmentally sensitive chemicals, (c) ensuring near total absorption
of chemicals used, (d) assessing the environmental impact of the resulting
process wastes, and (e) cost-benefit analysis and optimization of processes
for best economic returns. The commonly used criteria for the selection of
cleaner leather processing are (a) environmental impact of process wastes,
(b) treatability of process wastes, (c) environmental quality of treated wastes,
(d) costs of after-treatment and (e) optimization of process water.
V. CLEANER LEATHER PROCESSING: EMERGING

TECHNOLOGICAL OPTIONS
Prevention or redution of pollution at the source through in-process con-

trol measures is assuming greater significance in the leather industry due to
the realization that end-of-pipe treatment alone is not enough to meet the
stringent specifications laid down for the discharge of treated wastewater by
pollution control authorities. The strategy for in-process control for pollution
reduction should attempt to integrate cleaner process options with efficient
water management practices, as the volume of effluent has a direct influ-
ence on the cost of treatment of effluent (Parthasarathy, 1995). The reuse
of spent liquor after the removal of the pollutants in suitable unit opera-
tions should be considered. The ideal strategy should be aimed at zero or
near-zero discharge of waste liquors (Sykes, 1997a). The cleaner processing
options recommended need to be cost-effective in order to be economically
viable. Costing should take into consideration the cost of the treatment of
effluents in the absence of such options. The success of cleaner technologies
depends on the following factors: (a) reduction of pollution in terms of quan-

tity and quality, (b) tanners’ benefits in terms of leather quality improvement
and/or cost reduction, (c) reproducibility of the process, (d) cost effective-
ness to be economically viable, and (e) wide market opportunities.
A. Curing
One of the major sources of pollution from tannery wastewater has been
identified to be common salt or sodium chloride (Sundar and Muralidharan,
1999). This emanates largely from the curing, pickling, and chrome tan-
ning practices used in the leather processing. Saltless or less-salt curing
as an alternative to wet salting presents an interesting technological op-
tion (Ludvik and Orlita, 1986). Some of the cleaner curing methods are
(a) solar drying, (b) freeze drying (Stephens, 1987), (c) microwave/dielectric
drying (Komanowsky, 2000), (d) use of KCl in place of NaCl (Bailey, 1995a),
(e) borax–phenol (Selvarangan and Shanmugasundaram, 1984), (f) zinc chlo-
ride (Money, 1974), (g) silica gel and a low amount of salt (Kanagaraj et al.,
2000) and (g) metal oxinates (Bailey et al., 1976; Barrett, 1986). Management
options include processing green hides and skins, gamma (Bailey, 1999) and
electron beam (Bailey et al., 2001; Bailey and Haas, 1988) irradiation tech-
niques, and transportation in refrigerated trucks (Bailey, 1995b). Although
saltless curing processes do exist, wet salting is the most commonly followed
in commercial practice due to its low cost and high efficiency.
B. Desalting
Desalting of wet-salted raw stock prior to soaking forms an easy and imple-
mentable mode of reducing salt concentrations in tannery wastewater. De-
salting can be done either manually or mechanically. Manual methods impli-
cate dusting or brushing off the physically adhering crystalline salt. Through
this method, it has been observed that nearly 30–40% of the total salt con-
tained in wet salted skin or hide material can be removed (Rajamani and
Viswanathan, 1998). Mechanical desalting is carried out by the drumming of
wet-salted stock in a specially made slotted drum at 4–6 rpm. Air blowing
or the use of small amounts of rinse water can further facilitate the process.
Such desalting technologies also lead to better opening of fiber bundles and
significant reduction of the carryover of salt into the subsequent streams like
liming. Wheel-type desalting machines have been designed and used for ef-
ficient desalting of skins (Rao et al., 2001). The recovered salt can be reused
for curing fresh hides/skins as well as in pickling processes. The benefits
of desalting include (a) increase in the efficiency of soaking, (b) reducing
the amount of carryover salt, thereby reducing the pollution load, and (c)
recovery of salt.
C. Soaking
In-process control in soaking should aim at the reduction of TDS due to
dissolved chloride as well as the volume of wastewater discharged. In total,
salt alone accounts for 60–70% of the TDS in processing (Ramasami et al.,
1999b). The waste soak stream is currently being segregated and taken for
solar evaporation. Efforts should be made to eliminate salt as much as pos-
sible for a better management of the problem. Generally, the soaking pro-
cesses adopted in commercial practices involve cocurrent flow of materials,
namely, skins and hides on the one hand and soak liquor on the other (with 3
changes of water of 300% of raw weight). To reduce the discharge of waste
soak liquor, a countercurrent soaking method has been found to be very
effective. Countercurrent flow of materials could lead to a reduction in the
amount of water used by nearly 50–60% in soaking operations (Rao et al.,
2003). This offers an opportunity to reduce the hydraulic load by 20% in total
volume of wastewater.
D. Green Fleshing
Green fleshing is advocated to reduce the consumption of chemicals on the
one hand and to get more uniform results in liming on the other. In Western
countries, efforts are made to remove the flesh as much as possible in the
abattoir itself. By green fleshing, it has been possible to reduce the weight
of the stock by nearly 10% (Langerwerf and Chandrababu, 1999).
E. Liming and Reliming

The conventional process uses lime and sulfide in high proportions (Money,
1996). Lime is a poorly soluble alkali, so there are advantages from limited
availability of dissolved alkalis. There are also disadvantages in generation
of a large quantity of solid wastes. Lime-free processes for the consolidation
of leather-making substances and enabling the removal of flesh are now
available, with limited success (Cantera et al., 1996). Although sulfide is toxic,
it is the prime depilant in the unhairing process. Reduction of sulfide at
the source is now possible using enzyme-assisted processes (Taylor et al.,
1987). The cleaner options for liming include (a) the use of enzymes or
other unhairing assists to reduce sulfide offer for a hair-saving liming process
(Money and Scroggie, 1971; Heidemann and Smidek, 1987), (b) the possibility
of recycling spent relime liquors for unhairing (Komanowsky and Senske,
1982; Money and Adminis, 1974), (c) completely replacing the hair pulping
method of the unhairing process (Cantera, 1998; Feigel, 1998a), (d) effective
methods of filtration to prevent the loosened hair from going into the effluent
(Fadel and Speranza, 1995; Cranston et al., 1986a) and (e) the optimization
of quantities of water used in pit or paddle liming.
Significant efforts have been made in the past five decades to render
the dehairing process in tanneries cleaner. Sirolime (Cranston et al., 1986a,
1986b) and Darmstadt through-feed unhairing processes (Heidemann and
Harenberg, 1972; Heidemann, 1993) are based on the conventional chemical
inputs. The sirolime process consists of an impregnation stage with hydro-
sulfide and then a brief wash followed by oxidation of hydrosulfide external
to the hide. Lime is then added and hair loosening occurs due to localized
attack on the hair root by the sulfide ions generated within the hide. Hair is
recovered by filtration and any residual hair is destroyed in a secondary lim-
ing stage by the addition of sulfide, additional lime, surfactant, and recycled
lime liquor. A Darmstadt University group has introduced a continuous-flow
unhairing technique. Fresh or well-soaked hides hung over the bars along
the backbone hair side up are sprayed with 5–10% sodium sulfide solution
in technical concentration in a cabin for 5–20 min. The hairs are transformed
into a pulp and then stripped off with a special stripping cylinder device with
plastic blades. These pelts are instantly fleshed and subsequently splitted.
Dimethylamine (Somerville et al., 1963; Hetzel et al., 1965, 1966), thio-
glycolic acid, sodium thioglycolate, and performic acid (Kamal et al., 1998;
Uehara et al., 1986; Goddard and Michaelis, 1934; Fava et al., 1957) have
been used to replace sulfide for dehairing. These, however, are not commer-
cially successful for various reasons, such as cost, efficiency, and toxicity (von
Vlimmeren, 1976). Rosenbusch (1965) reported the use of chlorine dioxide
for dehairing. Morera et al. (1997) studied the use of hydrogen peroxide in
alkaline medium for dehairing by an oxidative mechanism. However, the
reduction in pollution load, especially COD, is not significant. Sehagal et al.
(1996) developed a nonenzymatic, sulfide-free dehairing process using 1%
nickel carbonate, 1% sodium hydroxide, 5% lime, and kaolin, along with wa-
ter, through a painting technique. Disposal or recovery of nickel compounds,
however, poses serious health problems. Schlosser et al. (1986) reported the
use of Lactobacillus-based enzymes at acidic conditions for dehairing. This
method leads to the solubilization of collagen at the experimental condi-
tions. Valeika et al. (1997, 1998) found that the additons of salts such as
sodium chloride, sodium sulfate, sodium formate, or sodium hydrogen phos-
phate influences the extent of hair removal, as well as opening the dermis
structure.
Röhm (1910) developed the first successful enzymatic unhairing, the
Arazym process, as described by Green (1952). Enzymatic unhairing (using
enzymes, generally based on protease, along with small amounts of sulfide
and lime applied as paint on the flesh side) causes loosening of hair by selec-
tive breakdown of cementing substances and presents a hair-saving approach
(Green, 1952; Bose, 1955; Pilawski and Felicjaniak, 1976; Jones et al., 1968;
Dhar, 1974; Puvanakrishnan and Dhar, 1986; Brady et al., 1990). Enzyme-
assisted processes for the removal of hair are associated with both merits
and demerits (Feigel, 1998b; Taylor et al., 1987). The demerits perceived are
(a) fear of possible damage of leather-making substances, (b) inadequate

fiber opening, (c) flatter grain and substance, and (d) higher chemical costs.
The recognized merits are (a) higher area recovery, (b) smoother grain, (c)
better in-plant ecology, and (d) higher efficiency of wastewater treatment
devices. There is a possibility to overcome the demerits through proper pro-
cess optimization and control by using a combination of enzyme with sul-
fide (Technology Plan, 1997). An increase in the area of the final leather
by 2–3% due to enzymatic unhairing has been demonstrated (Thanikaivelan
et al., 2001a; Shrewsbury, 2002). It is now possible to use enzyme-assisted
dehairing methods as alternatives to sulfide-based processes with benefits
of reduced BOD, COD, TDS, and sulfide levels in wastewater, as well as
improved efficiencies of wastewater treatment plants (Rao et al., 2001).
Lime-free fiber opening methodologies have scarcely been attempted.
These include the use of strong alkalis (Herfeld and Schubert, 1969),
Lactobacillus-based enzymes (Schlosser et al., 1986), lyotropic agents (salts/
acids that cause lyotropic swelling), and bating enzymes (Thanikaivelan et al.,
2001a). These methodologies, however, have limited applications due to im-
proper opening of fiber bundles.
Lime splitting for heavier hides would considerably reduce the cost of
chemicals used, apart from reducing the water consumed in processing.
There is also the possibility of a reduction in processing time. Area yield
has also been found to increase by about 5% when lime splitting is done
(Borge, 1986; Mance, 2000; Langerwerf and Chandrababu, 1999). Although
Indian cow hides are not thick enough for lime splitting, this method would
be tremendously useful for buffalo and imported hides. The washings of
limed pelts can be reused for liming. This would considerably reduce the
pollution load as well as the volume of wastewater discharged.
F. Deliming
The use of ammonium chloride and ammonium sulfate adversely affects the
characteristics of the effluent (Huber and Satyendra, 1990). They contribute
to 75–80% of the ammonia in the effluent. Although the ammonium salts
are cheap and perform efficiently, the increase in COD of the wastewater
generated in the operation, apart from the generation of dissolved ammonia–
nitrogen, gives rise to difficulty in effluent treatment. The ammonium sulfate,
which is prevalently used, also contributes to dissolved sulfate. Hence, alter-
natives are sought to reduce the pollution load. These alternatives are based
on organic and inorganic acids, esters of carboxylic acids, and nonswelling
aromatic acids (Streicher, 1987; Frendrup, 1996). The costs of these products
are prohibitively high when compared to ammonium salts and hence they
are yet to be commercially exploited. Ammonia-free deliming has gained im-
portance in many countries. Carbon dioxide deliming has been carried out
in some cases with success (Munz and Toifl, 1992; Purushotham et al., 1993).
In these instances, environmental as well as other quality benefits have been
reported. The issues needing special process adjustments include (a) com-
plete removal of sulfide prior to deliming, (b) the need for acid rather than
conventional alkaline bate, and (c) rigorous process control systems.
G. Pickling
The pickling process contributes to TDS in the form of chlorides considerably,
and this is not amenable to treatment via currently used end-of-pipe treatment
methods. As mentioned earlier, the current management practice involves
the solar evaporation of this stream mixed with the soak liquors. The long-
range solutions should include the possibility of saltless pickling (Pojer and
Huynh, 1999) and pickleless chrome tanning options (Dasgupta, 1998). The
immediate solution would be to consider the pickle recycle options (Burrows,
2001), which would considerably reduce the load in solar evaporation, which
becomes the bottleneck in increasing the capacity of production. The concept
of using nonswelling acid in pickling is already known, but this has not been
commercially exploited due to the high cost involved (Pojer and Huynh, 1999;
Rao et al., 2002c). There are many commercial products available based
on naphthalene sulfonic acids, sulfonated aromatic dicarboxylic acid like
phthalic acids, and auxiliary agents (Palop and Marsal, 2002; Post, 1964;
Herfeld and Schubert; 1975). The latter class of compounds is quite interesting
because they also help in improving the exhaustion of chrome and hence
the increase in the cost can to some extent be justified.
The commercial practice is to retain 50% of the pickle float for tanning
(Sundar et al., 2002). The remaining 50% is currently taken for solar evapora-
tion. There exists a possibility of reusing this pickle liquor after the removal
of the fibrous materials safely through filtration, for the next batch after re-
plenishment with salt and water (Burrows, 2001). Such recycle and reuse
methods reduce TDS of the effluent discharged from the identified stream.
H. Chrome Tanning
Among the various tanning systems, mineral tanning in general, and chrome
tanning in particular, have been popularly followed in commercial practices
due to aforementioned reasons. Much of the efforts for pollution reduction
are mainly focused on chrome tanning because chromium is considered to
be toxic (Leonard and Lauwerys, 1980; Katz, 1991; Dartsch et al., 1998).
The biotoxicity of chromium has been a subject of active discussion. Al-
though the implication of chromium(III) in glucose and lipid metabolism has
been considered beneficial (Govindaraju et al., 1989; Anderson et al., 1997;
Mertz, 1998), epidemiological and animal studies have firmly established
hexavalent chromium compounds as potent carcinogens (Costa, 1991). Once

inside the cell, Cr(VI) is reduced to lower oxidation states (V, IV, and III)
(Arslan et al., 1987). Cr(III) species have been shown to be mutagenic and
genotoxic (Jennette, 1979). Although trivalent chromium compounds are ki-
netically inert to ligand substitution reactions, they do react strongly with
DNA and proteins (Balamurugan et al., 1999). Trivalent chromium leads
to the formation of different Cr–DNA adducts such as DNA–protein, inter-
strand DNA, and DNA–amino acids cross-links (Wedrychowski et al., 1985;
Zhitokovich et al., 1995, 2000). Some of the Cr(III) complexes containing
aromatic imine ligands have been found to be mutagenic in Salmonella ty-
phimurium (Beyersmann and Koster, 1987). Salen-based Cr(III) complexes
have been found to induce apoptosis in lymphocyte cell cultures (Rajaram
et al., 1995). Some of the Cr(III) complexes in specific ligand environments
have been proposed to bring about oxidative damage to plasma proteins,
glycoproteins, and DNA (Shrivastava and Nair, 2000, 2001; Tsou et al., 1997;
Voitkun et al., 1998; Vijayalakshmi et al., 2000). Effects of soil pollution by
the metal ion are observed when soil contains large amount of soluble and
biologically assimilable forms of chromium (Bartlett, 1991). A part of Cr(VI)
present in the soil may be reduced by soil reductants (Bartlett and Kimble,
1976). When soluble Cr(III) is added to soil, manganese oxides present in
the soil may cause oxidation to Cr(VI) (Bartlett and James, 1979). Cr(VI) is
shown to be 500 times more toxic than Cr(III) (Venier et al., 1982).
Conventional chrome tanning salts and methods give an uptake of only
40–70% of the material used during tanning, resulting in the wastage of
material on one hand and ecological concerns on the other (Gauglhofer,
1986; Prasad et al., 1987; Ramasami, 1996). The value of this loss is approxi-
mately US$10,000,000 per annum in India (Ramasami, 1996). The treatment
of chrome-bearing wastes through normal physicochemical methods results
in chrome-bearing sludge, whose disposal is a serious problem (Warrier et al.,
1995a, 1995b).
1. HIGH EXHAUST TANNING
It is now technologically possible to increase the absorption of chromium

during chrome tanning to above 85%. There are commercial external aids
(Luck, 1980; Chandrasekaran, 1987), intrinsically modified chrome tanning
salts (Rao et al., 1998; Suresh et al., 2001; Thanikaivelan et al., 2002a)
with high exhaustion level, and chrome tanning systems with more rational
pickling and tanning (Rao et al., 1992), which ensure higher absorption of
chromium. The preparation of high-exhaust chrome tanning salt has become
technically feasible through designed alterations in the process of manufac-
ture of the chrome tanning salts, wherein the formation of low-affinity species
has been avoided to increase the absorption levels (Rao et al., 1998). Most
high-exhaustion methods discharge wastewater from sectional chrome tan-
ning streams with chromium concentrations on the order of 300–750 ppm.
These streams are not directly amenable for discharge. While economic ad-
vantages of the high exhaustion chrome tanning are evident, further process-
ing of waste streams of the chrome tanning yard needs to be integrated.
2. DIRECT RECYCLING
Extensive studies have been made on the use of spent chrome liquor as a
pickling or tanning bath (Davis and Scroggie, 1973, 1980; France, 1975; Rao
et al., 2002c). Direct recycling of spent chrome tanning liquors for pickling
causes surface fixation of chromium due to high chromium concentrations.
Also, direct recycling of chrome liquors increases the concentration of neutral
salts, which reduce the chrome uptake in subsequent batches. Direct recy-
cling of spent chrome liquor after preacidification to a pH around 1.0 results
in leathers without any surface deposition of chromium (Davis and Scroggie,
1980). A system based on membrane separation for the selective removal
of chromium from neutral salts has been developed (Rao et al., 1989). This
system makes use of a chrome-rich stream for tanning and a neutral-salt-
rich stream for pickling. The economic viability of the technique is yet to be
established.
3. CLOSED PICKLE--TAN LOOP
High-exhaustion methods ensuring absorption of 85% of chromium are still

not environmentally acceptable. A typical method based on Alutan (an alu-
minum syntan)–BCS for tanning has been developed (Rao et al., 2002c;
Chandrababu et al., 1995; Ramasami et al., 1999a). The exhaustion levels
of chromium and aluminum exceed 90%. The spent solution is recycled as
pickle floats for subsequent batches instead of being discharged, thus gen-
erating a closed loop with zero discharge of chromium. The highlight of the
system is an overall saving of US$30–40 per ton of leather processed. The
system also ensures reductions in BOD, COD, and TDS loads on ETPs, as
well as saving water.
4. CHROME RECOVERY AND REUSE
Chromium in the sectional streams of wastewater can be recovered, regener-

ated, and reused effectively through a chrome recovery/reuse methodology
(Rao, 1987; Covington et al., 1983). In this method, chromium is precipi-
tated with an alkali as chromic hydroxide, allowed to settle under gravity,
separated from the supernatant, and redissolved in sulfuric acid (Sreeram
et al., 1999). The recovered chrome is reused as a tanning salt in the admix-
ture with fresh BCS after replenishment (Prasad and Nair, 1994; Venba et al.,
1999). Chrome recovery/reuse plants have already established commercial
viability. The process is simple and easy to adopt. It is financially attrac-
tive as the payback period is 1–2 years for a plant of 5–10 m3 capacities (Rao
et al., 1995; Langerwerf, 1999). A semicontinuous chromium recovery process
for large volumes of wastewater has been developed for commercialization
(Sreeram et al., 2000a). One such plant has been installed in Tamil Nadu,
India, at a capacity of 24 m3 . Because the chrome recovery process ensures
that the sectional wastewater from the chrome tanning operation is segre-
gated and handled, sulfate-bearing streams can be diverted away from the
biomethanation reactors (Rajamani et al., 1995). This would facilitate a greater
efficiency of biomethanation. The TDS problem, however, needs to be ad-
dressed separately even when a chrome recovery/reuse process is adopted.
Attempts have been made to recover chrome as high-purity chromium
from tannery effluents (Deep et al., 2001). A three-step process involving pre-
cipitation, extraction, and electrodeposition has been developed by Gupta
et al. (2002) for the recovery of chromium(III) from tannery effluent. A sol-
vent extraction technique for recovering chromium from spent chrome liquor
has been developed using Cyanex 301–toluene (Khwaja et al., 2000a) as
well as mono(2-ethylhexyl) phosphoric acid–n-hexane (Khwaja et al., 2000b)
systems. Recently, an attempt has been made to remove chromium from tan-
nery effluent using seaweed, Sargassum species, and to reuse the chromium-
bearing seaweed in the manufacture of BCS as a reductant (Aravindhan et al.,
2004a).
5. TWO-STAGE CHROME TANNING
A new two-stage chrome tanning system has been evolved to overcome the
environmental problems of chrome tanning (Muralidharan et al., 2001). In
this system, the pickled pelt is treated with 10% (w/w) BCS (on fleshed weight
of hides and skins) initially with a sufficient quantity of water. After ensuring
complete penetration of chromium in the skin matrix, the spent chrome
solution is drained before the basification process and reused in the place
of chrome tanning salt for subsequent batch. The chromium-treated skin
matrix is subjected to basification subsequently. The spent liquor from this
process contains a low concentration of chromium and hence is reused for
the preparation of pickle liquor for the next batch, for efficient management
of chromium.
6. PICKLELESS CHROME TANNING
Pickleless chrome tanning is a recently introduced concept (Venba et al.,

1995; Dasgupta, 1998) to not only do away with the use of salt (sodium
chloride) in tanning but also increase the exhaustion of chrome and consid-
erably reduce the salt generated in basification on account of the very low
pH associated with the conventional pickling prior to chrome tanning. It is
theoretically estimated that the reactivity of chrome can be enhanced by in-
creasing the starting pH from 2.8 to 5.5 (Covington, 1986). To start the chrome
tanning at such an elevated pH, one has to make sure that there is no prob-
lem with either penetration or distribution of chrome in the fibre matrix. Re-
cently, a method based on pretreatment with ethanolamine–formic acid has
been standardized, and its effect on the quality of leather has been studied
(Prentiss and Prasad, 1981; Chandrababu et al., 1995; Covington, 1997a,

1997b; Thanikaivelan et al., 2001a). By using this method, it is possible to get
a more uniform distribution of chrome even if the pickling pH is not uniform
throughout the cross section. Earlier reports, however, suffer from the use of
some specialty chemicals such as carbon dioxide (Munz et al., 1997), chrome
syntan (Suresh et al., 2001), modified BCS (Thanikaivelan et al., 2002a), or
a small amount of sodium chloride (Munz et al., 1997). Tanners around the
world are reluctant to use this method due to fear of grain swelling and sur-
face precipitation, although no evidence of these problems has been shown
to date.
7. LESSCHROME AND CHROMELESS TANNING TECHNOLOGIES
A chromium–iron tanning agent as a chrome-saver approach has been de-

veloped (Thanikaivelan et al., 2000a). In a select ligand environment, the
negative attributes of iron tanning such as deterioration and darkening of
color on aging were avoided. The leather made from this tanning agent ex-
hibits a shrinkage temperature of about 115◦ C and meets all the required
chemical and physical properties. Natural colors based on Cr–Fe tanned
leather by treating with vegetable tanning materials have also been de-
veloped (Rao et al., 2002b). Chromium–silica-, aluminum–zinc-, chromium–
zinc-, chromium–zinc–silica-, and aluminum–tannic acid–silica-based tanning
agents have been developed (Thanikaivelan et al., 2000; Madhan et al., 2001a,
2002; Fathima et al., 2003, 2004) for reducing the chromium emission and
improving the physical and bulk properties of the leathers.
The use of alternative mineral tanning salts has been proposed and
attempted with varying degrees of success (Chakravorthy and Nursten, 1958).
Aluminum has been considered as an alternative to chromium for many years
(Selvarangan and Nayudamma, 1964; Montgomery, 1987; Takenouchi et al.,
1997; Taqui-Khan, 1987). The majority of commercially adopted aluminum-
based tanning salts suffer from some limitations. Particularly, the fatliquoring
and retanning systems require substantial modification. This in part is because
of the high cationic potential of aluminum salts. It has been possible to
develop a suitable alternative approach to reduce the cationic potential and
render Al(III) with transition-metal-like behavior (Kanthimathi et al., 2002).
This has been possible because of insight into the aqueous chemistry of
Al(III) salts.
Zirconium(IV)-based tanning systems have remained an attractive possi-
bility but suffer from disadvantages associated with low pH values required to
avoid insolubility of the tanning salts (Ranganathan and Reed, 1958). Through
manipulation of acid–base behavior of the coordinated water ligands by in-
fluencing the ligand environment, it has been possible to raise the pH of
precipitation to values as high as 4.0 (Sreeram et al., 2000b). The use of zir-
conium oxychloride in a select ligand environment as a solo tanning agent
has been demonstrated (Sundararajan et al., 2003; Madhan et al., 2003). These
systems, if made costeffective, can emerge as chrome savers. Titanium-based

tanning salts and mixtures of metal oxides as combination tanning systems
have been developed (Covington et al., 1998; Covington, 1998; Tate, 1989).
Some of these salts are being commercially used to a limited extent.
Organic tanning. It has now been possible to avoid completely the use
of mineral tanning salts in the manufacture of soft types of leather includ-
ing suede garments (Covington and Shi, 1998). It is also possible to process
richly dyed garment suedes based on vegeable and some organic tanning
adjuncts (Madhan et al., 2001b). In these processes, the role and importance
of surface charges assume much significance. The underlying process chem-
istry is becoming well understood. These technological options open up new
avenues for ecofriendly tanning methodologies (Covington, 1998).
I. Posttanning and Finishing

Posttanning operations involve the use of retanning agents, fatliquors, dyes,
and finishing chemicals. Exhaustion levels of many of these materials have
not been quantitatively assessed. Treatability of posttanning chemicals and
the neutral salt content form two important criteria that need closer scrutiny.
Contributions to COD from many retanning agents and fatliquors are sig-
nificant. This can be mitigated by the use of optimized quantities of high-
performing chemicals, which would lead to less discharge of biotreatable
residues.
The various in-process control options for cleaner wet finishing are as
follows (Langerwerf and Chandrababu, 1999):
r Screening of retanning and fatliquoring agents for selection, based on their

biodegradability and uptake behavior.
r Retanning materials based on amino resins and other compounds that are
capable of contributing to BOD and COD should be avoided as far as
possible.
r Fatliquors based on chlorinated paraffins should be avoided; there is a
concern regarding absorbable organic halides in many countries (Cuq and
Delmas, 1999).
r Benzidine and other arylamine based azo dyes, which are potentially car-
cinogenic, should be totally eliminated (Turner, 1994; Püntener, 1998).
r Dyes should be screened for their exhaustion characteristics, and only
high-performing dyes should be used (Page and Fennen, 1998).
r Rationalization of the entire wet finishing operations is needed in order
to optimize the quantities of various chemicals used, thereby reducing the
discharge of chemicals in waste streams.
Optimization of such chemical inputs as well as the choice of inputs

based on treatability data form the most practical mitigation strategy. Such
data have now been compiled for a series of chemical formulations (Technol-
ogy Plan, 1997). Aqueous finishing formulations (Wenzel, 1991; Pulles, 1990),
formaldehyde-free finishing (Gill, 1995; Wu-Sheng et al., 2000), the audit of
azo dyes for environmental acceptability (Püntener, 1998), and biodegradable
biocides (Hauber, 1998) have attracted interest.
Pollution reduction in finishing-yard effluent would involve the follow-
ing measures (Grif, 1990):
r Minimizing the wastage and emission by proper control of spraying ma-

chines (Stockman, 1988; Mannouch, 2002).
r Use of new application methodologies such as roller coaters or low-
pressure spray pistols (Will, 1985; Biles et al., 1985; Pulles and Domanjko,
1985; Löbig, 1997).
r Elimination of lead and other toxic-metal-based pigment formulations
(Hay, 1979).
r Minimizing volatile organic compounds by resorting to water-based for-
mulations, especially in finishing (Gill, 1991, 1993; Walther, 1988; Cluthe
et al., 1978; Biles 1990; Lach et al., 1988; Hanson, 1982).
r Use of newer and safer cross-links in protein finish in place of formalde-
hyde (Gill, 1995).
VI. NOVEL CONCEPTS IN LEATHER PROCESSING: APPROACHING

ZERO-DISCHARGE TANNING
Leather processing activity involves the use of several chemicals, some of

which are not utilized completely (Ramasami et al., 1999b). Excessive use
and poor uptake of chemicals form inevitable sources of pollution. Some
of the chemicals used are inherently constrained with respect to their en-
vironmental consequences. To wipe out the negative image the activity has
created for itself and to move toward sustainable development, it now seems
more appropriate for the global leather sector to implement cleaner process
options to reduce the environmental risks from the sector. A closer audit of
various operations would provide not only the origin of current ecological
constraints from the leather industry but also clues to resolve them. The en-
vironmental protection authorities have specified discharge norms based on
carrying capacity and societal needs. Although end-of-pipe treatment tech-
nologies for achieving wastewater discharge norms do exist, real solution lies
in approaching zero discharge of pollutants (Pauli, 1997; McCleskey et al.,
2001).
There is a need to revisit the leather making operation anew. The wide
variations in pH of the skin matrix during the various steps in leather mak-
ing are bound to impair the bulk as well as surface properties, apart from
contributing to the generation and discharge of neutral salts. An appropriate
approach would be to render the tanning activities cleaner through near-
zero discharge of pollutants. This approach would target the development
of leather processing methods limiting the pH profile needed for various
operations to a narrow range. The net benefits from such an approach will
be
r Reduction in the use of chemicals.

r Reduction in cost.
r Reduction in utilities such as water and power.
r Rationalization of processes.
r Elimination of several processes, namely; liming, reliming, deliming, and
pickling.
r Reduction in process time.
r Reduction in TDS in tannery wastewaters.
r Reduction in sludge volume, especially the total removal of lime sludge.
r Higher utilization of materials like chromium.
Ideally, zero discharge of wastewater is most desirable. As a practical

measure, however, reduction of the discharge of water to 5–6 L/kg leather will
be a good initial step. Approaching the zero-discharge value is an intellectual
as well as a global challenge. This would need to consider and compare
several strategies that are possible to avoid pollution. The approach demands
the use of following concepts either alone or in combination:
r Usage of chemicals having low toxicity or less environmental impact.

r Near 100% utilization of chemicals.
r Recovery of water and valuable chemical inputs from each sectional stream
of wastes and reuse in leather processing to the extent possible.
r Process innovation.
r Product innovation.
r Integration of processes.
Leather processing generally involves a combination of single- and mul-

tistep processes that use as well as expel various biological, organic, and
inorganic materials (Germann, 1999). Hence, a strategy that involves com-
bined advantages of all possible approaches would be ideal. This implies that
the study of suitable zero discharge approaches for every single unit process
is important. Studies on the soaking process are not attempted due to (a) the
diverse nature of curing techniques, (b) availability of several in-plant control
and salt recovery techniques, and (c) the real solution being in designing an
ambient preservation technique. It is now possible to process green hides

without loss in quality (Taeger, 1996). Hence, it has been proposed to re-
design the pretanning and tanning processes excluding soaking by limiting
the working pH to the range of 4.0–8.5. To achieve this, liming and reliming
processes need to be redesigned such that the cross-section pH of the pelt
(pH within the pelt) is 8.0. This implies that the deliming operation could
be eliminated. The chrome tanning step needs to be designed without pick-
ling and basification processes. Finally, the developed processes have to be
integrated in order to achieve zero discharge of pollutants.
Proposed new research fields are as follows:
r Standardization of conventional liming and reliming chemical inputs and

unearthing the role of concentration.
r Countering the problem of sulfide and lime sludge through bioprocessing:
r Lime-free enzyme assisted dehairing.
r Enzyme-based fiber opening by targeting the proteoglycans (protein con-
jugated with carbohydrates) present in skin/hide.
r Sodium hydroxide-based fiber opening to eliminate the problem of lime
sludge.
r Design and development of a pickle and basification-free chrome tanning.
r Integration of best practices from dehairing, fiber opening and pickle-
basification-free chrome tanning processes.
A. Some Early Results

1. ENZYME-ASSISTED DEHAIRING FOR COWHIDES
An enzyme-assisted dehairing process using sodium sulfide in an amount

85% less than that used in the conventional lime sulfide dehairing process
has been developed (Thanikaivelan et al., 2000c). The process does not
require lime for dehairing, thereby ensuring not only 100% elimination of
lime sludge formation, but also complete removal of hair at an unusual pH
(8.0). The pelts, however, require a reliming process, which in turn creates
lime sludge and TDS problems.
2. NONLIME FIBER OPENING
A nonlime fiber opening method based on sodium hydroxide has been de-
veloped by Thanikaivelan et al. (2001b). An optimum concentration [1.0%
(w/w) offer with 350% (v/w) water, based on weight of the dehaired hide] of
sodium hydroxide has been established for optimal opening of fiber bundles.
This has been substantiated through scanning electron microscopy, spent al-
kali liquor and pelt analysis, softness measurements, and stratigraphic chrome
distribution analysis. The pelt analysis shows that the opening of fiber bun-
dles has attained equilibrium, and the pH of the cross section is 8.5. Per-
formance of the leathers is shown to be on par with conventionally treated
leathers through physical and hand evaluation. Softness of the leathers is nu-
merically proven to be comparable with that of control leather treated with
lime. The process also enjoys elimination of the deliming process coupled
with a 45% reduction in total solids (TS) load on the environment.
3. REDUCED FLOAT APPROACH
In an attempt to combat the pollution from beam-house processes, an

ecofriendly way of doing the conventional liming–reliming processes has
been found (Thanikaivelan et al., 2003a) by applying the beam-house chem-
icals optimally. This is based on the fact that swelling requires only 20 to
40% water (based on raw skin weight before soaking) for conventional fiber
opening. This would, in principle, make possible the use of only one-tenth of
the chemicals conventionally used in liming–reliming processes, maintaining
the same concentration gradient. The process uses 40% (v/w) water, 0.35%
(w/w) sodium sulfide, and 1% (w/w) lime for liming, and 40% (v/w) water
and 1% (w/w) lime (percentages based on wet weight of skins after soaking)
for reliming, with conventional process time of 1 day for each process, in a
drum that runs intermittently. It has been found that the dehairing is com-
plete and the extent of opening of fiber bundles is comparable to that of the
control. This has been demonstrated through scanning electron microscopy,
stratigraphic chrome distribution analysis, and softness measurements. Per-
formance of the leathers is shown to be on a par with conventionally opened
up leathers by means of physical and hand evaluation. Softness of the leathers
is proven to be numerically comparable with that of conventionally treated
leathers. The process enjoys reduction in COD and TS loads on the environ-
ment by 85% and 12%, respectively, compared to the conventional process.
The total dry sludge from the liming–reliming processes is brought down
from 152 kg to 6 kg for processing 1 ton of raw skins, which has been
demonstrated for the first time.
4. LEATHER PROCESSING IN NARROW PH PROFILE
A leather processing technique for tanning skins/hides without delim-

ing and pickling processes, in a narrow pH range, has been established
(Thanikaivelan et al., 2001a). The process envisions the use of lyotropic
agents for fiber opening and uses a pickleless chrome tanning system in a
narrow pH range (4.0–8.0). Thereby, the process claims an environmental
benefit of reducing the COD and TS loads by 67% and 64%, respectively.
The developed process claims substantial reduction in water and time re-
quirements as well.
5. BIOCATALYTIC FIBER OPENING: PARADIGM SHIFT FROM

CHEMICAL TO BIOPROCESSING
In an attempt to combat the pollution from beam-house processes, an

enzyme-based fiber opening process has been established (Thanikaivelan
et al., 2002b). An approach has been made to do the beam-house processes
using bioproducts. This is based on the fact that the enzymes specifically
act on the substrate. Suitable enzymes have been designed in order to target
hair and cementing substances, separately. The approach leads to paradigm
shift from chemical processing to bioprocessing. It has been found that the
dehairing is complete and the extent of opening of fibre bundles is compara-
ble to leathers treated with lime. Scanning electron microscopy, stratigraphic
chrome distribution analysis, and softness measurements confirm these find-
ings. Quality of the leathers is shown to be on a par with conventionally
opened leathers through physical and bulk property evaluation. Quantitative
measurement of softness reveals that enzyme treatment provides softness
for the experimental leathers numerically comparable to that of conventional
lime-treated leathers. The total dry sludge from the liming–reliming processes
is brought down from 152 kg to 12 kg for processing 1 ton of raw skins, due
to the replacement of lime with enzymes. The amylase-treated hides, how-
ever, are further processed conventionally, soaking them first in a pickle
bath consisting of a huge amount of salt and sulfuric acid and then chemi-
cally preventing them from rotting by treating with chrome tanning salt. This
results in a significant increase of dissolved solids as well as chromium in
the wastewater.
6. THREE-STEP TANNING TECHNIQUE: A MODEL FOR PROCESS INTEGRATION
The tailored pretanning process evolved in the earlier studies provides a

clean collagen matrix having neutral pH. This provdes a clue on how to tan
the skins directly without deliming and pickling (acidification), if one has
an effective tanning system without a preacidification process. Recently, a
chrome tanning system without a pickling process for conventionally limed
and delimed collagen matrix has been developed (Legesse et al., 2002;
Thanikaivelan et al., 2004a). Now it is possible to integrate the biodriven
process with a pickle-free chrome tanning process (Thanikaivelan et al.,
2004b). This results in complete revamping of the conventional leather pro-
cess sequence. Generally, conventional tanning process involves “do–undo”
processes like curing (dehydration)–soaking (rehydration), liming (swelling)–
deliming (deswelling), pickling (acidification)–depickling (basification). Fur-
ther wide variation in pH has been limited to a very short pH profile. The
net benefits of this approach are countless.
It has been now shown that this enzyme-driven three-step tanning pro-
cess is applicable not only to thin skins (Saravanabhavan et al., 2003a, 2003b;
Aravindhan et al., 2004b) but also to heavy and thick hides (Thanikaivelan
et al., 2003b, 2004c). The processed leathers show physical and tactile prop-
erties similar or comparable to those of conventionally processed leathers.
The cross-section view of tanned cowhides through a scanning electron mi-
croscopy shows that the fiber bundles are not modified due to the change in
a multistep process to an enzyme-driven three step tanning process. It has
also been demonstrated that the biodriven three-step tanning is economically
viable and attractive, if commercial enzyme products are used. Enzymatic
processing when synergized with compact chrome tanning results in reduc-
tion of COD, TS, and chromium emissions into the environment by 80%,
85%, and 80%, respectively, compared to traditional processing. It cuts the
amount of solid sludge that dehairing and fiber opening generate by 91%. It is
also interesting to note that the enzyme treatment softens the matrix, thereby
increasing the area of the final leather. This results in nearly US$100 savings
for processing 1 ton skins/hides, because leather is sold on an area basis. Re-
cently, there is also an approach to use plant-based polyphenol compounds
for tanning instead of chromium at pH 8.0 (Saravanabhavan et al., 2004a) in
the three-step tanning process (Saravanabhavan et al., 2004b).
VII. SUMMARY AND CONCLUSIONS
Leather processing involves cleaning of the skins or hides to remove un-

wanted materials, followed by preparing the stock for chrome tanning and
subsequently tanning using BCS to stabilize the raw material against micro-
bial degradation. The conventional cleaning processes (liming–reliming pro-
cesses) lead to the generation of substantial amounts of sulfide, lime sludge,
and BOD. The conventional preparatory process for chrome tanning, namely,
pickling, which involves the use of sodium chloride and sulfuric acid, gen-
erates more amounts of dissolved solids. The chrome tanning process by
virtue of its poor exhaustion behavior emanates liquor containing chromium
at levels 1000-fold higher than the norm specified by pollution control
authorities.
A critical review on the conventional leather processes and the princi-
ples behind each steps reveals that the bulk of the pollution rests in pretan-
ning and tanning processes. Nevertheless, posttanning and finishing steps do
pollute the environment by way of effluent as well as volatile organic com-
pounds air emissions. State-of-the art technologies comprising both in-plant
and end-of-pipe treatment solutions have been reviewed for their techni-
cal suitability and commercial feasibility. It turned out that a combination of
both technologies is essential for protecting the leather industry from envi-
ronmental consequences. The sustainability of the leather industry, however,
relies solely on revamping the leather process sequence, avoiding do–undo
methodologies based on first principles. An account of such developments
has been catalogued and their technical features and practicability have been
reviewed. Preliminary results show that the process schemes are capable of
lowering environmental threats drastically. Further studies and commercial
follow-up, however, would validate the developments.
REFERENCES
Aloy, M., Mermet, R., and Sanejouand, J. Biomethanization of tannery waste: An

industrial experiment, J. Am. Leather Chem. Assoc. 84, 97–109, 1989.
Anderson, R.A., Cheng, N.Z., Bryden, N.A., Polansky, M.M., Cheng, N.P., and Chi,
J.M. Elevated intakes of supplemental chromium improve glucose and insulin
variables in individuals with type 2 diabetes, Diabetes 46, 1786–1791, 1997.
Aravindhan, R., Madhan, B., Rao, J.R., Nair, B.U., and Ramasami, T. Bioaccumulation
of chromium from tannery wastewater: An approach for chrome recovery and
reuse, Environ. Sci. Technol. 38, 300–306, 2004.
Aravindhan, R., Saravanabhavan, S., Thanikaivelan, P., Chandrasekaran, B., Rao, J.R.,
and Nair, B.U. A bio-driven lime and pickle free tanning paves way for greener
garment leather production, J. Am. Leather Chem. Assoc. 99, 53–66, 2004.
Arslan, P., Beltrame, M., and Tomasi, A. Intracellular chromium reduction, Biochim.
Biophys. Acta 931, 10–15, 1987.
Bailey, D.G. Preservation of cattle hides with potassium chloride, J. Am. Leather
Chem. Assoc. 90, 13–20, 1995a.
Bailey, D.G. Ecological concepts in rawhide conservation (preservation), World
Leather 8(3), 43–47, 1995b.
Bailey, D.G. Gamma radiation preservation on cattle hides. A new twist on an old
story, J. Am. Leather Chem. Assoc. 94, 259–266, 1999.
Bailey, D.G., and Haas, M.J. Electron beam irradiation of fresh hides, salted hides
and leather. Microbial control and effect of physical properties, J. Am. Leather
Chem. Assoc. 83, 46–55, 1988.
Bailey, D.G., DiMaio, G.L., Gehring, A.G., and Ross, G.D. Electron beam irradiation
preservation of cattle hides in a commercial-scale demonstration, J. Am. Leather
Chem. Assoc. 96, 382–392, 2001.
Bailey, D.G., Hopkins, W.J., Taylor, H.H., Filachione, E.M., and Koeppen, R.G. Preser-
vation of hides with sulfite III. Statistical evaluation of shoe upper leather pre-
pared in a matched side study of brine cured and sulfite–acetic acid treated cow
hides, J. Am. Leather Chem. Assoc. 71, 400–408, 1976.
Bailey, D.G., Tunick, M.H., and Kuzma, M.A. Effect of sulfide, chromium and phos-
phate ions on methane production by an anaerobic sludge acclamatised of tan-
nery beamhouse effluent, Proceedings of the 14th Industrial Waste Mid Atlantic
Conference, 1982.
Balamurugan, K., Vasant, C., Rajaram, R., and Ramasami, T. Hydroxopentammine
chromium(III) promoted phosphorylation of bovine serum albumin: Its potential
implications in understanding biotoxicity of chromium, Biochim. Biophys. Acta
1427, 357–366, 1999.
Balasubramani, M., Babu, M., and Sehgal, P.K. In vitro biocompatibility test for
collagen-based dressings, In Vitro Cell Dev. Biol. Anim. 33, 223–227, 1997.
Barrett, J.C. Short-term preservation of hides in Zimbabwe, J. Soc. Leather Technol.

Chem. 70, 83–89, 1986.
Bartlett, R.J., and James, B.R. Oxidation of chromium in soils, J. Environ. Qual. 8,
31–35, 1979.
Bartlett, R.J., and Kimble, J.M. Behaviour of chromium in soils: II. Hexavalent forms,
J. Environ. Qual. 5, 383–385, 1976.
Bartlett, R.J. Chromium cycling in soils and water: Links, gaps and methods, Environ.
Health Perspect. 92, 17–24, 1991.
BASF, Information on legislation and consumer protection, World Leather
August/September, 65–67, 1998.
Beyersmann, D., and Koster, A. On the role of trivalent chromium in chromium
genotoxicity, Toxicol. Environ. Chem. 14, 11–22, 1987.
Bienkiewicz, K. Physical Chemistry of Leather Making, Robert E. Krieger, Malabar,
FL, 1983.
Biles, J., DiCandilo, N., Gehlhaus, P., and Prentiss, W.C. Viscosity parameters of
finishes applied by roll and precision coating, J. Am. Leather Chem. Assoc. 80,
284–292, 1985.
Biles, J. Parameters in the application of water based topcoats, J. Am. Leather Chem.
Assoc. 85, 163–178, 1990.
Borge, J.O. Leather processing for area yield, J. Soc. Leather Technol. Chem. 70,
111–113, 1986.
Bose, S.M. Enzymatic unhairing, Leather Sci. 2, 140–144, 1955.
Brady, D., Duncan, J.R., and Russell, A.E. A model for proteolytic depilation of skins,
J. Am. Leather Chem. Assoc. 85, 334–342, 1990.
Buljan, J. Pollution limits for discharge of tannery effluents in water bodies and
sewers, World Leather November, 65–68, 1996.
Buljan, J., Sahasranaman, A., Sampathkumar, S., Mani, A., and Venkatesh, A. Accel-
erated evaporation of saline streams in solar pans, Proceedings of the XXVI
IULTCS Congress, Cape Town, 2001.
Burrows, G.H. Clean technology in the processing of leather, Proceedings of the
XXVI IULTCS Congress, Cape Town, 2001.
Cantera, C.S. The hair-saving unhairing process, World Leather 11(7), 29,
1998.
Cantera, C.S., Angelinetti, A.R., Altobelli, G., and Gaita, G. Hair saving enzyme as-
sisted unhairing: Influence of enzymatic products upon final leather quality, J.
Soc. Leather Technol. Chem. 80, 83–86, 1996.
Chakravorthy, H.P., and Nursten, H.E. Uncommon inorganic tannages, J. Soc. Leather
Technol. Chem. 42, 2–22, 1958.
Chandrababu, N.K., Rao, J.R., Rao, P.S., Ramesh, R., Babu, M.S., Ramasami, T.,
Langerwerf, J.S.A., Covington, A.D., and Walker, W.P. Low waste closed loop
chrome tanning method, Proceedings of the 30th LERIG, Chennai, 23–36,
1995.
Chandrasekaran, B. An approach towards better exhaustion chrome in tanning,
Leather Sci. 34, 91–102, 1987.
Chandrasekaran, B., Rao, J.R., Prasad, B.G.S., and Nair, B.U. Management of
chromium wastes in tanneries, J. Ind. Assoc. Environ. Manage. 16, 168–173,
1989.
Chandrasekaran, B., Rao, J.R., Sreeram, K.J., Nair, B.U., and Ramasami, T. Chrome
tanning: State-of-art on the material composition and characterisation, J. Sci. Ind.
Res. 58, 1–10, 1999.
Cluthe, C.E., Desiderio, F.A., and Prentiss, W.C. Aqueous topcoats for leather, J. Am.
Leather Chem. Assoc. 73, 22–29, 1978.
Corning, D.R., Cory, N.J., Nott, S.W., and Sykes, R.L. The impact of air pollution
controls on tannery operations, J. Soc. Leather Technol. Chem. 75, 183–189,
1991.
Costa, M. DNA–protein complexes induced by chromate and other carcinogens,
Environ. Health Perspect. 92, 45–52, 1991.
Covington, A.D. The use of aluminium(III) to improve chrome tannage, J. Soc.
Leather Technol. Chem. 70, 33–38, 1986.
Covington, A.D. Modern tanning chemistry, Chem. Soc. Rev. 26, 111–126, 1997a.
Covington, A.D. Chrome management, Proceedings of the 32nd LERIG, Chennai,
97–128, 1997b.
Covington, A.D. New tannages for the new millennium, J. Am. Leather Chem. Assoc.
93, 168–182, 1998.
Covington, A.D., and Shi, B. High stability organic tanning using plant polyphenols.
Part 1. The interactions between vegetable tannins and aldehydic cross linkers,
J. Soc. Leather Technol. Chem. 82, 64–71, 1998.
Covington, A.D., Lambard, G.S., and Pennington, M. An investigation of titanium(III)
as a tanning agent, J. Soc. Leather Technol. Chem. 82, 78–80, 1998.
Covington, A.D., Sykes, R.L., Barlow, J.R., and White, E.T. A practical chrome re-
covery system using magnesium oxide, J. Soc. Leather Technol. Chem. 67, 5–12,
1983.
Cranston, R.W., Davis, M.H., and Scroggie, J.G. Development of the Sirolime unhair-
ing process, J. Am. Leather Chem. Assoc. 81, 347–355, 1986a.
Cranston, R.W., Davis, M.H., and Scroggie, J.G. Practical considerations on the
Sirolime process, J. Soc. Leather Technol. Chem. 70, 50–55, 1986b.
Cuq, M.H., and Delmas, M. The Cr.A.B. process: A new ecological process for the
transformation of pickled hides into leather Part 3: Fatliquoring, J. Soc. Leather
Technol. Chem. 83, 210–214, 1999.
Daniels, R. Overview: Avoiding salts, World Leather 10(7), 41, 1997.
Daniels, R.P. Working with nature: reed bed technology, World Leather 8(5), 41–45,
1995.
Dartsch, P.C., Kimmel, R., Schmahl, F.W., and Germann, H.P. Nephrotoxic and
hepatotoxic effects of a chromium(VI) compound in comparison to a basic
chromium(III) tanning agent, World Leather May, 66–70, 1998.
Dasgupta, S. Minimising the environmental impact of chrome tanning: The ThruBlu
process, J. Soc. Leather Technol. Chem. 82, 15–21, 1998.
Davis, M.H., and Scroggie, J.G. Investigation of commercial chrome tanning
systems—Part IV, Recycling of chrome liquors and their use as a basis for pick-
ling, J. Soc. Leather Technol. Chem. 57, 81–83, 1973.
Davis, M.H., and Scroggie, J.G. Theory and practice of direct chrome liquor recycling,
Das Leder 31, 1–8, 1980.
Dederle, T., Rehak, P., Svoboda, V., and Ludvik, J. Koželužské operace v mokré dilně
VI. Odvápňovánı́ a mořenı́, Kozarstvi 34, 45–50, 1984.
D’Souza, A., and Vedarajan, R. Pollution control in beamhouse operation, Proceed-

ings of the 32nd LERIG, Chennai, 81–90, 1997.
Deep, A., Malik, P., Gupta, B., and Tandon, S.N. Efficient trivalent bath for the re-
covery of chromium, Plat. Surf. Finish. March, 76–77, 2001.
Deselinicu, V., Albu, L., Chiria, L., Bucevsehi, M.D., and Colt, M. New products for en-
vironmentally friendly leather finishing, Proceedings of XXIV IULTCS Congress,
London, 323–327, 1997.
Dhar, S.C. Production and application of enzymes in the pretanning processes of
leather manufacture, Leather Sci. 21, 39–47, 1974.
Dix, J.P. Chemical developments leading to cleaner production. Part 1:
Beamhouse and chrome tanning operations, World Leather May, 42–45,
2000.
Fadel, A.A., and Speranza, M. The hair recovery liming system and its advantages,
Leather Manuf. 113(9), 11–16, 1995.
FAO, World Statistical Compendium for Raw Hides and Skins, Leather and Leather
Footwear 1982–2000, Food and Agriculture Organization of the United Nations,
Rome, 2001.
Fathima, N.N., Rao, J.R., and Nair, B.U. Chromium(VI) formation: Thermal studies
on chrome salt and chrome tanned hide powder, J. Am. Leather Chem. Assoc.
96, 444–449, 2001.
Fathima, N.N., Madhan, B., Rao, J.R., and Nair, B.U. Mixed metal tanning using
chrome–zinc–silica: A new chrome-saver approach, J. Am. Leather Chem. Assoc.
98, 139–146, 2003.
Fathima, N.N., Saravanabhavan, S., Rao, J.R., and Nair, B.U. An eco-benign tan-
ning system using aluminium, tannic acid and silica combination, J. Am. Leather
Chem. Assoc. 99, 73–81, 2004.
Fava, A., Iliceto, A., and Camera, E. Kinetics of the thiol–disulfide exchange, J. Am.
Chem. Soc. 79, 833–838, 1957.
Feigel, T. The hair-save liming process: A tool for environment friendly manufacture,
World Leather 11(7), 31–32, 1998a.
Feigel, T. Use of enzymes in the beamhouse—Possibilities and limitations, World
Leather May, 54–59, 1998b.
France, H.G. Recycle of tan liquor from organic acid pickle tan process, J. Am. Leather
Chem. Assoc. 70, 206–219, 1975.
Frendrup, W. UNEP Cleaner Production Industrial Sector Guide Leather Production,
Taastrup, 1996.
Gauglhofer, J. Environmental aspects of tanning with chromium, J. Soc. Leather Tech-
nol. Chem. 70, 11–13, 1986.
Gayatri, R., Rajaram, R., Nair, B.U., Chandrasekaran, F., and Ramasami, T. Chromium-
induced molecular assemblies and long range ordering in collagenous tissues: A
conceptual insight into chromium tanning, Proc. Indian Acad. Sci. 111, 133–145,
1999.
Germann, H.P. Chrome tannage from the viewpoint of ecology, J. Soc. Leather Tech-
nol. Chem. 79, 82–85, 1995.
Germann, H.P. The ecology of leather production—Present state and development
trends, in Science and Technology for Leather Into the Next Millennium, Tata
McGraw-Hill, New Delhi, p. 283, 1999.
Gill, C.J. Low VOC topcoats for the leather industry, J. Am. Leather Chem. Assoc. 86,
42–48, 1991.
Gill, C. Improving the performance of aqueous topcoats, J. Am. Leather Chem. Assoc.
88, 197–206, 1993.
Gill, C.J. Aromatic carbodiimides: A new class of cross linkers for aqueous leather
coatings, Proceedings of the XXIII IULTCS Congress, Germany, 1995.
Gish, A. Leather board, a practical use of tannery offal, J. Am. Leather Chem. Assoc.
95, 43–47, 2000.
Goddard, D.R., and Michaelis, L. A study on keratin, J. Biol. Chem. 106, 605–614,
1934.
Govindaraju, K., Ramasami, T., and Ramaswamy, D. Chromium(III)-insulin deriva-
tives and their implication in glucose metabolism, J. Inorg. Biochem. 35, 137–147,
1989.
Green, G.H. Unhairing by means of enzymes, J. Soc. Leather Technol. Chem. 36,
127–134, 1952.
Greif, M. Environmental issues in leather finishing, J. Am. Leather Chem. Assoc. 85,
36–41, 1990.
Gupta, B., Deep, A., and Tandon, S.N. Recovery of chromium and nickel from in-
dustrial waste, Ind. Eng. Chem. Res. 41, 2948–2952, 2002.
Hanson, E.L. Volatile organic compound (VOC) emissions—Recycling requirements
and control options, J. Am. Leather Chem. Assoc. 77, 35–37, 1982.
Hauber, C. Preservation of raw and wet blue hides and skins, in Unit 1. Background
Information and Cleaner Technologies in Raw Material Preservation and in the
Beamhouse Processes, UNIDO, pp. 206–239, 1998.
Hay, P.M. Safety and handling of dyes and pigments, J. Am. Leather Chem. Assoc. 74,
254–258, 1979.
Healy, J.B., Jr., and Young, L.Y. Catechol and phenol degradation by a methanogenic
population of bacteria, Appl. Environ. Microbiol. 35, 216–218, 1978.
Heidemann, E., and Harenberg, O. Ein sehr schnelles, a bwassėrarames
Äscherverfahren, Das Leder 23, 85–96, 1972.
Heidemann, E., and Smidek, V.J. Entwicklung von Sulfidfreien und sulfidarmen En-
thaarungen, Das Leder 38, 48–57, 1987.
Heidemann, E. Fundamentals of Leather Manufacturing, Eduard Roether KG, Darm-
stadt, 1993.
Herfeld, H., and Schubert, B. The influence of swelling and plumpness of animal
hides in the liming process on the properties of leather, J. Am. Leather Chem.
Assoc. 64, 198–226, 1969.
Herfeld, H., and Schubert, B. Untersuchungen über die quelling und prallheit
tierischer haut in säurelösungen, Das Leder 26, 117–128, 1975.
Herlihy, T.E., and Billings, W.H. An environmental assessment and feasibility study of
using vegetable tannery biosolids as soil conditioners/plant growth supplement,
Hetzel, L.V., Somerville, I.C., and Cares, C.J. The use of dimethylamine in hair-
destroying processes, J. Am. Leather Chem. Assoc. 60, 364–379, 1965.
Hetzel, L.V., Somerville, I.C., and Cares, C.J. Further studies on dimethylamine
in hair-destroying processes, J. Am. Leather Chem. Assoc. 61, 536–547,
1966.
Huber, C.F., and Satyendra, M.D. Toxicity of tannery effluent—The next concern, J.
Am. Leather Chem. Assoc. 85, 276–285, 1990.
Huc, A. Collagen biomaterials. Characteristics and applications, J. Am. Leather Chem.
Assoc. 80, 195–212, 1985.
ITC, Trade analysis system on personal computer 1994–1998 SITC3, International
Trade Centre UNCTAD/WTO, United Nations Statistics Division, Geneva, 1999.
Jennette, K.W. Chromate metabolism in liver microsomes, Biol. Trace Elem. Res. 1,
55–62, 1979.
Jones, H.W., Cordon, T.C., and Windus, W. Light leather from enzyme unhaired hides,
Kamal, A.M.S., Nomura, Y., Ishii, Y., and Shirai, K. Properties of bovine hair keratins
solubilized with thioglycolate, J. Am. Leather Chem. Assoc. 93, 272–282, 1998.
Kanagaraj, J., Chandrababu, N.K., Sadulla, S., Rajkumar, G.S., Visalakshi, V., and
Chandrakumar, N. A new approach to less-salt preservation of raw skin/hide, J.
Kanthimathi, M., Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. A process
for the preparation of a novel synthetic aluminium tanning agent, Indian Patent
Application No. 88/DEL/2002, 2002.
Katz, S.A. The analytical biochemistry of chromium, Environ. Health Perspect. 92,
13–16, 1991.
Kaul, S.N., and Ravindranath, E. Waste treatment: Experience and outlook, Interna-
tional consultation meeting on technology and environmental upgradation in
leather sector, New Delhi, 1999.
Khwaja, A.R., Singh, R., and Tandon, S.N. Recovery of Cr(III) from tannery spent
chrome liquor for reuse, J. Environ. Eng. 126, 307–312, 2000a.
Khwaja, A.R., Singh, R., and Tandon, S.N. Mono(2-ethylhexyl) phosphoric acid as
an extractant for Cr(III) and its application to industrial waste, Sep. Sci. Technol.
35, 447–455, 2000b.
Komanowsky, M., and Senske, G.E. Reduction of tannery waste volume through
countercurrent reuse of process streams, J. Am. Leather Chem. Assoc. 77, 206–
221, 1982.
Komanowsky, M. Microwave drying of hides under vaccum, J. Am. Leather Chem.
Assoc. 95, 179–188, 2000.
Kumar, K.V., Sai, K.P., and Babu, M. Application of frog (Rana tigerina daudin) skin
collagen as a novel substrate in cell culture, J. Biomed. Mater. Res. 61, 197–202,
2002.
Lach, D., Knoll, I., and Fischer, K. Waterborne coatings based on different film form-
ing polymers, J. Am. Leather Chem. Assoc. 83, 87–94, 1988.
Langerwerf, J.S.A. Philosophies on a sustainable leather world, in Science and Tech-
nology for Leather Into the Next Millennium, Tata McGraw-Hill, New Delhi,
389–409, 1999.
Langerwerf, J.S.A., and Chandrababu, N.K. Cleaner production: Options and di-
rections, International consultation meeting on technology and environmental
upgradation in leather sector, New Delhi, 1999.
Legesse, W., Thanikaivelan, P., Rao, J.R., and Nair, B.U. Underlying principles in
chrome tanning: Part 1. Conceptual designing of pickle-less tanning, J. Am.
Leonard, A., and Lauwerys, R.R. Carcinogenicity and mutagenicity of chromium,

Mutat. Res. 76, 227–239, 1980.
Löbig, W. Foam systems—A novel type of finishing technology, J. Soc. Leather Tech-
nol. Chem. 81, 1–4, 1997.
Luck, W. Chrome tanning processes with particularly good exhaustion, J. Am. Leather
Chem. Assoc. 75, 378–388, 1980.
Ludvik, J., and Orlita, A. Vliv zpu̇sobu konzervace ku̇žena odpadnı́ vody, Kozarstvi
36, 83–87, 1986.
Ludvik, J. Study on the scope for decrease of pollution load in leather processing,
UNIDO Report, March, 1997.
Madhan, B., Rao, J.R., and Nair, B.U. Tanning salts based on mixed metal complexes
of aluminium and zinc, J. Am. Leather Chem. Assoc. 96, 343–349, 2001a.
Madhan, B., Jeyakumar, R., Muralidharan, C., and Gnanasekaran, C.S. Improvements
in vegetable tanning—Can acrylics be co-tanning agents, J. Am. Leather Chem.
Assoc. 96, 120–126, 2001b.
Madhan, B., Fathima, N.N., Rao, J.R., and Nair, B.U. A new chromium–zinc tanning
agent: A viable option for less chrome technology, J. Am. Leather Chem. Assoc.
97, 189–196, 2002.
Madhan, B., Sundararajan, A., Rao, J.R., and Nair, B.U. Studies on tanning with zir-
conium oxychloride: Part II, Development of a versatile tanning system, J. Am.
Mance, C. Lime splitting—A case study, J. Soc. Leather Technol. Chem. 84, 6–19, 2000.
Mannouch, S. A comparison of spray suns, World Leather 15(3), 49–53, 2002.
McCleskey, T.M., Foreman, T.M., Hallman, E.E., Burns, C.J., and Sauer, N.N. Ap-
proaching zero discharge in uranium processing: Photochemical reduction of
uranyl, Environ. Sci. Technol. 35, 547–551, 2001.
Mertz, W. Chromium research from a distance: From 1959 to 1980, J. Am. Coll. Nutr.
17, 544–547, 1998.
Miller, A.T. Current and future uses of limed hide collagen in the food industry, J.
Money, C.A., and Adminis, U. Recycling of lime-sulfide unhairing liquors I. Small-
scale trials, J. Soc. Leather Technol. Chem. 58, 35–40, 1974.
Money, C.A., and Scroggie, J.G. Lysosomal hair loosening of hides, J. Soc. Leather
Technol. Chem. 55, 333–343, 1971.
Money, C.A. Short term preservation of hides. II The use of zinc chloride or calcium
hypochlorite as alternatives to sodium chlorite, J. Am. Leather Chem. Assoc. 69,
112–120, 1974.
Money, C.A. Unhairing and dewooling—Requirements for quality and the environ-
ment, J. Soc. Leather Technol. Chem. 80, 175–186, 1996.
Montgomery, K.C. Alternatives to chromium tanning—Part III: Effect of organic acid
anions on aluminium sulfate tannage of collagen, J. Soc. Leather Technol. Chem.
71, 59–67, 1987.
Morera, J.M., Bartoli, E., Borras, M.D., and Marsal, A. Study on an unhairing process
with hydrogen peroxide and amines, Proceedings of the XXIV IULTCS Congress,
London, 436–440, 1997.
Munz, K.H., and Toifl, G. Entkalken mit Kohlendioxid (Teil 3), Das Leder 43, 41–46,
1992.
Munz, K.H., Sundar, V.J., Muralidharan, C., and Parthasarathi, K. Chrome tannage
without pickling, Das Leder 48, 128–133, 1997.
Muralidharan, C., Sundar, V.J., and Rao, V.S.S. Two stage tanning—A new ap-
proach for chrome management, J. Am. Leather Chem. Assoc. 96, 61–66,
2001.
O’Flaherty, F., Roddy, W.T., and Lollar, R.M. Preparation for tannage, in The Chemistry
and Technology of Leather, Vol. I, Krieger, Malabar, FL, 1978.
Okamura, H., and Shirai, K. Basic studies on the manufacture of leather board
from chrome collagen fiber, J. Am. Leather Chem. Assoc. 67, 148–162,
1972.
Page, C.T., and Fennen, J. The challenge of manufacturing leather dyes today, J. Soc.
Palon, P., and Marsal, A. Auxiliary agents with non-swelling capacity used in pick-
ling/tanning processes. Part I, J. Soc. Leather Technol. Chem. 86, 139–142, 2002.
Parks, B.E. Fuel value of spent hemlock bark, J. Am. Leather Chem. Assoc. 11, 361–
364, 1916.
Parthasarathy, K. Water management in tanneries, International conference on water
management—Water 95, Madras, 1995.
Pauli, G. Zero emissions: The ultimate goal of cleaner production, J. Cleaner Prodn.
5, 109–113, 1997.
Pilawski, S., and Felicjaniak, B. Die einwirkung von pankreasenzymen auf schwein-
shaute im enthaarungsprozeß, Das Leder 27, 102–109, 1976.
Pojer, P.M., and Huynh, C.P. A salt free pickling regime for hides and skins, in Science
and Technology for Leather Into the Next Millennium, Tata McGraw-Hill, New
Delhi, 308–313, 1999.
Post, D. Die quellung von kalbsblobe im sauren Ph-gebiet unter mitwirkung ver-
schiedener zusatze (Ein beitrag zur gesteuerten quellung im pickel), Das Leder
15, 69–77, 1964.
Prasad, B.G.S., and Nair, B.U. Recovery and recycling of regenerated chromium from
spent chrome liquor, Indian. J. Environ. Health 36, 267–271, 1994.
Prasad, B.G.S., Chandrasekaran, B., Rao, J.R., Chandrababu, N.K., Kanthimathi, M.,
and Ramasami, T. Prospects for chromium management in tanneries: A critical
review, Leather Sci. 34, 132–148, 1987.
Prasad, B.G.S., Rao, B.V.S.G., Madhavakrishna, W., and Sastry, C.A. Studies on
the treatment of tannery wastewater—Part I Laboratory studies for setting up
demonstration treatment unit, Leather Sci. 28, 221–229, 1981.
Prentiss, W.C., and Prasad, I.V. Improved chrome utilisation in chrome tanning, J.
Pulles, F., and Domanjko, D. Reverse roll coating of splits and side leather,
Pulles, F.A.P. The impact of aqueous polyurethanes on leather finishing technology,
Püntener, A.G. Risk assessment of leather dyestuffs, J. Soc. Leather Technol. Chem.
82, 1–4, 1998.
Purushotham, H., Chandrababu, N.K., Khanna, J.K., and Raghavan, K.V. CO2
delimining—An environmentally friendly option for Indian tanneries, J. Soc.
Puvanakrishnan, R., and Dhar, S.C. Recent advances in the enzymatic depilation of
hides and skins, Leather Sci. 33, 177–191, 1986.
Rajagopalan, N., and Thimmapuram, P. Innovative technologies for a cleaner envi-
ronment: Opportunities in the leather industry, Proceedings of the 32nd LERIG,
Chennai, 62–85, 1997.
Rajamani, S., and Viswanathan, M. Desalting of hides and skins, in Unit 1. Back-
ground Information and Cleaner Technologies in Raw Material Preservation
and in the Beamhouse Processes, UNIDO, 255–275, 1998.
Rajamani, S. Feasible options for handling dissolved solids problems in tanneries,
Proceedings of the 32nd LERIG, Chennai, 14–20, 1997.
Rajamani, S., Suthanthararajan, R., Ravindranath, E., Mulder, A., van Groenestijn, J.W.,
and Langerwerf, J.S.A. Treatment of tannery wastewater using upflow anaerobic
sludge blanket system (UASB), Proceedings of the 30th LERIG, Chennai, 57–66,
1995.
Rajaram, R., Nair, B.U., and Ramasami, T. Chromium(III) induced abnormalities in
human lymphocyte cell proliferation: Evidence for apoptosis, Biochem. Biophys.
Res. Commun. 210, 434–440, 1995.
Ramamurthy, G., Sehgal, P.K., and Kumar, M. Improved uptake of basic chromium
salts in tanning operations using keratin hydrolysates, J. Soc. Leather Technol.
Chem. 73, 168–171, 1989.
Ramasami, T., and Prasad, B.G.S. Environmental aspects of leather processing, Pro-
ceedings of the LEXPO XV, Calcutta, 43–71, 1991.
Ramasami, T., and Sahasranaman, A. Biomethanation of fleshings and sludge from
tannery and effluent treatment plants, World Leather 13(7), 38, 2000.
Ramasami, T. Approach towards a unified theory for tanning: Wilsons dream, J. Am.
Ramasami, T. Biological Nitrogen Fixation, Popular lecture sponsored by DBT de-
livered at CLRI, Madras, 1993.
Ramasami, T. Greening of chrome tanning in Indian leather industry, ILIFO J. Cleaner
Tanning, 1(2), 12–14, 1996.
Ramasami, T., Rajamani, S., and Rao, J.R. Pollution control in leather industry: Emerg-
ing technological options, International symposium on surface and colloid sci-
ence and its relevance to soil pollution, Madras, 1994.
Ramasami, T., Rao, J.R., Chandrababu, N.K., Parthasarathi, K., Rao, P.G., Saravanan,
P., Gayatri, R., and Sreeram, K.J. Beamhouse and tanning operations:
Process chemistry revisited, J. Soc. Leather Technol. Chem. 83, 39–45,
1999a.
Ramasami, T., Sreeram, K.J., and Gayatri, R. Sources of pollution in tanneries, miti-
gation and case studies, in Unit 1. Legal Requirements, Manual on Design, Op-
eration and Maintenance of Tannery Effluent Treatment Plants, RePO–UNIDO,
Chennai, 20–33, 1999b.
Ramasami, T., Rao, J.R., Chandrasekaran, B., and Chandrababu, N.K. Leather chem-
icals: Emerging trends, Leather Age August, 23–30, 1999c.
Ramasami, T., Sreeram, K.J., and Gayatri, R. Emerging leather processing strategies
for waste minimisation, in Unit 1. Background Information and Cleaner Tech-
nologies in Raw Material Preservation and in the Beamhouse Processes, UNIDO,
183–197, 1998.
Ranganathan, T.S., and Reed, R. Studies on zirconium tannage, J. Soc. Leather Technol.
Chem. 42, 351–360, 1958.
Rao, J.R. Recovery and reuse techniques for chromium salts in tanneries, Leather Sci.
34, 201–212, 1987.
Rao, J.R. Studies on the approaches to the better management of chromium (III) salts
as tanning agents, PhD thesis, Anna University, Chennai, 1991.
Rao, J.R., and Ramasami, T. Waste management in leather processing: A case of
chromium, International Conference on Industrial Pollution and Control Tech-
nologies (ICIPACT-97), Hyderabad, 1997.
Rao, J.R., Chandrasekaran, B., and Ramasami, T. High exhaust chrome tanning sys-
tems, Proceedings of the 27th LERIG, Madras, 75–101, 1992.
Rao, J.R., Venba, R., Nair, B.U. Suthanthararajan, R., Rajamani, S., Ramasami, T., and
Langerwerf, J.S.A. Chromium reuse, Proceedings of the 30th LERIG, Chennai,
37–56, 1995.
Rao, J.R., Chandrasekaran, B., Subramaniam, V., Nair, B.U., and Ramasami, T.
Physico-chemical and structural studies on leathers tanned using high exhaust
basic chromium sulfate salt, J. Am. Leather Chem. Assoc. 93, 139–147, 1998.
Rao, J.R., Nair, B.U., and Ramasami, T. Isolation and characterization of low affinity
chromium(III) complex in chrome tanning solutions. J. Soc. Leather Technol.
Chem. 81, 234–238, 1997.
Rao, J.R., Prasad, B.G.S., Narasimhan, V., Ramasami, T., Shah, P.R., and Khan, A.A.
Electrodialysis in the recovery and reuse of chromium in industrial effluents, J.
Membrane Sci. 46, 215–224, 1989.
Rao, J.R, Sreeram, K.J., Nair, B.U., and Ramasami, T. Some strategies towards mitiga-
tion of pollution from tanneries: A review, in Advances in Wastewater Treatment
Technologies, Goel, P.K., ed., Technoscience Publications, Jaipur, 135–152, 1999.
Rao, J.R., Ramasami, T., Sahasranaman, A., Hashim, M.M., and Ahmed, M.R. Do-
ecology solutions for leather sector: Technology initiatives, Regional IULTCS
Conference of South and South East Asian Countries on Leather and Allied
Technologies, Kolkata, 2001.
Rao, J.R., Thanikaivelan, P., Sreeram, K.J., and Nair, B.U. Green route for the disposal
of chrome shavings (chromium containing solid waste) in tanning industry,
Environ. Sci. Technol. 36, 1372–1376, 2002a.
Rao, J.R., Thanikaivelan, P., Malathi, J., Rajaram, R., and Nair, B.U. Development of
natural colors in Cr–Fe tanned garment leathers, J. Soc. Leather Technol. Chem.
86, 106–111, 2002b.
Rao, J.R., Chandrasekaran, B., Nair, B.U., and Ramasami, T. Eco-benign management
options for cleaner chrome tanning, J. Sci. Ind. Res. 61, 912–926, 2002c.
Rao, J.R., Chandrababu, N.K., Muralidharan, C., Nair, B.U., Rao, P.G., and Ramasami,
T. Recouping the wastewater: A way forward for cleaner leather processing, J.
Clean. Prod. 11, 591–599, 2003.
Rao, J.R., Thanikaivelan, P., Sreeram, K.J., and Nair, B.U. Tanning studies with basic
chromium sulfate prepared using chrome shavings as a reductant: A call for
“wealth from waste” approach to the tanning industry, J. Am. Leather Chem.
Assoc. 99, 170–176, 2004.
Röhm, O. Verfahren zum Beizen von Häuten, German Patent DE 200,519, July 21,
1910.
Rose, C. Ranganayaki, M.D., Srinivasan, T.S., Ramakrishnan, S., Seethalaksmi, S.,

and Sastry, T.P. A process for the preparation of a parchment like material,
Indian Patent Application No. 300/DEL/2001, 2001.
Rosenbusch, K. Neuere erfahrungen bei der oxydativ enthaarung, Das Leder 16,
237–248, 1965.
Sahasranaman, A., and Buljan, J. Environmental management in Indian tanneries,
Proceedings of the 34th LERIG, Chennai, 34–44, 2000.
Sai, K.P., Reddy, P.N., and Babu, M. Investigations on wound healing by using am-
phibian skin, Indian J. Exp. Biol. 33, 673–676, 1995.
Saravanabhavan, S., Aravindhan, R., Thanikaivelan, P., Rao, J.R., and Nair, B.U. Green
solution for tannery pollution: Effect of enzyme based lime-free unhairing and
fibre opening in combination with pickle-free chrome tanning, Green Chem. 5,
707–714, 2003a.
Saravanabhavan, S., Aravindhan, R., Thanikaivelan, P., Rao, J.R., Chandrasekaran, B.,
and Nair, B.U. An integrated eco-friendly tanning method for the manufacture
of upper leathers from goatskins, J. Soc. Leather Technol. Chem. 87, 149–158,
2003b.
Saravanabhavan, S., Thanikaivelan, P., Rao, J.R., and Nair, B.U. Studies on the de-
velopment of pickle-less vegetable tanning, J. Am. Leather Chem. Assoc. 99,
281–288, 2004a.
Saravanabhavan, S., Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. Natu-
ral leathers from natural materials: Progressing toward a new arena in leather
processing, Environ. Sci. Technol. 38, 871–879, 2004b.
Scheijgrond, J.W. A legal perspective on sludge, World Leather 11(7), 22–27, 1998.
Schlosser, L., Keller, W., Hein, A., and Heidemann, E. The utilisation of a Lacto-
bacillus culture in the beamhouse, J. Soc. Leather Technol. Chem. 70, 163–168,
1986.
Sehgal, P.K., Ramamurthy, G., Muralidharan, C., and Gupta, K.B. Unhairing of goat
skins by an alternative non-enzymatic and sulfide free process, J. Soc. Leather
Technol. Chem. 80, 91–92, 1996.
Sekaran, G., Jayanthi, S., Shanmugasundaram, K.A., Mariappan, M., and Ramasami, T.
An integrated biological and chemical oxidative system for treatment of tannery
effluent: A review, in Advances in Wastewater Treatment Technologies, Goel,
P.K., ed., Technoscience Publications, Jaipur, India, 153–163, 1999.
Selvarangan, R., and Nayudamma, Y. Alum tannages: Part II, Tanning action of basic
aluminium sulphate, Leather Sci. 11, 431–439, 1964.
Selvarangan, R., and Shanmugasundaram, K. Saltless curing and preservation of hides
and skins, Leather Sci. 31, 241, 1984.
Sharphouse, J.H. Leather Technicians Handbook, Vernon Lock Ltd., London, 1983.
Shrewsbury, C. Biotechnology for improved product quality, World Leather February,
40–42, 2002.
Shrivastava, H.Y., and Nair, B.U. Cleavage of human orosomucoid by a chromium(V)
species: Relevance in biotoxicity of chromium, Biochem. Biophys. Res. Commun.
279, 980–983, 2000.
Shrivastava, H.Y., and Nair, B.U. Chromium(III) mediated structural modification of
glycoprotein: Impact of the ligand and the oxidants, Biochem. Biophys. Res.
Commun. 285, 915–920, 2001.
Shuttleworth, S.G. The theory of chrome tanning, J. Soc. Leather Technol. Chem. 34,
410–437, 1950.
Simoncini, A., and Sammarco, U. The possibility of reducing the CODs deriving from
the fatliquoring of the softy leathers in residual baths, Proceedings of the XXIII
IULTCS Congress, Germany, 1995.
Somerville, I.C., Hetzel, L.V., Fisher, R.F.M., Wendkos, J., and Cares, C.J. Rapid
unhairing with dimethylamine, J. Am. Leather Chem. Assoc. 58, 254–268,
1963.
Sreeram, K.J., Rao, J.R., Venba, R., Nair, B.U., and Ramasami, T. Factors in gravitational
settling of chromic hydroxide in aqueous media, J. Soc. Leather Technol. Chem.
83, 111–114, 1999.
Sreeram, K.J., Rao, J.R., Sundaram, R., Nair, B.U., and Ramasami, T. Development of
semi-continuous method for chrome recovery from waste waters, Green Chem.
2, 37–41, 2000a.
Sreeram, K.J., Kanthimathi, M., Rao, J.R., Sundaram, R., Nair, B.U., and Ramasami, T.
Development of an organo-zirconium complex—Organozir as possible alterna-
tive to chromium, J. Am. Leather Chem. Assoc. 95, 359–367, 2000b.
Stephens, L.J. The effect of preservation by freezing on the strength of Kangaroo
leathers, J. Am. Leather Chem. Assoc. 82, 45–49, 1987.
Steven, W. Treatment of beamhouse and fellmongering waste waters, J. Soc. Leather
Technol. Chem. 67, 127–131, 1983.
Stockman, G. Determination of spray machine transfer efficiency for leather finishing,
Streicher, V.R. Entkälkung mit ammoniumsalzfreien Entkälkungsmitteln, Leder
Hautemarkt 39(14), 7–12, 1987.
Sundar, V.J., and Muralidharan, C. Cleaner tanning technologies, J. Indian Leather
Technol. Assoc. 49, 110–137, 1999.
Sundar, V.J., Rao, J.R., and Muralidharan, C. Cleaner chrome tanning—Emerging
options, J. Clean. Prod., 10, 69–74, 2002.
Sundararajan, A., Madhan, B., Rao, J.R., and Nair, B.U. Studies on tanning with zir-
conium oxychloride: Part I Standardization of tanning process, J. Am. Leather
Chem. Assoc. 98, 101–106, 2003.
Suresh, V., Kanthimathi, M., Thanikaivelan, P., Rao, J.R., and Nair, B.U. An improved
product–processs for cleaner chrome tanning in leather processing, J. Clean.
Prod. 9, 483–491, 2001.
Swarna, V.K., Jeevan, R.G., Chandrababu, N.K., Sadulla, S., Rao, V.S.S., and Ra-
masami, T. Formaldehyde free leather, in Science and Technology for Leather
Into the Next Millennium, Tata McGraw-Hill, New Delhi, 322–328, 1999.
Sykes, R. Environmental management, Leather June, 17–22, 1996.
Sykes, R. Zero emissions—Pattern for the future? Leather No. 2, 35–38, 1997a.
Sykes, G. Leather board manufacture, World Leather 10(7), 60–61, 1997b.
Taeger, T. Progress in leather chemistry: What kind of milestones are to be expected?
An excursion four years before the millenium, J. Am. Leather Chem. Assoc. 91,
211–224, 1996.
Takenouchi, K., Kondo, K., and Nakamura, F. Composition of complexes in citrate
masked aluminium solutions and their affinity for collagen, Proceedings of the
Centenary IULTCS Congress, London, 500–510, 1997.
Taqui-Khan, M.M. Approach towards low waste chrome tanning. In Trends in Min-
eral Tanning and Resource Potential, Ramasami, T., and Thyagarajan, G., Eds.,
CLRI COSTED, Chennai, 115–128, 1987.
Tate, I.P. The use of aluminium, titanium and magnesium complexes in pretanning,
tanning and retanning operations, Proceedings of the XX IULTCS Congress,
Philadelphia, 1989.
Taylor, M.M., Bailey, D.G., and Feairheller, S.H. A review of the uses of enzymes in
the tannery, J. Am. Leather Chem. Assoc. 82, 153–164, 1987.
Taylor, M.M., Cabeza, L.F., DiMaio, G., Brown, E.M., Marmer, W.N., Carrio, R., Celma,
P.J., and Cot, J. Processing of leather waste: Pilot scale studies on chrome shav-
ings. Part I. Purification of chrome cake and tanning trials, J. Am. Leather Chem.
Assoc. 93, 83–98, 1998.
Taylor, M.M., Diefendorf, E.J., Thompson, C.J., Brown, E.M., Marmer, W.N., and
Cabeza, L.F. Extraction of value added byproducts from treatment of chromium
containing collagenous leather industry wastes, J. Am. Leather Chem. Assoc. 81,
5–13, 1997.
Technology plan for environmental sustainability of the tanning sector in Tamilnadu,
Status report submitted to AISHTMA by CLRI, Chennai, 1997.
Thanikaivelan, P., Geeta, V., Rao, J.R., Sreeram, K.J., and Nair, B.U. A novel chomium–
iron tanning agent: Cross fertilization in solo tannage, J. Soc. Leather Technol.
Chem. 84, 82–87, 2000a.
Thanikaivelan, P., Rao, J.R., Kanthimathi, M., Nair, B.U., and Ramasami, T. An im-
proved process for the preparation of a tanning agent, Indian Patent Application
No. 770/DEL/2000, 2000b.
Thanikaivelan, P., Rao, J.R., and Nair, B.U. Development of a leather processing
method in narrow pH profile. Part 1. Standardisation of unhairing process, J.
Soc. Leather Technol. Chem. 84, 276–284, 2000c.
Thanikaivelan, P., Rao, J.R., and Nair, B.U. Development of a leather processing
method in narrow pH profile. Part 2. Standardisation of tanning process, J. Soc.
Leather Technol. Chem. 85, 106–115, 2001a.
Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. Approach towards zero dis-
charge tanning: Exploration of NaOH based opening up method, J. Am. Leather
Chem. Assoc. 96, 222–233, 2001b.
Thanikaivelan, P., Kanthimathi, M., Rao, J.R., and Nair, B.U. A novel formaldehyde-
free synthetic chrome tanning agent for pickle-less chrome tanning: Comparative
study on syntan versus modified basic chromium sulfate, J. Am. Leather Chem.
Assoc. 97, 127–136, 2002a.
Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. Zero discharge tanning: A
shift from chemical to biocatalytic leather processing, Environ. Sci. Technol. 36,
4187–4194, 2002b.
Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. Approach to-
wards zero discharge tanning: Role of concentration on the develop-
ment of eco-friendly liming–reliming processes, J. Clean. Prod. 11, 79–90,
2003a.
Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. Biointervention makes
leather processing greener: An integrated cleansing and tanning system, Envi-
ron. Sci. Technol. 37, 2609–2617, 2003b.
Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. Underlying principles in
chrome tanning: Part 2. Underpinning mechanism in pickle-less tanning, J. Am.
Leather Chem. Assoc. 99, 82–94, 2004a.
Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. Ecofriendly bio-process for
leather processing, US Patent 6,708,531, 2004b.
Thanikaivelan, P., Rao, J.R., Nair, B.U., and Ramasami, T. Progress and recent trends
in biotechnological methods in leather processing, Trends Biotechnol. 22, 181–
188, 2004c.
Tsou, T.C., Lin, R.J., and Yang, J.L. Mutational spectrum induced by chromium(III)
in shuttle vectors replicated in human cells: Relationship to Cr(III)-DNA inter-
actions, Chem. Res. Toxicol. 10, 962–970, 1997.
Turner, P. The effect of environmental legislation on the selection of dyestuffs, J. Soc.
Uehara, K., Matsunaga, A., Arai, K., Toyoda, H., and Chonan, Y. Solubilization
of cattle and pig hair keratins by reduction with sodium thioglycolate or
oxidation with performic acid, J. Am. Leather Chem. Assoc. 81, 331–337,
1986.
Valeika, V., Balčiūnienė, J., Beleška, K., Skrodenis, A., and Valeikienė, V. Use of
NaOH for unhairing hides and the influence of salts on the hide properties, J.
Soc. Leather Technol. Chem. 81, 65–69, 1997.
Valeika, V., Balčiūnienė, J., Beleška, K., Skrodenis, A., and Valeikienė, V. Lime free
unhairing: Part 2, Influence of added salts on NaOH unhairing and on hide
properties, J. Soc. Leather Technol. Chem. 82, 95–98, 1998.
van Groenestijn, J.W., Mariappan, M., Sekaran, G., and Rajamani, S. Evaluation of
performance of lagooning systems for tannery effluent treatment in South India,
Proceedings of the 30th LERIG, Chennai, 10–22, 1995.
Velappan, K.C., and Muralidharan, C. Integrated investment requirements for the
leather sector, Proceedings of the 35th LERIG, Chennai, 15–46, 2001.
Venba, R., Ramesh, R., Rao, P.S., Babu, M.S., Chandrababu, N.K., and Parthasarathy,
K., Pickleless high exhaust chrome tanning process, Proceedings of the 30th
LERIG, Chennai, 1995.
Venba, R., Malathy, J., and Chandrababu, N.K. Studies on the effect of recovered
chrome on dyeing of leathers, in Science and Technology for Leather into the
Next Millennium, Tata McGraw-Hill, New Delhi, 446–452, 1999.
Venier, P., Montaldi, A., Majone, F., Bianchi, V., and Levis, A.G. Cytotoxic, mutagenic
and clastogenic effects of industrial chromium compounds, Carcinogenesis 3,
1331–1338, 1982.
Venkatachalapathi, K., Nair, M.S., Ramaswamy, D., and Santappa, M. Binary and
ternary complexes of chromium(III) involving iminodiacetic acid, L(+)-aspartic
acid, L(+)-glutamic acid, or L(+)-cysteine as ligands, J. Chem. Soc. (Dalton
Trans.) 291–297, 1982.
Vijayalakshmi, R., Kanthimathi, M., Subramanian, V., and Nair, B.U. DNA cleavage
by a chromium(III) complex, Biochem. Biophys. Res. Commun. 271, 731–734,
2000.
Voitkun, V., Zhitkovich, A., and Costa, M. Cr(III)-mediated crosslinks of glutathione
or amino acids to the DNA phosphate backbone are mutagenic in human cells,
Nucleic Acids Res. 26, 2024–2030, 1998.
von Vlimmeren, P.J. New beamhouse development to simplify tannery wastewater

management, J. Am. Leather Chem. Ass. 71, 318–335, 1976.
Walther, W. All aqueous finishing systems for leather, problems and solutions, J. Am.
Warrier, K.G.K., Nair, K.M., Damodaran, A.D., de Vries, A.H., van der Zwan, J., Prasad,
B.G.S., Nair, B.U., Venba, R., Mahadevan, T.S.K., and Ramasami, T. Safe utili-
sation of chrome containing sludges in brick making, Proceedings of the XXIII
IULTCS Congress, Germany, 1995a.
Warrier, K.G.K., Nair, K.M., Perumal, P., Mukundan, P., Damodaran, A.D., de Vries,
A.H., van Der Zwan, J., Ramasami, T., and Prasad, B.G.S. Effective disposal of
tannery sludge as admixture to building bricks, Proceedings of the 30th LERIG,
Chennai, 84–95, 1995b.
Wedrychowski, A., Ward, W.S., Schmidt, W.N., and Hnilica, L.S. Chromium induced
cross linking of nuclear proteins and DNA, J. Biol. Chem. 260, 7150–7155, 1985.
Wenzel, W. Aqueous finishing of leather—Products, processes and problems, J. Am.
Will, H. The latest experiences in leather finishing by roll coating and printing, J.
Windus, W., and Showell, J.S. An interpretation of the mechanism of unhairing as a
nucleophilic displacement, J. Am. Leather Chem. Assoc. 63, 258–274, 1968.
Wu-Sheng, W., Jun, Z., De-Li, R., Feng, Z., and Cai-Yuan, P. Expoxysilane: A new
crosslinker for waterborne polyurethane finishes, J. Soc. Leather Technol. Chem.
84, 45–47, 2000.
Zhitkovich, A., Voitkum, V., and Costa, M. Glutathione and free amino acids form
stable complexes with DNA following exposure intact mammalian cells to chro-
mate, Carcinogenesis 16, 907–913, 1995.
Zhitkovich, A., Shranger, S., and Messer, J. Reductive metabolism of Cr(VI) by cysteine
leads to the formation of binary and ternary Cr–DNA adducts in the absence of
oxidative DNA damage, Chem. Res. Toxicol. 13, 1114–1124, 2000.

Recent Trends in Leather Making: Processes, Problems, and Pathways

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Recent Trends in Leather Making: Processes, Problems, and Pathways

Uploaded by

Copyright:

Available Formats

Critical Reviews in Environmental Science and

ISSN: 1064-3389 (Print) 1547-6537 (Online) Journal homepage: http://www.tandfonline.com/loi/best20

Recent Trends in Leather Making: Processes,

Palanisamy Thanikaivelan , Jonnalagadda Raghava Rao , Balachandran Unni

To link to this article: https://doi.org/10.1080/10643380590521436

Published online: 12 Jan 2007.

Submit your article to this journal

Article views: 1166

Citing articles: 50 View citing articles

Full Terms & Conditions of access and use can be found at

Recent Trends in Leather Making: Processes,

Jonnalagadda Raghava Rao∗ and Balachandran Unni Nair

Leather processing has emerged as an important economic activity

KEY WORDS: chemical oxygen demand, dehairing, effluent treat-

B. Leather and Environment: A Challenging Issue

Leather processing is one of the earliest industrial activities taken up by

II. LEATHER PROCESSING: SOURCE OF POLLUTION

Leather processing involves a series of operations, as shown in the flow di-

FIGURE 1. Various unit processes and operations in leather processing (Saravanabhavan

FIGURE 2. Inflow–outflow diagram for leather processing (Rao et al., 2003).

operations aim at cleaning hides/skins, tanning stabilizes the skin/hide ma-

TABLE 1. Typical Range of Emission Factors for Conventional Leather Processing

Volume of 6–9 3–4 1–2 0.5–1.0 0.5–2 1–2 1–2 30–40

quantity of sulfide discharge is from the dehairing operations (Steven, 1983).

The pH of the limed pelt is highly alkaline. The reduction of pH or alkalin-

The complete removal of unwanted interfibrillary materials and short

Pickling is a process in which the partially anionic matrix is temporarily con-

contain chromium (Covington, 1997a; Germann, 1995, 1999). In chrome tan-

III. COMBATTING ENVIRONMENTAL CHALLENGES:

TABLE 2. Nature and Quantity of Solid Wastes Produced from Processing

Nature of solid waste Quantity (kg)

Salt from handshaking 80

offer physicochemical treatment followed by biological and tertiary treatment

accelerated evaporation and crystallization of saline streams using flat-plate

IV. WASTE MINIMIZATION IN LEATHER PROCESSING:

used, amount of wastes generated, and possible technological and manage-

V. CLEANER LEATHER PROCESSING: EMERGING

Prevention or redution of pollution at the source through in-process con-

depends on the following factors: (a) reduction of pollution in terms of quan-

E. Liming and Reliming

(a) fear of possible damage of leather-making substances, (b) inadequate

hexavalent chromium compounds as potent carcinogens (Costa, 1991). Once

It is now technologically possible to increase the absorption of chromium

High-exhaustion methods ensuring absorption of 85% of chromium are still

Chromium in the sectional streams of wastewater can be recovered, regener-

Pickleless chrome tanning is a recently introduced concept (Venba et al.,

(Prentiss and Prasad, 1981; Chandrababu et al., 1995; Covington, 1997a,

A chromium–iron tanning agent as a chrome-saver approach has been de-

systems, if made costeffective, can emerge as chrome savers. Titanium-based

I. Posttanning and Finishing

r Screening of retanning and fatliquoring agents for selection, based on their

Optimization of such chemical inputs as well as the choice of inputs

r Minimizing the wastage and emission by proper control of spraying ma-

VI. NOVEL CONCEPTS IN LEATHER PROCESSING: APPROACHING

Leather processing activity involves the use of several chemicals, some of

r Reduction in the use of chemicals.

Ideally, zero discharge of wastewater is most desirable. As a practical

r Usage of chemicals having low toxicity or less environmental impact.

Leather processing generally involves a combination of single- and mul-

ambient preservation technique. It is now possible to process green hides

r Standardization of conventional liming and reliming chemical inputs and

A. Some Early Results

An enzyme-assisted dehairing process using sodium sulfide in an amount