Environ Sci Pollut Res
DOI 10.1007/s11356-014-3055-9
REVIEW ARTICLE
A review on management of chrome-tanned leather
shavings: a holistic paradigm to combat the environmental issues
Anupama Pati & Rubina Chaudhary &
Saravanabhavan Subramani
Received: 5 February 2014 / Accepted: 16 May 2014
# Springer-Verlag Berlin Heidelberg 2014
Abstract Raw hide/skins come to the tanners as a by-product
of meat industry which is converted into value-added leather
as product for fashion market. Leather manufacturing is a
chemical process of natural biological matrix. It employs a
huge quantity of water and inorganic and organic chemicals
for processing and thereby discharges solid and liquid wastes
into the environment. One of the potential solid wastes gen-
erated from leather industry is chrome-tanned leather shavings
(CTLSs), and its disposal is increasingly becoming a huge
challenge on disposal to tanners due to presence of heavy
metal chromium. Hence, finding a sustainable solution to the
CTLS disposal problem is a prime challenge for global tanners
and researchers. This paper aims to the deeper review of
various disposal methods on CTLS such as protein, chromi-
um, and energy recovery processes and its utilization meth-
odologies. Sustainable technologies have been developed to
overcome CTLS solid wastes emanating from leather process-
ing operations. Further, this review paper brings a broader
classification of developed methodologies for treatment of
CTLSs.
Responsible editor: Vera Slaveykova
A. Pati : R. Chaudhary (*)
School of Energy and Environmental Studies, Takshashila Campus,
Devi Ahilya University, Khandwa Road, Indore 452001, Madhya
Pradesh, India
e-mail: rubinachaudhary.sees@gmail.com
A. Pati
e-mail: anupama.sees@yahoo.com
A. Pati : S. Subramani
Research and Development, Tata International Limited,
Dewas 455001, Madhya Pradesh, India
S. Subramani
e-mail: s.saravanabhavan@tatainternational.com
Keywords Leather Industry . Solid waste . Chromium .
Recovery . Protein hydrolysate . Environment
Introduction
Leather industry and environment: two sides of the coin
Leather industry recycles an organic waste originated from the
meat industry into leather. Raw hide/skin is transformed into
leather by means of a series of chemical and mechanical
operations. The series of operation involved in leather making
generates substantial quantities of solid, liquid, and gaseous
wastes (Germann 1999). The quantum of solid wastes pro-
duced while processing 1 ton of raw hide/skins is given in
Table 1 (Chakraborty 2003). The processing of 1 metric ton of
raw hide/skin provides 200 kg of a leather-final product, along
with 250 kg of non-tanned waste, 200 kg of tanned waste, and
50-m3 volume of wastewater. Thus, only 20 % of the raw
material weight is converted to leather (Kolomaznik et al.
2003). The World Bank reported that solid wastes can repre-
sent up to 70 % of the wet weight of the original hides (World
Bank 1999). Worldwide chromium-based tanning process is
predominantly followed (Stein and Schwedt 1994; Rajamani
1995; Agrawal et al. 2006) due to versatility of chromium.
Leather industry generates chromium-based waste such as
chromium sludge, chrome-tanned leather shavings (CTLSs),
and chrome leather trimmings. These wastes are unavoidable
and possess a serious threat to the environment. It has been
estimated that 0.02 million tons of chromium shaving is
generated in India per annum. Nearly, 0.8 million tons of
CTLSs could be generated per year globally (Sangeeth et al.
2009). Most of these wastes are disposed of through landfill or
incineration processes, although effective reutilization is
greatly desirable, as the methods of disposal involve economic
and environmental losses. This creates serious environmental
 Environ Sci Pollut Res

Table 1 Quantity of proteinous

solid wastes produced from pro-
cessing 1 ton of raw hides/skins
Solid wastes Quantity (kg/ton of raw hide processing) Present status on disposal
Raw hide trimmings 120–150 kg Glue and gelatin manufacturing
Fleshings 70–230 kg Glue manufacturing
Tanned splits 115–140 kg Reused for making suede leathers
Tanned leather 100–120 kg Landfill (incineration banned)
trimmings and shavings
Buffing dust 2–5 kg Particle boards making
Finished leather trimmings 30–40 kg Used in manufacturing metal
polish brushes and leather articles

challenges in leather industry (Veeger 1993; Ramasami et al. cost, which is explained by the combination of the overall
1998; Popescu et al. 2008; Gaidau et al. 2009). In order to save high pollution emissions and low energy recovery. The avail-
the environment from further degradation or increases in the ability of landfill sites rapidly reaches their total capacity, and
accumulated amounts of hazardous waste in the future, most the authorization for a new site becomes challenging (Kirk
industrial operations should be designed based on “4Rs” et al. 2002). In the European state, the pressure over landfilling
(reduction, recycling, reuse, and recovery) concept. of wastes with high organic content and toxic substances is
continuously increasing (IPPC Report 2001). The improper
and the manual handling and transfer of CTLS waste in open
CTLS: physio-chemical nature and disposal issues vehicles create unhygienic conditions. Disposal of waste in
low-lying areas without proper liners allows the leachate to
CTLSs are small, thin pieces of leather formed during shaving mix with groundwater which leads to deterioration of water
operation, which is being done to achieve the desired thick- quality in neighbourhood areas. In indiscriminate landfills of
ness for various end uses of the leather. It accounts for 15– CTLSs, approximately 40–50 % methane gas liberates which
30 % of total proteinous waste generated from tannery. CLTS contributes significantly to global warming. Chromium also
is a chromium cross-linked protein collagen that contains leaching into the soil making it unfit for cultivation and other
higher amount of protein (Saravanabhavan et al. 2005). The uses. With increased environmental restrictions, landfill dis-
physical and chemical characteristics of CTLSs are presented posal method has been discouraged by environmental experts
in Table 2 by Pati et al. (2013b). CTLS is a fibrous matter and pressure on using clean technologies; their processing into
containing 30–40 % moisture content. Elemental analysis data secondary raw materials is one of the requirements for the
of CTLS is given in Table 3. The chromium oxide content in
CLTS is about 4.4 % (Tahiri et al. 2007).
Large quantities of CTLSs are disposed by landfill in many
Table 3 ICP-OES mul-
parts of the world (Brown et al. 1996). Distraction of land for tielement determination Element Concentration (g/kg)
waste disposal would be physically impossible since areas in CTLS
with the largest concentration of CTLSs would also be the Na 93.86
areas with serious scarcity of vacant land. Therefore, if the Ca 6.91
current methods of disposal persist, the waste would have to Mg 0.60
be carried over a long distance, which would require transport Fe 0.80
facilities and infrastructure. This would involve enormous Mo 0.008
additional finances. Landfilling scenario faces the highest Al 0.43
Zn 0.47
Ti 0.02
Table 2 Physical and V 0.02
chemical characteristics Parameters Values
Cd <LOD
of CTLS
% Moisture content 35.1±0.6 Co <LOD
% Cr2O3 3.12±0.12 Cu 0.05
% Inorganic ash 5.21±0.11 Li 0.05
% Nitrogen 16.4±0.1 Ni 0.008
% Oils and fat 1.5±0.05 Cr 30.10
pH (10 % aqueous leather) 3.4±0.2 Mn 0.008
Apparent density 0.91 g/mL Pb 0.05
Environ Sci Pollut Res
survival of the leather industry (Sekaran et al. 2007). Many
countries have banned disposal of CTLSs through landfill and
incineration due to the presence of chromium content (Lipsett
1982; Mukherjee et al. 2005). In India, 90 % of tanneries
engaged in the chrome tanning process (Rajamani 1995).
The consumption of basic chromium sulfate (BCS) has in-
creased from 25,000 to 40,000 tons per annum (Agrawal et al.
2006). A major problem concerns the possibility of oxidation
of Cr(III) into Cr(VI) in gentle conditions by air in a wide
range of pH. Principally, oxidation can be realized after the
following equations (Kolomaznik et al. 2008):
2Cr2 O3 þ 8OH− þ 3O2 ¼ 4CrO4 − þ 4H2 O ðin alkali mediumÞ
ð1Þ
2Cr2 O3 þ 3O2 þ 2H2 O ¼ 2Cr2 O7 − þ 4Hþ ðin acid mediumÞ
ð2Þ
The chromium present in CTLSs exists in the non-toxic +3
oxidation state, but there is growing concern that chromium
could possibly be converted to a toxic state +6. Cr(VI) is the
most toxic form, being carcinogenic and mutagenic to living
organisms. In addition, it leads to liver damage and pulmonary
congestion and causes skin irritation resulting in ulcer forma-
tion. Trivalent Cr(III) is about 300 times less toxic than
Cr(VI), and due to the fact that it has limited hydroxide
solubility, it is less mobile and less bioavailable. Cr (III) is
essential to animals and plants and plays an important role in
sugar and fat metabolism, although in excess can cause aller-
gic skin reactions and cancer (IARC 1987; Cieslak-Golonka
1996; Kotas and Stasicka 2000; Krishnani and Ayyappan
2006; Miretzky and Fernandez Cirelli 2010). The US
Environmental Protection Agency (2004) has classified chro-
mium as a group “A” human carcinogen and is one of the
main pollutants based on data available for 976 National
Priorities List (NPL) Sites with fiscal year 1982–2003
(Fig. 1; Dhal et al. 2013). The most mobile forms of chromium
in soils are CrO42− and HCrO4− ions. They can be taken up by
plants and easily be leached out into the deeper soil layers,
leading to ground and surface water pollution (Calder 1988).
Chromium is an essential micro-nutrient in the diet of animals
and humans, and its deficiency in the diet causes alteration to
lipid and glucose metabolism in animals and humans
(Mordenti and Piva 1997). However, elevated levels of chro-
mium are always toxic, although the toxicity level is related to
the oxidation state of chromium. Cr(VI) is not only highly
toxic to all forms of living organisms, mutagenic in bacteria,
and mutagenic and carcinogenic in humans and animals (Losi
et al. 1994) but is also involved in causing birth defects and the
decrease of reproductive health (Kanojia et al. 1998). The
positive and negative effects of Cr(III) and Cr(VI) for humans
are described by Bielicka et al. (2005). The occupational
safety and health administration (OSHA) has set limits of
500-μg water-soluble Cr(III) compounds per cubic meter of
workplace air (500 μg L−1), 1,000 μg L−1 for metallic chro-
mium(0) and insoluble chromium compounds, and 52 μg L−1
for chromium(VI) compounds for 8-h work shifts and 40-h
work weeks (Das and Singh 2011). The stringent enforcement
of the environment protection has prompted industrialists and
scientists to re-look at the decontamination of wastes and
transform to valuable products.
Disposal of CTLSs attempted by researchers to combat
the problem
Research studies have been carried out to investigate safe
disposal, recovery of chromium and protein, and their reuse
in various fields of industry. There are several treatment
methods or systems that have been attempted by researchers
around the world, and they are broadly classified into (I) direct
use, (II) different treatment processes, and (III) make value-
added products and its application in different industries
(Fig. 2) and reviewed in this article.
Leather board/sheets
CTLSs in combination with cotton and kraft pulp were used to
manufacture leather boards, which are strong and flexible and
have a high elongation at break (Okamura and Shirai 1972;
Sykes 1997; Gish 1999; Crispim and Mota 2003; Vedaraman
et al. 2002). The direct application of CTLSs is many folds
such as the manufacture of bonded leather, leather boards,
fibrous sheets grafted with acrylates, insulators, building ma-
terials after reacting with polyisocyanates, composites for
footwear, soundproof roofing material, flexible composite
sheets using cellulose derivatives, filler for nitrile and butadi-
ene–acrylonitrile rubbers, portland cement clinker, ceramics
as pigment (Lollar 1981; Gyurko et al. 1985; Edmund et al.
2003; Sastry et al. 2005; Rose et al. 2007; Przepiorkowska
et al. 2007; Trezza and Scian 2007; Abreu and Toffoli 2009;
Ashokkumar et al. 2011; Chrońska-Olszewska and
Przepiórkowska 2011; Lakrafli et al. 2012).
Adsorbent
Direct use of CTLS as adsorbent
The CTLS has the potential to be used as a low-cost adsorbent
for the removal of surfactants, dyes, and heavy metals (As(V)
and Cr(VI)) from wastewater (Na et al. 2006; Oliveira et al.

Fig. 1 The frequencies of most
common contaminants at NPL
sites (USEPA 2004; Dhal et al.
2013)
2007, 2008a). The removal of vegetable tannins from mixed
effluents using CTLS has been attempted by Saravanabhavan
et al. (2007). Use of CTLSs for the removal of dyes from
wastewater has been studied, and the dye-adsorbed solid
wastes were used for the preparation of pigments (Sreeram
et al. 2004). Many researchers have studied the possibility of
dye removal from textile effluents by CTLSs. The ability of
CTLSs to remove motor oils, oily wastes, and hydrocarbons
from contaminated water has been studied, and it was found
that they are capable of absorbing many times their weight in
oil or hydrocarbons due to low density and high buoyancy of
fibers and porosity (Tahiri et al. 2002; Sreeram et al. 2004;
Fig. 2 Critical appraisal of CTLS waste management methodologies
Environ Sci Pollut Res
Saravanabhavan et al. 2004, 2007; Piccin et al. 2012). The
preparation of ecological agent from CTLSs for removing
environmentally hazardous organic substances such as
chromate and arsenate has been attempted by
Przepiorkowska et al. (2003) and Gammoun et al. (2007a,
b). Low-cost Fe(III) and Al(III) loaded adsorbent was pre-
pared using CTLS as supporting matrix (Huang et al. 2009).
Kantarli and Yanik (2010) have attempted to make activated
carbon from CTLSs. Treatment and cleaning of water polluted
by oils, hydrocarbons (Gammoun et al. 2007b), and organic
dyes (Tahiri et al. 2003) using CTLSs have also been studied.
The use of chestnut and mimosa tannins immobilized on
Environ Sci Pollut Res
CTLS matrices as adsorbents for the recovery of Cr (VI) from
polluted aqueous systems has been established by Chabaane
et al. (2011). Fathima et al. (2004) have studied the dye
removal behavior of CTLS after stabilization with
glutaraldhyde. Marsal et al. (2013) have attempted
adsolubilization of 2-naphthol onto modified CTLSs.
Sanjuán-Herráez et al. (2012) have demonstrated the capacity
of CTLS to adsorb VOC in LDPE tubes. Adsorptive removal
process for removal of As(V) from aqueous solution by
Zr(IV)-loaded CTLSs has been studied by Jiao et al. (2009).
Activated carbon prepared from CTLS used as adsorbent
Adsorption is the most versatile and widely used technology,
and activated carbon is the most commonly used sorbent for
all kinds of wastewater treatment. However, the use of acti-
vated carbon is expensive, so there has been increased interest
in the past years in the use of low-cost adsorbent materials.
CTLS is used as raw material for activated carbon production
by physical and chemical activation methods. The CTLS after
controlled pyrolysis under CO2 flow was transformed into
chromium-containing activated carbons. The chromium oxide
was nanodispersed on the activated carbon, and the particle
size increased with the activation time. The activated carbon
having the highest surface area (799.5 m2 g−1) was presented
as an adsorbent for the adsorption of dyes from aqueous
solution (Langmaier et al. 1999; Yilmaz et al. 2007).
Chrome-containing activated carbon prepared from CTLS
was studied for removal of organic dyes in wastewater.
CTLS was pyrolyzed in a fixed bed reactor at temperatures
of 450 and 600 °C under N2 atmosphere. The carboneous
residue (chars) was activated by CO2 to obtain the activated
carbon. The collagen fiber, with hierarchical super molecular
structures, can be used to prepare well-defined porous carbon
fiber, which has a large surface area, a high mesopore ratio,
and a controllable pore size, which has great potential in
selective adsorption and as chemical sensors and catalyst.
The controlled pyrolysis of CTLS is done to produce
chromium-containing activated carbons with microporous
and mesoporous structure (Deng et al. 2008; Oliveira et al.
2008a, b, c). Activated carbon produced from CTLS had a
high specific surface area and high capacity for removal
organic substance in aqueous medium (Oliveira et al. 2011).
The potential applications of these activated carbons obtained
from CTLS as adsorbent for removal of water pollutants have
been studied for phenol, methylene blue, and Cr (VI) (Kantarli
and Yanik 2010; Oliveira et al. 2008a, b, c; Kong et al. 2013).
Thermal treatments of CTLS for energy recovery
The thermal treatment of wastes involves incineration, gasifi-
cation, and pyrolysis as a mean of disposal, while also recov-
ering energy from waste. The thermal incineration is
considered as the cheapest alternative and attractive method
for its simultaneous energy production and volume reduction
of solid waste. The thermal incineration of solid wastes from
tanneries needs a special attention on the issues such as release
of toxic chromium (VI), halogenated organic compounds, and
poly-aromatic hydrocarbons into the environment (IPPC re-
port 2001).
Chrome recovery through incineration of CTLS
Disposal of CTLS through direct incineration converts Cr
(III) to Cr (VI), which is highly carcinogenic in nature
(Zahid et al. 1989; Williams 1990; Oppelt 1990, Oppelt
and Dempsey 1993; Andre et al. 1998). The chromium
recovery from this waste is necessary for environmental
protection and economic reasons. The major species
formed from Cr (III) during thermal incineration of solid
waste are Cr2(SO4)3, CrOCl2, and Cr2O3 which later ac-
counts a path for the formation of Cr (VI) (Skrypski-
Mantele and Bridle 1995; Chen et al. 2003). CTLS is
subjected to starved air combustion to utilize its maximum
calorific value as well as to inhibit the oxidation of Cr 3+ to
Cr 6+. The process produces bottom ash 3+ containing
toxic heavy metals mainly Cr and partially burnt carbon.
The highly toxic properties of ash prohibit its direct land co-
disposal. An effective solidification and stabilization of
bottom ash were resorted to change potentially hazardous
solid wastes into less hazardous or non-hazardous solids
before it is disposed off as landfill (Filibelix et al. 2000;
Ioaninides and Zouboulis 2003). The bottom ash was so-
lidified and stabilized using portland cement, fine aggre-
gate, coarse aggregate, and blue metal dust. Investigations
were performed on the incinerating conditions of CTLS to
reduce the toxic gas compounds and on the effect of remov-
ing them using the scrubber. The amount of the various
components of gas was within acceptable levels, and the
recovered ash could be used as a material in the process of
preparing bichromate (Imai and Okamura 1991). Ashes
contain meaningful amounts of chromium and some in
hexavalent form and are used as a source of chromium for
various applications, including pigment for ceramic glazes.
Chromium recovered in the form of soluble chromate by
oxidation has been reused in tanning by reduction with
Na2SO3. It is desirable to recover chromium ashes and
reuse them in the leather tanning process, through a basic
chromium sulfate (Okamura and Shirai 1976; Poulopoulou
et al. 1998; Carneiro et al. 2003; Erdem 2006; Tahiri et al.
2007). Swarnalatha et al. (2009) demonstrated that the
organic fractions of chrome shavings could be incinerated
without oxidizing trivalent chromium into hexavalent chro-
mium through starved air combustion and for better recov-
ery of energy.

Recovery of energy from CTLSs: pyrolysis
Pyrolysis is one of the alternative routes for the treatment of
solid wastes from tannery. Three different types of tannery
wastes can be pyrolyzed, resulting in gas, oil, ammonium
carbonate, and carboneous residues. The gas can be used as
fuel, and the oil can be used either as fuel or as raw material for
chemicals. The carbonaceous residue can be burned as fuel or
safely disposed. In addition, this residue is also suitable for
production of activated carbon (Yilmaz et al. 2007). The
elimination of the organic matter resulted in chromium-rich
material, which could be suitably used as a ceramic pigment
(Lollar 1981; Abreu and Toffoli 2009). CTLS was treated with
NaOH before pyrolysis, and it was found that the volatile
products obtained from NaOH-treated samples contain higher
amounts of nitrogen compounds than those obtained from
untreated samples (Marcilla et al. 2011). A double-pyrolysis
(first pyrolysis (PI) followed by second pyrolysis (PII)) meth-
od was employed to dispose hazardous chrome-tanned leather
solid waste by converting it into useful products. In this
process, the three major products obtained were (i) energy-
enriched combustible gas (32.01 %, PI; 42.45 %, PII), (ii) a
high fraction condensate (33.32 % (PI and PII)), and (iii) a
carbonaceous residual ash containing trivalent chromium
(34.67 %, PI; 24.23 %, PII). In addition, 2.73 % of liquid fuel,
75.24 % of nitrogen-enriched liquid, and 22.03 % distillate tar
as sub-products from the high fraction condensate
(Sethuraman et al. 2013).
Gasification of CTLSs: energy generation
Gasification technology has the potential to provide signifi-
cant cost benefits in terms of power generation and waste
disposal, and increase sustainability within the leather indus-
try. The gasification process converts any carbon-containing
material into a combustible gas comprised primarily of carbon
monoxide, hydrogen, and methane, which can be used as a
fuel to generate electricity and heat. A wide range of tannery
wastes can be macerated, flash dried, densified, and gas-
ified to generate a clean syngas. As a result, up to 70 %
of the intrinsic energy value of the waste can be recovered
as syngas, with up to 60 % of this being surplus to
process drying requirements that can be recovered for
on-site boiler or thermal energy recovery uses. The tan-
nery wastes disposed contain more than half of the energy
value of coal, and if recovered and converted into useful
energy, it could satisfy all of a tannery’s own heat energy
requirements for leather processing. Bowden (2003) has
made an attempt to combine drying and gasification to
eliminate tannery solid wastes while providing combustible
gas as a renewable energy source that the tannery can
directly reuse.
Environ Sci Pollut Res
Chemical/biocatalytic treatment process of CTLSs
Green chemistry as a concept represents the chemical process-
es, where environmental pollutants can be replaced by eco-
friendly alternatives. It involves designing newer routes for
chemical synthesis and products, which protect our environ-
ment through the entire life cycle process as well as product.
The safe disposal of process wastes is also important while
designing a new synthesis route. The impact of such disposal
on environment is often neglected. The enforcement of laws
protecting the environment has prompted industrialists, envi-
ronmentalists, and scientists to re-look at the decontamination
of wastes and transform chrome shavings in usable to valuable
products. Significant research work has been carried out in
development of innovative methods of treatment and utiliza-
tion of wastes. Various efforts have been made to mitigate the
problem of CTLS. Basically, removal of chromium from
CTLSs takes place after detanning of the waste. Depending
on a kind of the applied detanning agent, three fundamental
means of chromium removal are known chemical and enzy-
matic methods. Several investigations developed some
methods of treatment generally based on the chemical hydro-
lysis of waste (Holloway 1978; Maire and Lipsett 1980;
Guardini 1983; Galatik et al. 1988; Berry et al. 2002; Tahiri
et al. 2001a, b, 2007; Wojciech et al. 1998a, b) or enzymatic
hydrolysis (Parvathi et al. 1986a, 1986b; Taylor et al. 1990,
1992; Pati et al. 2013).
Acid hydrolysis
The process for the removal of chromium from leathers and/or
leather wastes is based on contacting them with solutions of
salts, indicating at least sufficiently good complexing proper-
ties toward chromium cations, with addition of acids and/or
anhydrides of acids, being parent acids for the aforementioned
salts and/or at least moderately strong mineral acids. Process
results in recovering of the untanned collagen of contacted
leather wastes with the possibility of preserving its fibrous
structure, possessing a high degree of purity. Recovered col-
lagen can be used. Solutions of chromium compounds are
another result of the process. They can be directed back to the
technological process of tanning (Wojciech et al. 1998a, b).
Ferreira et al. (2010) have attempted hydrolysis of CTLSs
with sulfuric acid solutions at low temperature and aiming at
maximum chromium removal with minimum attack of the
leather matrix. The effects of leather scrap dimension,
sulfuric acid, and sodium sulfate concentration in the
solutions, as well as extraction time and temperature on
chromium recovery, were studied. Recovery of chromium
and protein from CLTS by organic salts and acids such as
potassium oxalate, potassium tartrate, and acetic and citric
acids has been attempted by Malek et al. (2009). The high-
protein content of chrome shavings has been utilized as a
Environ Sci Pollut Res
reductant in the preparation of chrome tanning agent, and
developed products exhibit more masking due to the hydro-
lysis of protein and formation of intermediate organic
oligopeptides (Rao et al. 2002, 2004; Sharaf et al. 2013).
Alkaline hydrolysis
The alkaline digestion of CTLSs to recover protein products
uses three alkaline agents; calcium hydroxide, sodium hy-
droxide, and sodium carbonate and organic bases like cyclo-
hexylamine, isopropylamine, and diisopropylamine were
found to be effective (Kolomaznik et al. 2007). Alkaline agent
concentration and reaction time were main parameters, and
the comparisons of various alkali and enzymatic hydrolysis
showed that calcium oxide had advantage over MgO, NaOH,
and enzymes plus MgO pretreatment(Cantera et al. 1997;
Basak and Vibhavari 2003; Mu et al. 2003; Saha et al.
2003a; Martinelango and Shelly 2004; Tahiri et al. 2006;
Zhao et al. 2009). The collagen hydrolysate obtained and
chrome cake had potential applications in the tanning industry.
Detanning can also be done using strong oxidizing agents
such as hydrogen peroxide or chlorine under slightly alkaline
conditions to produce protein hydrolysates. This technology is
developed for production-scale hydrolysis for commercial
applications, as the end product had many potential uses
(Heidemann 1991; Kosmac et al. 1995; Stockman 1996;
Amir et al. 2008). Cot et al. (1999) found that the presence
of peroxochromates generated in situ during the oxidation, in
alkaline conditions, can produce a partial hydrolysis to the
fibers of collagen, accelerating the process of isolation of
gelatin. With the oxidative dechroming using hydrogen per-
oxide augmented with ultrasound, the chrome removal rate
can be over 99 %, which would greatly favor wider utilization
of the collagen products obtained (Sun et al. 2003; Tahiri et al.
2004; Malek et al. 2009). However, the one-step hydrolysis of
chrome shavings have some disadvantages, such as long
reaction time, a lot of energy consumed, and the secondary
pollution to the environment. Moreover, due to the low mo-
lecular weight and high ash content, the isolated protein
hydrolysate cannot be used for the manufacture of high
value-added product. Process of alkaline removal of chromi-
um is performed in aqueous medium at elevated temperatures,
by means of strong or moderately strong metal hydroxides.
This results in formation of collagen degradation products,
usually water-soluble, practically—solutions of a relatively
low viscosity, always contaminated to a certain extent by
chromium compounds. Processes of alkaline removal of chro-
mium known so far reveal many drawbacks. They do not
allow recovering of the collagen with its original fibrous
structure and lead basically to preparation of sticky solutions.
This is a serious limitation for the extent of application for
chromium removal products of this kind; moreover, it makes
necessary for further, troublesome purification of acquired
products to get rid of residual chromium compounds. The
process of alkaline detanning and chromium removal is car-
ried out in the aqueous medium at temperatures ranging from
90 to 100 °C by action of MgO as the moderately strong base.
As a result, collagen glue can be produced, but yield of the
product does not exceed 56 % (based on the weight of the
starting material) and chromium recovery is less than 68 %
(Wojciech et al. 1998a, b). As a commercial perspective, the
high value-added material (technical gelatin) having low con-
tent of chromium, high bloom strength, and high yielding was
produced from chrome-tanned leather waste shaving by alka-
line hydrolysis (Na2Co3). Mohamed et al. (2013) have studied
the different parameters (pH, time of swelling, temperature,
extraction time) and examined their effects on gelatin extrac-
tion from chrome-tanned leather with the required quality. It
was found that the optimum conditions to obtain gelatin from
chrome shaving leather wastes are pH 9.5, 5-h extraction at
80 °C, and 1 swelling day.
Recovery of chromium and protein through biocatalytic
hydrolysis of CTLS
Enzymatic hydrolysis of CTLS is a viable method and pro-
vides a 50–60 % yield of hydrolysate, which shows low ash
content and a low content of chromic compounds. The use of
commercially available proteolytic enzymes used at moderate
temperatures and for short periods of time to give a chromium
product and a protein product that has potential use as a
fertilizer is a simple treatment that provides a practical and
economical solution. Proteolytic enzymes, active at moderate
temperatures, are effective in solubilizing the protein, and as
the reaction takes place at an alkaline pH, the chromium
remains insoluble. The processes can be made cost-effective
by reduction in enzyme concentration and isolation of a
gelable protein. Taylor et al. (1990, 1991, 1992, 1994, 1998)
have made extensive study on the enzymatic hydrolysis of
CTLS and developed a two-step process. In the two-step
process, the chrome shavings are treated with alkali to isolate
gelatin, and in a second step, the enzyme is used to recover the
remaining protein so that the chrome cake can be treated and
recycled. Protein products with varying properties can be
obtained using alkaline protease with reproducibility. The
effects of various alkaline salts on polypeptide size and the
stability of triple helical conformations were evaluated to
reduce the amount of enzyme used in the recovery process
and increase the value of the protein product recovered.
Pepsin behaved as a mild enzyme with a controllable effect
on leather wastes, trypsin gave a better yield, and isolated
gelatin was of high quality and cost-effective. Gelatin prod-
ucts can be deionized and the recovered chrome cake was
purified in a chemical process. This was used in the chrome
tanning without decrease in the quality of the leather (Brown
et al. 1994, 1996; Cabeza et al. 1997, 1998a, b, 1999a, b, d, e;

Taylor et al. 2000). Collagen hydrolysate was extracted from
CTLSs using alkali and enzyme. CaO is 3 % (based on the
mass of CTLS), MgO is 3 %, H2O is 300 %, hydrolysis
temperature is 80 °C, and the reaction time is 4 h. The
extraction efficiency of the gelatin is more than 40 %; when
the quantity of the enzymes is 0.125 % and the hydrolysis
temperature is 46 °C, the extraction efficiency of the protein
polypeptide can reach to 20 %. The quantities of Cr2O3 in both
gelatin and protein polypeptide are lower than 50 mg/kg, and
the content of ashes is lower than 2 % (Qiang and Feng 2011).
Pati et al. (2013b) have developed a biochemical method for
extraction and reuse of protein and chromium from CTLS. In
this method, the combination of chemical and enzyme pro-
cesses have been employed to achieve the optimum extraction
of protein. It was found that there was a significant change in
the protein extraction by protease in the presence of α-
amylase. The protein extraction efficiency by conventional
and biochemical method is found to be 60 and 80 %, respec-
tively. The potential utilization of chrome cake, aerobic bio-
logical degradation in an aqueous environment was developed
(Hrncirik et al. 2005; Kupec et al. 2002; Dvorackova et al.
2007). Pillai and Archana (2012) have attempted using
Bacillus subtilis P13 for effective degradation and grow on
CTLS as the protein source and produce in the spent medium
high levels of a keratinolytic serine protease that can be
proficiently applied for the pre-tanning processing step of hide
dehairing. The bacterium was moderately chromium resistant
tolerating up to 35 and 350 ppm of Cr(VI) and Cr(III) salts,
respectively, and showed bioaccumulation and bio-sorption of
Cr(III) and Cr(VI). An efficient waste management process is
described using solid substratum column reactor, leading to
the liquefaction of the proteinaceous waste and the recovery of
dehairing protease as concentrated product as well as Cr
recovery for reuse in tanning. Chromium-tolerant bacteria
were isolated from tannery soil and screened for high proteo-
lytic activity by zone clearance assay and caseinolytic activity.
The most potent bacterium, with a high proteolytic and
chromium-tolerant ability, was found to degrade about 90 %
of the chrome shavings in 120 h and was identified as
Alcaligenes faecalis. The hydrolysates at various time inter-
vals of proteolysis were collected; chromium was removed
and characterized. The hydrolysate was found to have 12 %
ash and 80 % protein or peptide contents after 120 h of
proteolysis with 3.14±2.0 μg of chromium per gram of pro-
tein (Shanthi et al. 2013). Sivaparvathy et al. (1986) have
explored the possibility of biodegradation of chrome shavings
using microbial enzymes (Pseudomonas aeruginosa) to min-
imize the time required for the hydrolysis. The enzyme
Paecilomyces lilacinus was used, the efficient removal of
chrome and protein hydrolysate from CTLS (Sastry et al.
1999; Chakraborty 2004). Enzymatic hydrolysis of CTLS
through Aspergillus tamerii has been attempted by Senthil
Kumar et al. (2012). The isolated fungi were optimized and
Environ Sci Pollut Res
used in the production of enzyme (alkaline Proteases) by the
solid-state fermentation. The enzyme extracted from the fungi
was used in the hydrolysis of leather protein present in the
CTLS, and the recovered chromium was recycled and used in
the tanning process. To completely hydrolyze 1 g of leather
wastes, 6 units of the enzyme protease is required. In the
optimization, the fungi maximum production shows at
72 hrs, the nitrogenous source are the milk extract, and the
optimum temperature to hydrolyze is 55 °C and the pH is 9.5.
Application of recovered chromium and protein hydrolysate
from CLTS
Chromium and protein hydrolysate extracted from CTLSs
finds application in various industries. Chromium recovered
from CTLSs was used in leather processing, commercial
pigments for paints, and ceramic industries. Protein hydroly-
sate can be used in several applications such as leather, adhe-
sive, polymer, fertilizer, animal feed, cosmetic, and medical
industries. Hence, recovery process can add value by using a
cleaner production pathway.
In leather processing
The use of protein hydrolysates leather tanning process is
proven to be a useful contributor to increase the chromium
oxide content of the leathers at the end of the chrome tanning
process (Narasimhan et al. 1980). Protein hydrolysate derived
from CTLS in post-tanning showed attractive properties by its
cosmetic, lubricating, and restoring effects by developing a
synergetic action with acrylic-retanning agents, oxazolidine,
by forming polyelectrolyte complexes by enhancing the leath-
er grain properties and providing softness and improved ten-
sile strength. Protein hydrolysates are also used as dye exhaust
aids in leather dyeing processes (Afsar et al. 2010; Aslan et al.
2006; Cantera et al. 1997, 1999, 2002, 2003; Munoz et al.
2002). The hydrolysates of protein have potential to be chem-
ically modified to produce value-added leather finishing
agents. Glutaraldehyde-modified collagen hydrolysate was
used in filling of veiny areas in chrome-tanned calfskin leath-
er. Modified protein hydrolysate products are also used in
leather processing, more specifically in preparation of coat-
ings and fillers for leather (Cao et al. 2005; Chen et al. 2001;
Crispim and Mota 2003; Mu et al. 2003; Taylor et al. 2005).
Utilize the recovered chromium from CTLS wastes via basic
chromium sulfate production to be subsequently applied in a
hide tanning (Walawska and Kowalski 2001; Fengxia et al.
2005; Dettmer et al. 2012). Collagen hydrolysate extracted
from CTLS has been used as a finishing agent in leather
making (Catalina et al. 2008, 2010). Collagen hydrolysate
recovered may contain a number of hydrophilic groups such
as carboxylic, hydroxylic, amino, imino, and amid. The reac-
tions between these collagen hydrolysate active groups and
Environ Sci Pollut Res
the urethane reactive groups (-NCO) resulted in the synthe-
sis of new polyurethane finishing agents which offered
increased permeability. The modified polyurethane finishing
agent has good elongation at break and extensibility, indi-
cating a potential application in leather sealing finishes
(Tang et al. 2010)
Pigments
The recovered chromium from CTLS showed the possibility
of producing commercial pigments for paints (Berry et al.
2001, 2002; Tahiri et al. 2001a, b). The possibility of
thermoresistant pigments for the ceramic industry was ex-
plored, and the improvement of environment quality and
decrease in pigments cost were noticed (Lazau et al. 2007).
Chromium was recovered from CTLS by controlled closed
furnace incineration, and the protein matrix provides the ad-
vantage of reducing the chromium residues. Meanwhile, pro-
ducing chromite ore is ultimately useful in the preparation of
pigmented coatings. The dry pigment obtained was green
colored and could be further processed and formulated as a
pigmented coating (paint). When the CTLSs were mixed with
iron sulfate and then incinerated, a brown-colored paint coat-
ing was achieved (Sreeram et al. 2011)
Adhesives
Gels, adhesives, and films of high molecular weight gelable
protein fraction have been obtained from CTLS under mild
alkaline conditions. However, characteristics of the products
depend on composition of the original chromium waste prod-
uct and on the specific treatment conditions (Brown et al.
1994, 1996). Urea-formaldehyde (UF) adhesives were modi-
fied with glutaraldehyde (GA) and protein hydrolysate. The
results showed that presence of protein hydrolysate and GA in
the UF adhesive mixture increased the shear strength of glued
joints. CTLS waste hydrolysate reacts with epichlorhydrin
used as a biodegradable packing material for agricultural
chemicals including herbicides, insecticides, pesticides, and
fertilizers. (Langmaier et al. 2004a, b, 2006). Innovative poly-
condensation adhesives for application in woodworking
industry is made from collagen hydrolysate extracted from
CTLS. Condensation adhesives based on urea-formaldehyde
and phenol-formaldehyde were modified with protein hydro-
lysates to reduce the free formaldehyde content (Sedliacik
et al. 2011).
Composites
Brasack et al. (2000) have made biocomposite layers of silica
from coatings of silica sols mixed with protein hydrolysate in
water/dioxane and revealed that such coatings are highly
biocompatible, with excellent mechanical properties. A scale
inhibitor was prepared by modified CTLS hydrolyzing colla-
gen and had good ability on calcium carbonate scale inhibition
(Qiang et al. 2013). Collagen hydrolysate was isolated from
CTLS and was used as a wall material with chitosan in
microencapsulation (Ocak et al. 2011). The optical study on
CTLSs show that it can be utilized as a possible source of
natural organic semiconductors with direct and indirect energy
gap (Nashy et al. 2012). Ashokkumar et al. 2010 have made
an attempt to utilize collagen hydrolysate and CTLSs to
prepare composite sheets employing polyvinylpyrrolidone
(PVP). The PVP incorporation in composite sheets has
enhanced physical characteristics and hence suitable for
numerous applications in footwear, clothing, and related
industries (Ashokkumar et al. 2010). Protein hydrolysate
reacted with dialdehyde starch produces hydrogels applicable
as biodegradable packaging materials for food, cosmetic,
and pharmaceutical products (Langmaier et al. 2008).
Krummenauer and Andrade (2009) have investigated the
usability of leather sawdust in asphalt micro-surface layer
mixtures and found it to be technically and economically
feasible. The incorporation of 0.3 % of CTLS has increased
the engineering properties of asphalt mixtures and minimized
the cracking of pavement surface layer due to the fiber incor-
poration in the asphalt micro-surface. Collagen hydrolysate of
CTLS waste reacted with diglycidyl ethers of bisphenol A
which leads to form biodegradable polymers that might facil-
itate recycling of plastic parts in products of the automotive
and/or aeronautics industry provided with protective films
(Langmaier et al. 2007). Protein hydrolysate produced by
enzymatic hydrolysis of CTLS wastes reacted with polyvinyl
alcohol for producing biodegradable plastics; application in
agriculture requires management of the breakdown of modi-
fied compounds of synthetic polymers which are used in
agriculture (Kresalkova et al. 2002).
Anaerobic digestion of protein hydrolysate for generation
of biogas
Collagen hydrolysate recovered from CTLS through chemical
process was fed to the anaerobic digester to generate biogas.
CTLSs were hydrolyzed by two different modes, i.e., using
lime and KOH followed by neutralization with HCl and
H3PO4 subsequently. COD reduction efficiencies of 34–
46 % and 45–54 % were observed in lime-HCl and KOH-
H3PO4 digesters, respectively. Gas generation is increased
30 % in KOH-H3PO4 digester as compared to that in Lime-
HCl, and CO2 in KOH-H3PO4 digester was in the range of
19–20 % as compared to that in Lime-HCl were it was 30–
40 %. Hence, it shows that CO2 produced by the acidogens is
effectively utilized by the methanogens in producing methane
gas and potassium and phosphates are the macronutrients for
the growth of microorganisms (Pati and Chaudhary 2013a).
Anaerobic biological degradation of protein hydrolysate

recovered from CTLS has cross-linked with higher molecular
weight diepoxides. Biodegradation of tested modified hydro-
lysate samples produced recorded quantities of biogas (CH4,
CO2). These modified hydrolysates were studied as materials
which have the potential to be used as good biodegradable
films, e.g., for agricultural applications (Hrncirik et al. 2009).
Plastics/rubber/resin
Successful commercial applications for the protein hydro-
lysate include its use in the manufacture of biodegradable
polymers for agriculture sowing tapes (Kolomaznik et al.
1999; Pearson 1982). There has been an increasing interest
in the development of biodegradable polymers owing to
the growing problem of waste disposal of plastics. Protein
hydrolysate is easily and uniformly blended with
metallocene-based linear low-density polyethylene
(mLLDPE), and the obtained polymer film retains me-
chanical strength properties and biodegradability behavior.
The hydrolysate is also used to modify biodegradable
plastics. The film based on polyvinyl alcohol (PVA) is
modified with protein hydrolysate to be used in agricul-
tural applications (Kresalkova et al. 2002; Saha et al.
2003b; Shin et al. 2007). The utilization of collagen as a
filler for isoprene and butadiene-acrylonitritle rubber mixes
was found to have good resistance to aging and also
provides increased recaptivities to microbiological decom-
position. The leather powder mixed with zinc oxide is the
best form of its addition to rubber mixes. The mechanical
properties of collagen-added carboxylated butadiene-
acrylonitrile rubber indicate an increase in tensile strength
and elongation at break (Przepiorkowska et al. 2003,
2004, 2005, 2006, 2007). The chrome wastes used as
filler in a polymer matrix and PVC–leather fiber compos-
ites were prepared due to their leather-like appearance.
The leather-like sheets are flexible and exhibit sufficient
water absorption to be suitable for several applications in
the footwear and clothing industry (Santana et al. 1998).
Further, the short leather fibers were modified by emulsion
polymerization of methyl methacrylate (MMA) in order to
increase the compatibility of leather fibers with several
commodity polymers used in shoe industries. The treat-
ment significantly improved the thermal stability of fibers
and reduced water adsorption capacity, as a coating of
PMMA is produced over the leather surface (Babanas
et al. 2001; Santana et al. 2002). By reacting hydrolysates
with glutaraldehyde, inexpensive UF adhesives were de-
veloped with reduced formaldehyde emissions (Langmaier
et al. 2003, a, b). The application of collagen hydrolysates
in the cross-linking of epoxide resins resulted in solvent-
free biodegradable epoxide films. Cross-linking of hydro-
lysate with epichlorhydrin is an advantage for applications
such as degradable packing materials.
Environ Sci Pollut Res
Biofertilizer
The protein hydrolysate recovered from CTLSs was utilized
as biofertilizer. Several plants can also take up and absorb
amino acids; these amino acids are sometimes better nitrogen
sources than ammonia or nitrate (Taylor et al. 1999; Ashmead
et al. 1986). Protein hydrolysate was recovered and channeled
as an organic nitrogenous fertilizer to increase the yield of the
crop (Kolomaznik et al. 1999). The combination of enzymatic
and acid hydrolysis resulted in tailor-made, predefined molec-
ular weight products fitting the intended use. Low molecular
weight products are used as the plant biostimulator
(Kasparkova et al. 2009). Protein hydrolysate was extracted
from natural plants or animal in fertilizer composition; these
represent substances with chelated micro-nutrient properties
important for plant metabolism. With numerous products
containing phosphates, polyphosphates, potassium, and nitro-
gen compounds, protein hydrolysates are used as fertilizers at
both in high culture and in intensive greenhouses and solari-
ums. Micro-elements like iron, copper, zinc, calcium, magne-
sium, and manganese chelated with hydrolyzed proteins are
more easily absorbed by both plant and animal organisms. It
also mentions use of protein hydrolysates in combination with
potassium polyphosphates to increase agricultural production
by increasing the absorption of phosphorus and potassium
(Sirbu et al. 2008, 2009; Ashmed and Hsu 1985). Katsifas
et al. (2004) reported an Aspergillus carbonarius which could
perform biodegradation of CTLS in solid-state fermentation
experiments, where 97 % liquefaction of the tannery waste
was achieved and the liquid obtained from long-term experi-
ments was used to recover chromium and proteinaceous liquid
fertilizer. Collagen hydrolysates obtained by chemical and
chemical-enzymatic processes under moderate reaction con-
ditions were used in preparing foliar fertilizers (Gaidau et al.
2007, 2008). Hydrolysates of CTLSs are used as nitrogen
source for growth of common bean plants (Lima et al.
2010). Oliveira et al. (2008b) have studied the use of leather
waste after chromium extraction (collagen) as a nitrogen
source to elephantgrass. CTLS wastes include the highest
amount of nitrogen (64 %). Chrome in these shaving wastes
may be removed to a great extent by treating the samples with
alkali or with the help of enzymes(Taylor et al. 1990, 1992,
1997b). Chrome content in the protein hydrolysates derived
from CTLS may be <5 ppm; hence, it can be used as a
fertilizer.
Protein hydrolysate for making animal feed/chicken feed
It is possible to transform recovered materials from
CTLS wastes into feed proteins. Hydrolyzed protein, be-
cause of its high-nitrogen content, has potential applica-
tions as animal feed additive, which provides food supple-
ment amino acids (Bataille et al. 1983; Brown et al. 1996;
Environ Sci Pollut Res
Hauck 1974; Smith and Donovan 1982; Langmaier et al.
1999, 2001). It is possible to produce an almost chromium-
free leather meal (less than 0.1 ppm Cr), which is high in
protein with a high digestibility. Its amino acid pattern is of
a better quality than that in feather meal and is equal to
those in meat meal and soybean meal with regard to cost
competitiveness. Recovered protein was also used as food
supplement for Tilspia oreochromis niloticus (Boushy et al.
1991; Chakraborty and Sarkar 1999; Katsifas et al. 2004;
Langmaier et al. 2002; Montoneri et al. 1994; Nogami et al.
2000; Reis and Beleza 1991). The hydrolysates of CTLSs
were used as leather meal, which is hydrolyzed in a similar
manner to poultry feathers and used as a supplemental
protein source for livestock (Taylor et al. 1999). Alkaline
protein hydrolysate is preferred to be neutralized with
phosphoric acid because of the equivalence of calcium
phosphates to bone meal. Riaz and Alam (2006) have
studied the growth performance of quail chicks with differ-
ent levels of CTLS feeding. Enhanced body weight of the
quail chicks were found at 2.5 and 5 % of CTLS feed. The
protein content present in CTLS are often used in the
manufacture of poultry feed along with corn flour. It was
found, after an analysis of the poultry feed collected from
different chicken shops, that the samples contained very
high concentration of chromium. Chickens that ate the feed
were often found to have high levels of chromium in dif-
ferent parts of the body. The use of the leather wastes as
chicken feed was a good alternative, provided that the
chromium and other toxic substances were properly re-
moved (Sudha 2010). The hydrolysis of CTLS wastes un-
der suitable conditions and in the presence of better hydro-
lyzing agents can help us in recovering the value-added
products which are used as ingredients in poultry feed
(Sudha et al. 2011; Alves and Beleza 1991a, b).
Biological uses: medical application
High value-added, industrially reusable bioproducts whose
application areas could include veterinary medicine, medicine,
and pharmacology were isolated from CTLSs (Cot et al.
1986). Biopolymers were prepared from protein hydrolysates
of CTLS wastes and its application in tissue engineering
within fields such as cosmetics, medicine, or veterinary (Cot
et al. 2009; Catalina et al. 2011b). Composite films were made
using sago starch (SG), soya protein (SY), and collagen (C)
and were cross-linked with glutaraldehyde (GA). The com-
posite films prepared were used as wound dressing material on
the experimental wounds of rats and revealed better wound
healing capacity (Ramnath et al. 2012). Shanthi and Shelly
(2003) established the usefulness of the collagen hydrolysate
from chrome shavings as a support matrix for immobilization
of organophosphorus hydrolyze enzyme. The collagen
hydrolysate represents a good mixture and a good source of
amino acids as a carbon and nitrogen source (Aslan et al.
2007).
Cosmetics/films
Cakl et al. (1998) have attempted to use high-purity and
demineralized protein hydrolysates in cosmetics (e.g.,
moisturizing creams, lotions, and hair sprays) and bio-
medical products (e.g., burn dressings and implant cov-
erings). The hydrolytic products from collagen, such as
technical gelatin and animal glue, were used as eco-
friendly adhesives, paints, encapsulating agents, floccu-
lating agents, and fireproofing agents. The gelatin was
used in the application of microencapsulation to micro-
encapsulate drugs, essential oils, perfumes, and other
materials. Depending on the application of the gelatin,
different modifiers can be used to get the desired func-
tional proper ties. Films were prepared from commercial
gelatins by enzymatic treatment and glycerol as a plas-
ticizer to be used in the preparation of coatings, edible
films, and packaging material. The addition of polyvinyl
alcohol further improved the tensile strength and me-
chanical properties of films, which were biodegradable
(Cabeza et al. 1998a, b, c, d, 1999a, b, c; Taylor et al.
1995, 1997a, b, 1998, 2001, 2002, 2003). Modified
protein hydrolysates have potential to be used as good
biodegradable films, e.g., agriculture applications
(Hrncirik et al. 2009). Gelatin was extracted from
chrome-tanned leather waste with the aim to produce a
durable coating or film. Cross-linking has shown to
improve the physical performance of a film/coating
(Catalina et al. 2011a). The hybrid biodegradable films
are from collagenous wastes and natural polymers for
biomedical applications. Protein was extracted from skin
waste using acetic acid and blended with starch (ST)/
soy protein (SP) to prepare C/ST/SP hybrid films. It
was envisaged that the promising mechanical, thermal,
swelling, biostability, and biocompatibility properties of
the developed hybrid films suggest a beneficial role for
the biomedical applications (Murali et al. 2011).
Conclusion
The leather industry is as such a sustainable solution provider
for the meat in terms of disposal of raw hides/skins. Most of
the solid waste generated from tannery industries is presently
unutilized and wasted. Leather wastes can be processed at
industrial scales to generate value-added products, which
can emerge as an important commercial activity on its own
while eliminating environmental concerns of the leather

process industry. The growing environmental concerns pose a
new challenge to tanners and leather chemists, calling for
renewed research and development to facilitate sustenance
of the traditional industry. Generation of industrial
bioproducts and development of biomedical applications for
some of them would ensure higher profitability for leather
making and lead to the development of new economic models
exclusively for waste processing. In this path of journey, the
main product “leather” may become the by-product and
“waste” would be the main product of the leather industry.
References
Abreu MA, Toffoli SM (2009) Characterization of a chromium-rich
tannery waste and its potential use in ceramics. Ceram Int 35:
2225–2234
Afsar A, Gulumser G, Aslan A, Ocak B (2010) A study on usability of
collagen hydrolysate along with oxazolidine in leather processing. J
Textile Apparel 20:37–40
Agrawal A, Kumar V, Pandey BD (2006) Remediation options for
the treatment of electroplating and leather tanning effluent
containing chromium-a review. Miner Process Extra Metal
Rev 27:99–130
Alves Dos Reis M, Beleza V (1991a) Utilization of leather waste: animal
feedstuff from chrome shavings, part I. J Soc Leather Technol Chem
75(1):15–19
Alves Dos Reis M, Beleza V (1991b) Utilization of leather waste: Animal
feedstuff from chrome shavings, part II. J Soc Leather Technol
Chem 75(2):45–47
Amir S, Benlboukht F, Cancian N, Winterton P, Hafidi M (2008) Physico-
chemical analysis of tannery solid waste and structural characteri-
zation of its isolated humic acids after composting. J Hazard Mater
160:448–455
Andre N, Paut O, Arditti J, Fabre P, Bremond V, Alhmana T, Bellus JF,
Jouglard J, Camboulives J (1998) Severe potassium dichromate
poisoning after accidental nasal introduction. Arch Pediatr 5:145–
148
Ashmead HD, Ashmead HH, Miller GW, Hsu HH (1986) Foliar feeding
of plants with amino acids chelates. Park Ridge. NJ: Noyes publi-
cations 370 page
Ashmed HH, Hsu HH (1985) Potassium polyphosphate protein hydroly-
sate fertilizer. US Patent 4491464
Ashokkumar M, Thanikaivelan P, Murali R, Chandrasekaran B (2010)
Preparation and characterization of composite sheets from collage-
nous and chromium-collagen complex wastes using polyvinylpyr-
rolidone: Two Problems, One Solution. Waste Biomass Valor 1(3):
347–355
Ashokkumar M, Thanikaivelan P, Krishnaraj K, Chandrasekaran B
(2011) Transforming chromium containing collagen wastes into
flexible composite sheets using cellulose derivatives: Structural,
thermal, and mechanical investigations. Polym Compos 32(6):
1009–1017
Aslan A, Gulumser G, Ocak B (2006) Increased chromium tanning
efficiency with collagen hydrolysates. J Soc Leather Technol
Chem 90:201–204
Aslan A, Karavana HA, Gulumser G, Yasa I, Cadirci BH (2007)
Utilization of collagen hydrolysate in keratinase production from
Bacillus subtilisATCC6633. J Am Leather Chem Assoc 102:129–
134
Environ Sci Pollut Res
Babanas K, Tarantili PA, Andreopoulos AG (2001) Plasticized poly
(vinyl chloride) filled with waste leather particles. J Elastomers
Plast 33:72–85
Basak N, Vibhavari S (2003) Isolation of protein products from chrome
shavings by acidic treatment: a study. J Indian Leather Technol
Assoc 53:935–940
Bataille P, Gagnon F, Smith WE (1983) Upgrading leather and felt scrap
into proteins. J Am Leather Chem Assoc 78:328–337
Berry FJ, Costantini N, Smart LE (2001) Recovery and reuse of chromi-
um from leather shavings: formation of chromium-containing ce-
ramic pigments. J Am Leather Chem Assoc 96:46–53
Berry FJ, Costantini N, Smart LE (2002) Synthesis of chromium pig-
ments from chromium recovered from leather waste. Waste Manag
22:761–772
Bielicka A, Bojanowska I, Wi’sniewski A (2005) Two faces of chromi-
um—pollutant and bio element. Pol J Environ Stud 14(1):5–10
Boushy ARE, Poel AFBV, Koene JIA, Dieleman SH (1991)
Tanning waste by-product from cattle hides, its suitability as a
feedstuff. Bioresour Technol 35:321–323
Bowden W (2003) Gasification: Achieving zero waste. J Am Leather
Chem Assoc 98:19–26
Brasack I, Bottcher H, Hempel U (2000) Biocompatibility of modified
silica-protein composite layers. J Sol-Gel Sci Technol 19:479–482
Brown EM, Thompson CJ, Taylor MM (1994) Molecular size and
conformation of protein recovered from chrome shavings. J Am
Leather Chem Assoc 89:215–220
Brown EM, Taylor MM, Marmer WN (1996) Production and potential
uses of co-products from solid tannery waste. J Am Leather Chem
Assoc 91:270–276
Cabeza LF, Taylor MM, Brown EM, Marmer WN (1997) Influence of pepsin
and trypsin on chemical and physical properties of isolated gelatin from
chrome shavings. J Am Leather Chem Assoc 92:200–207
Cabeza LF, McAloon AJ, Yee WC, Taylor MM, Brown EM, Marmer
WN (1998a) Process simulation and cost estimation of treatment of
chromium-containing leather waste. J Am Leather Chem Assoc 93:
299–315
Cabeza LF, Taylor MM, Brown EM, Marmer WN (1998b) Chemical and
physical properties of protein products isolated from chromium-
containing leather waste using two consecutive enzymes. J Soc
Leather Technol Chem 82:173–179
Cabeza LF, Taylor MM, DiMaio GL, Brown EM, Marmer WN, Carrio R,
Celma PJ, Cot J (1998c) Processing of leather waste: pilot scale
studies on chrome shavings. Isolation of potentially valuable protein
products and chromium. Waste Manag 18:211–218
Cabeza LF, Taylor MM, DiMaio GL, Brown EM, Marmer WN, Carrio R,
Celma PJ, Cot J (1998d) Processing of leather waste: pilot scale
studies on chrome shavings. Part II. Purification of chrome cake and
tanning trials. J Am Leather Chemical Assoc 93:83–98
Cabeza LF, Clauson SM, Taylor MM, Brown EM, Marmer WN,
Merck KB (1999a) The effect of surfactants on the isolation
of protein products from chromium-containing solid tannery
waste: influence on the process and on the chemical, physical
and functional properties of the resultant gelatin. J Am
Leather Chem Assoc 94:190–198
Cabeza LF, Taylor MM, Brown EM, Marmer WN (1999b) Potential
applications for Gelatin isolated from chromium-containing solid
tannery waste: Microencapsulation. J Am Leather Chem Assoc 94:
182–189
Cabeza LF, Taylor MM, Brown EM, Marmer WN (1999c) Isolation
of protein products from chromium-containing leather waste
using two consecutive enzymes and purification of final chro-
mium product: Pilot plant studies. J Soc Leather Technol Chem
83:14–19
Cabeza LF, Taylor MM, Brown EM, Marmer WN, Carrio R, Grau E,
Celma PJ, Cot J, Manich M (1999d) Treatment of sheep skin chrome
shavings. Isolation of high value protein products and reuse of
Environ Sci Pollut Res
chromium in the tanning process. J Am Leather Chem Assoc 94:
268–287
Cabeza LF, Taylor MM, DiMaio GL, Brown EL, Marmer WN, Carrio R,
Celma PJ, Cot J (1999e) Cost effective processing of leather waste:
pilot scale studies on chrome shavings from cattle hides and sheep
skins isolation of potentially valuable protein products and utiliza-
tion of recovered chromium. XXV IULTCS Congress India
(Chennai) Waste Manage Technol pp 465-472
Cakl J, Sir J, Medvedikova L, Blaha A (1998) Demineralization of
protein hydrolysates from enzymatic hydrolysis of leather shavings
using membrane diafilteration. Sep Sci Technol 33:1271–1281
Calder LM (1988) Chromium contamination of groundwater. In: Nriagu
JO, Nieboer E (eds) Chromium in Natural and Human
Environments. Wiley Interscience, New York, pp 215–231
Cantera CS (2003) Adding value to chrome shavings: hydrolysates as
retanning materials. World Leather 16:27–29
Cantera CS, De Giuste M, Sofia A (1997) Hydrolysis of chrome shav-
ings: application of collagen hydrolysate and “acrylic–protein” in
post tanning operations. J Soc Leather Technol Chem 81:183–191
Cantera CS, Goya L, Mingo R (1999) Collagen hydrolysate: ‘soluble
skin’ applied in post tanning processes Part 1: Characterization. J
Soc Leather Technol Chem 84:29–37
Cantera CS, Martegani J, Esterelles G, Vergara J (2002) Collagen hy-
drolysate: ‘soluble skin’ applied in post tanning processes Part 2:
Interaction with acrylic retanning agents. J Soc Leather Technol
Chem 86:195–202
Cao J, Lu Y, Chang G, Tang K (2005) Glutaraldehyde modification
of collagen hydrolysate obtained from chrome shavings. J Am
Leather Chem Assoc 100:265–272
Carneiro S, Almeida MF, Ferreira MJ (2003) Factors influencing chro-
mium recovery from chromium sulphate tanned leather scrap ashes.
J Soc Leather Technol Chem 87:1–10
Catalina M, Attenburrow GE, Cot J, Covington AD, Antunes, APM
(2008) Application of gelatin extracted from chrome-tanned waste
as a finishing agent for leather.4th Freiberg Collagen Symposium,
Freiberg, Germany, September11-12
Catalina M, Attenburrow GE, Cot J, Covington AD, Antunes APM
(2010) Application of gelatin extracted from chrome shavings for
the glazed finishing of leather. J Am Leather Chem Assoc 105(5):
138–174
Catalina M, Attenburrow GE, Cot J, Covington AD, Antunes APM
(2011a) Influence of crosslinkers and crosslinking method on the
properties of gelatin films extracted from leather solid waste. J Appl
Polym Sci 119(4):2105–2111
Catalina M, Celma P, Cot J, Manich A, Marsal A (2011b) Tailor-made
biomaterials from collagenic wastes. J Am Leather Chem Assoc
106:153–160
Chabaane L, Tahiri S, Albizane A, Krati ME, Cervera ML, de la Guardia
M (2011) Immobilization of vegetable tannins on tannery chrome
shavings and their use for the removal of hexavalent chromium from
contaminated water. Chem Eng J 174:310–317
Chakraborty R (2003) Ecofriendly solid waste management in the leather
industry. Environmental biotechnology newsletter, University of
Kalyani, India 3, 2
Chakraborty R (2004) Optimization of hydrolysis of chrome shav-
ings by enzyme from P Lilacinus. J Am Leather Chem
Assoc 99:103–109
Chakraborty R, Sarkar SK (1999) Eco-friendly biofertilizer from solid
waste. Proc. XXV IULTCS Congress, India (Chennai) Waste
Manage Technol pp 481-483
Chen W, Cooke PH, DiMaio G, Taylor MM, Brown EM (2001) Modified
collagen hydrolysate, potential for use as a filler for leather. J Am
Leather Chem Assoc 96:262–267
Chen J, Wey MY, Chiang B, Hsieh S (2003) The simulation of hexavalent
chromium formation under various incineration conditions.
Chemosphere 36(7):1553–1564
Chrońska-Olszewska K, Przepiórkowska A (2011) A mixture of buffing
dust and chrome shavings as a filler for nitrile rubbers. J Appl Polym
Sci 122(5):2899–2906
Cieslak-Golonka M (1996) Toxic and mutagenic effects of chromium
(VI). Polyhedron 15:3667–3918
Cot J, Aramon C, Baucells M, Lacort G, Roura M (1986) Waste
processing in the tannery: production of gelatin, Reconstituted
collagen and glue from chrome-tanned leather splits and trim-
mings subjected to a modified detanning process. J Soc Leather
Technol Chem 70:69–76
Cot J, Manich AM, Marsal A, Fort M, Celma PJ, Carrio R, Choque R,
Cabeza LF (1999) Processing of collagenic residues isolation of
gelatin by the action of peroxochromates. J Am Leather Chem
Assoc 94:115–128
Cot J, Catalina M, Celma P, Manich A, Marsal A (2009) Taylor-made
biomaterials from collagenic wastes: feasible link between
tanning industry and tissue engineering.XXX, IULTCS, China
pp 257-264
Crispim A, Mota M (2003) Leather shavings treatment: an enzymatic
approach. J Soc Leather Technol Chem 87:203–207
Das AP, Singh S (2011) Occupational health assessment of chromite
toxicity among Indian miners. Indian J Occup Environ Med 15:6–13
Deng D, Liao X, Shi B (2008) Synthesis of porous carbon fibers from
collagen fiber. ChemSusChem 1:298–301
Dettmer A, Nunes KGP, Gutterres M, Marcílio NR (2012) Production of
basic chromium sulfate by using recovered chromium from ashes of
thermally treated leather. J Hazard Mater 176:710–714
Dhal B, Thatoi HN, Das NN, Pandey BD (2013) Chemical and microbial
remediation of hexavalent chromium from contaminated soil and
mining/metallurgical solid waste: A review. J Hazard Mater 250–
251:272–291
Dvorackova M, Julinova M, Mikulcakova H, Kupec J (2007) Testing
aerobic degradation of the protein portion of filter cake after filtra-
tion of chrome tanned waste. J Am Leather Chem Assoc 102:77–84
Edmund FJJR, Bohdan A, Stephen HF (2003) Polymer-leather compos-
ites. J Appl Polym Sci 26:463–487
Erdem M (2006) Chromium recovery from chrome shaving generated in
tanning process. J Hazard Mater B129:143–146
Fathima N, Madhan B, Rao JR, Nair BU, Ramasami T (2004) Interaction
of aldehydes with collagen: Effect on thermal, enzymatic and con-
formational stability. Int J Biol Macromol 34:241–247
Fengxia C, Hanbo Z, Yahong Z, Weihua L, Xianyong J (2005)
Preparation of chrome liquor using chrome shavings as reducing
agent. J Am Leather Chem Assoc 100:217–224
Ferreira MJ, Almeida MF, Pinho SC, Santos IC (2010) Finished leather
waste chromium acid extraction and anaerobic biodegradation of the
products. Waste Manag 30(6):1091–1100
Filibelix A, Buyukkamaci N, Senol H (2000) Solidification of tannery
wastes. Resour Conserv Recycl 29:251–261
Gaidau C, Ghiga M, Stepan E, Taloi D, Filipescu L (2007) Bioactive
protein-based additives and new materials obtained from leather
manufacture by-products. XXIX, IULTCS Congress, Washington
June 20-24
Gaidau C, Ghiga M, StepanE, LacatusV, Cirjaliumurgea M, Ionita
AD, Filipescu L (2008) Emulsified foliar fluids from waste
leather hydrolysis products. Ceex conference, proceedings Romania
pp 1–7
Gaidau C, Niculescu M, Stepan E, Taloi D, Filipescu L (2009) Additives
and advanced biomaterials obtained from leather industry by-
products. Rev Chim 60:501–507
Galatik A, Duda J, Minarik L (1988) Pressure hydrolysis of leather waste
with sodium hydroxide. Czech Patent CS 252382
Gammoun A, Tahiri S, Albizane A, Azzi M, Moros J, Garrigues S,
Guardia MDL (2007a) Separation of motor oils, oily wastes and
hydrocarbons from contaminated water by sorption on chrome
shavings. J Hazard Mater 145:148–153

Gammoun A, Tahiri S, Albizane A, Azzi M, Guardia MDL (2007b) De-
contamination of water polluted with oil through the use of tanned
solid wastes. J Environ Eng Sci 6:553–559
Germann HP (1999) The ecology of leather production—present state
and development trends, science and technology for leather into the
next millennium. Proc XXV IULTCS Congress. McGraw-Hill
Publishing Company Ltd., India (New Delhi), p 283
Gish AJ (1999) Leather board, a practical use of tannery offal. J Am
Leather Chem Assoc 94:43–47
Guardini G (1983) Extraction of proteins and chromium sulphate from
chromium tanned-skin wastes. US 4483829
Gyurko I, Czeininger C, Mosko K, Nagy F (1985) Sound-insulating
leather powder compositions. US 4544676
Hauck RA (1974) Some notes on utilization of fleshings and blue shav-
ings. J Am Leather Chem Assoc 69:195–203
Heidemann E (1991) Disposal and recycling of chrome-tanned materials.
J Am LeatherChem Assoc 86:331–333
Holloway DF (1978) Recovery and Separation of Nutritious Protein
Hydrolysates and Chromium from Chrome Leather Scrap. US
4100154
Hrncirik J, Dvorackova M, Hruska F, Kupec J, Kolomaznik K (2005)
Kinetics of alkaline hydrolysis of the insoluble protein fraction
following enzymatic hydrolysis of chrome-tanned shavings. J Am
Leather Chem Assoc 100:1–7
Hrncirik JH, Pseja J, Kupec J, Noskova R, Olsak J (2009) Anaerobic
biological degradation of protein hydrolysate cross-linked with
higher-molecular weight diepoxides. J Am Leather Chem Assoc
104:36–45
Huang X, Liao X, Shi B (2009) Adsorption removal of phosphate in
industrial wastewater by using metal-loaded skin split waste. J
Hazard Mater 166:1261–1265
IARC (International Agency for Research on Cancer), IARC monographs
on the evaluation of carcinogenic risks to humans: overall evaluation
of carcinogenicity (1987) An updating of IARC Monographs, vols.
1–42, Supplement 7, WHO, Lyon, France
Imai T, Okamura H (1991) Studies on incineration of chrome leather
waste. J Am Leather Chem Assoc 86:281–294
Ioaninides TA, Zouboulis J (2003) Detoxification of a highly toxic lead-
loaded industrial solid waste by stabilization using apatites. J Hazard
Mater B97:173–191
Jiao L, Liao X, Shi B (2009) Adsorptive removal of As(V) from aqueous
solution by Zr(IV) loaded skin shavings. J Am Leather Chem Assoc
104:308–315
Kanojia RK, Junaid M, Murthy RC (1998) Embryo and fetotoxicity of
hexavalent chromium: a long-term study. Toxicol Lett 95:165–172
Kantarli IC, Yanik J (2010) Activated carbon from leather shaving wastes
and its application in removal of toxic materials. J Hazard Mater
179:348–356
Kasparkova V, Burketova L, Kolomaznik K, Sasek V, Simek L (2009)
Characterization of low-molecular weight collagen hydrolysates
prepared by combination of enzymatic and acid hydrolysis. J Am
Leather Chem Assoc 104:46–51
Katsifas EA, Giannoutsou E, Lambraki M, Barla M, Karagouni AD
(2004) Chromium recycling of tannery waste through microbial
fermentation. J Ind Microbiol Biotechnol 31:57–62
Kirk DW, Chan CCY, Marsh H (2002) Chromium behavior
during thermal treatment of MSW fly ash. J Hazard Mater
90(1):39–49
Kolomaznik K, Mladek M, Langmaier F, Janacova D, Taylor MM (1999)
Experience in industrial practice of enzymatic dechromation of
chrome shavings. J Am Leather Chem Assoc 94:55–63
Kolomaznik K, Mladek M, Langmaier F, Shelly DC, Taylor MM (2003)
Closed loop for chromium in tannery operation. J Am Leather Chem
Assoc 98(12):487–490
Kolomaznik K, Adamek M, Uhlirova M (2007) Potential danger of
chromium tanned wastes. Proceedings of the 5th IASME/WSEAS
Environ Sci Pollut Res
Int. Conference on Heat Transfer, Thermal Engineering and
Environment, Athens, Greece, August 25-27 pp 137-141
Kolomaznik K, Adamek M, Andel I, Uhlirova M (2008) Leather waste:
potential threat to human health, and a new technology of its
treatment. J Hazard Mater 160:514–520
Kong J, Yue Q, Huang L, Gao Y, Sun Y, Gao B, Li Q, Wang Y (2013)
Preparation, characterizationand evaluation of adsorptive properties
of leather waste based activated carbon via physical and chemical
activation. Chem Eng J 221:62–71
Kosmac VSE, Gantar A, Anzur I (1995) Modification of collagen hydro-
lysates. Resour Conserv Recycl 13:97–104
Kotas J, Stasicka Z (2000) Chromium occurrence in the environment and
methods of its speciation. Environ Pollut 107:263–283
Kresalkova M, Hnanickova L, Kupec J, Kolomaznik K, Alexy P (2002)
Application of protein hydrolysate from chrome shavings for poly-
vinyl alcohol-based biodegradable material. J Am Leather Chem
Assoc 97:143–149
Krishnani KK, Ayyappan S (2006) Heavy metals remediation of water
using plants and lignocellulosic agrowastes. Rev Environ Contam
Toxicol 188:59–84
Krummenauer K, Andrade JJDO (2009) Incorporation of chromium
tanned leather residue to asphalt micro-surface layer. Constr Build
Mater 23:574–581
Kupec J, Dvorackova M, Rudlova S, Ruicka J, Kolomaznik K (2002) De-
proteination of chrome waste by washing and enzymatic hydrolysis.
J Am Leather Chem Assoc 97:349–354
Lakrafli H, Tahiri S, Albizane A, Otmani MEE (2012) Effect of wet blue
chrome shaving and buffing dust of leather industry on the thermal
conductivity of cement and plaster based materials. Constr Build
Mater 30:590–596
Langmaier F, Kolomaznik K, Sukop S, Mladek M (1999) Products of
enzymatic decomposition of chrome-tanned leather waste. J Soc
Leather Technol Chem 83:187–195
Langmaier F, Stibora M, Mladek M, Kolomaznik K (2001) Gel-sol
transitions of chrome tanned leather waste hydrolysate. J Soc
Leather Technol Chem 85:100–105
Langmaier F, Mladek M, Kolomaznik K, Sivarova J, Sukop S (2002)
Calorimetry of the reactions of hydrolysates of chromed shavings
with aldehydes. J Therm Anal Calorim 67:659–666
Langmaier F, Kolomaznik K, Mladek M (2003) Modifying products of
enzymatic breakdown of chrome-tanned leather wastes with glutar-
aldehyde. J Soc Leather Technol Chem 87:55–61
Langmaier F, Sivarova J, Kolomaznik K, Mladek M (2004a) Curing of
urea-formaldehyde adhesives with collagen type hydrolysates under
acid condition. J Therm Anal Cal 76:1015–1023
Langmaier F, Sivarova J, Mladek M, Kolomaznik K (2004b)
Curing adhesives of urea: formaldehyde type with collagen
hydrolysates of chrome-tanned leather waste. J Therm Anal
Calorim 75:205–219
Langmaier F, Mokrejs P, Karnas R, Mladek M, Kolomaznik K
(2006) Modification of chrome-tanned leather waste hydroly-
sate with epichlorhydrin. J Soc Leather Technol Chem 90:29–
34
Langmaier F, Mokrejs P, Kolomaznik K, Mladek M, Karnas R (2007)
Cross-linking epoxide resins with hydrolysates of chrome-tanned
leather waste. J Therm Anal Calorim 88:857–862
Langmaier F, Mokrejs P, Kolomaznik K, Mladek M (2008) Plasticizing
collagen hydrolysate with glycerol and low-molecular weight poly
(ethyleneglycols). Thermochim Acta 469:52–58
Lazau RI, Pacurariu C, Becherescu D, Ianos R (2007) Ceramic pigments
with chromium content from leather wastes. J Eur Ceram Soc 27:
1899–1903
Lima DQ, Oliveira LCA, Bastos ARR, Carvalho GS, Marques JGSM,
Carvalho JG, de Souza GA (2010) Leather industry solid waste as
nitrogen source for growth of common bean plants. Appl Environ
Soil Sci 2010:1–7
Environ Sci Pollut Res
Lipsett VA (1982) Offal blue: Sources and current deposition of chrome
offals. J Am Leather Chemical Assoc 77:291–301
Lollar RM (1981) Potential uses of tanned collagen. J Am Leather Chem
Assoc 76:192–193
Losi ME, Amrhein C, Frankenberger JRWT (1994) Environmental bio-
chemistry of chromium. Rev Environ Contam Toxicol 136:91–131
Maire MS, Lipsett VA (1980) Offal enhancement. J Am Leather Chem
Assoc 75(1):16–33
Malek A, Hachemi M, Didier V (2009) New approach of depollution
of solid chromium leather waste by the use of organic chelates:
economical and environmental impacts. J Hazard Mater 170:156–162
Marcilla A, García AN, León M, Martínez P, Bañón E (2011) Study of the
influence of NaOH treatment on the pyrolysis of different leather
tanned using thermogravimetric analysis and Py/GC–MS system. J
Anal Appl Pyrolysis 92(1):194–201
Marsal A, Elena Bautista M, Manich AM, Cuadros S, Maldonado F (2013)
Use of modified leather shavings in the adsolubilization of 2-naphthol:
thermodynamic and kinetics studies. Chem Eng J 222:77–84
Martinelango K, Shelly DC (2004) Multidimensional analysis of magne-
sium oxide hydrolysis of wet-blue shavings. J Am Leather Chem
Assoc 99:258–268
Miretzky P, Fernandez Cirelli A (2010) Cr(VI) and Cr(III) removal from
aqueous solution by raw and modified lignocellulosic materials: a
review. J Hazard Mater 180:1–19
Mohamed OA, Taha GM, El-Sayed NH (2013) Technical gelatin from
chrome tanned shavings. Int J Environ Waste Manag 11(4):335–349
Montoneri E, Rizzi G, Rizzi A, Mordenti A, Bauli A, Riolfatti M, Pelle-
grini L (1994) Hydrolysis of tannery wastes to protein meal for
animal feed-stuffs: a process and product evaluation. J Chem
Technol Biotechnol 59:91–99
Mordenti A, Piva G (1997) Chromium in animal nutrition and possible
effects on human health. In: Canali S, Tittarelli F, Sequi P (eds)
Chromium Environmental Issues. Franco Angeli s.r.l, Milan, pp
131–151
Mu C, Lin W, Zhang M, Zhu Q (2003) Towards zero discharge of
chromium-containing leather waste through improved alkali hydro-
lysis. Waste Manag 23:835–843
Mukherjee G, Chakraborty S, Biswas GK, Basu SK (2005) Chromium
tanned leather and its environmental impact. J Indian Leather
Technol Assoc 55:239–246
Munoz JM, Maldonado MV, Rangel AS (2002) Development of a tan-
ning process based on using hydrolyzated material collected from
leather scrap. J Am Leather Chem Assoc 97:83–87
Murali R, Anumary A, Ashokkumar M, Thanikaivelan P,
Chandrasekaran B (2011) Hybrid biodegradable films from collag-
enous wastes and natural polymers for biomedical applications.
Waste Biomass Valor 2(3):323–335
Na ZM, Pin LX, Bi S (2006) Adsorption of surfactants on chromium
leather waste. J Soc Leather Technol Chem 90:1–6
Narasimhan K, Sehgal PK, Joseph KT (1980) Condensation of aromatic
sulfonic acid with hydrolysates from leather wastes. J Am Leather
Chem Assoc 75:211–215
Nashy ESHA, Al-Ashkar E, Abdel Moez A (2012) Optical and spectro-
scopic studies on tannery wastes as a possible source of organic
semiconductors. Spectrochim Acta A:Mol Biomol Spectro 86:33–
38
Nogami EM, Kimura CCM, Malagutti AR, Galli D, Gallo D, Castilho TJ,
Rodrigues C, Nozaki J (2000) Recovery of protein from chrome
shavings and application as a food supplement for Tilapia
Oreochromis Niloticus. J Am Leather Chem Assoc 95:119–124
Ocak B, Aslan A, Gulumser G (2011) Utilization of Chromium-tanned
leather solid wastes in microencapsulation. J Am Leather Chem
Assoc 106:232–238
Okamura H, Shirai K (1972) Basic studies on the manufacture of leather
board from chrome collagen fiber. J Am Leather Chem Assoc
67:148–162
Okamura H, Shirai K (1976) Recovery of chromium from shavings by
wet air oxidation. J Am Leather Chem Assoc 71:173–179
Oliveira LCA, Gonçalves M, Oliveira DQL, Guerreiro MC, Guilherme
LRG, Dallago RM (2007) Solid waste from leather industry as
adsorbent of organic dyes in aqueous-medium. J Hazard Mater
141(1):344–347
Oliveira DQL, Gonçalves M, Oliveira LCA, Guilherme LRG (2008a)
Removal of As(V) and Cr(VI) from aqueous solutions using solid
waste from leather industry. J Hazard Mater 151(1):280–284
Oliveira DQL, Carvalho KTG, Bastos ARR, Oliveira LCA, Melo
Marques JJG DSe, Nascimento RS DMPd (2008b) Use of leather
industry residues as nitrogen sources for elephantgrass. Brazilian
Soc Soil Sci 32:417–424
Oliveira LCA, Guerreiro MC, Gonçalves M, Oliveira DQL, Costa LCM
(2008c) Preparation of activated carbon from leather waste: a new
material containing small particle of chromium oxide. Mater Lett 62:
3710–3712
Oliveira LCA, Coura CVZ, Guimaraes IR, Goncalves M (2011) Removal
of organic dyes using Cr-containing activated carbon prepared from
leather waste. J Hazard Mater 192(3):1094–1099
Oppelt ET (1990) Air emission from the incineration of hazardous waste.
Toxicol Ind Health 6:23–31
Oppelt ET, Dempsey CR (1993) Incineration of hazardous waste: a
critical review update. J Air Waste Manage Assoc 43:25–73
Parvathi MS, Suseela K, Nanda SC (1986a) Hydrolytic action of
Pseudomonas aeruginosa on chrome shavings. Leather Sci 33:8–11
Parvathi MS, Suseela K, Nanda SC (1986b) Purification and properties of
Pseudomonas aeruginosa protease causing hydrolysis of chrome
shaving. Leather Sci 33:303–307
Pati A, Chaudhary R (2013) Studies on the generation of biogas from
collagen hydrolysate obtained from chrome shavings by alkaline
hydrolysis: a greener disposal method. Res J Recent Sci 2(1):234–
240
Pati A, Chaudhary R, Subramani S (2013) Biochemical method for
extraction and reuse of protein and chromium from chrome leather
shavings: a waste to wealth approach. J Am Leather Chem Assoc
108:365–372
Pearson CL (1982) Animal glue in industry and the use of chrome-tanned
hide collagen in the production of animal glue. J Am Leather Chem
Assoc 77:306–311
Piccin JS, Gomes CS, Feris LA, Gutterres M (2012) Kinetics and iso-
therms of leather dye adsorption by tannery solid waste. Chem Eng J
183:30–38
Pillai P, Archana G (2012) A novel process for biodegradation and
effective utilization of chrome shavings, a solid waste generated in
tanneries, using chromium resistant Bacillus subtilis P13. Process
Biochem 47(12):2116–2122
Popescu C, Budrugeac P, Wortmann FJ, Miu L, Demco DE, Baius
M (2008) Assessment of collagen-based materials which are
supports of cultural and historical objects. Polym Degrad
Stab 93:976–982
Poulopoulou VG, Katakis D, Vrachnou E (1998) A method for the
removal of chromium from tanned leather wastes. J Air Waste
Manage Assoc 48:846–852
Przepiorkowska A, Janowska G, Slusarski L, Wolniak S (2003) Leather
powder as an agent for removing environmentally hazardous organ-
ic compounds. J Soc Leather Technol Chem 87:223–226
Przepiorkowska A, Prochon M, Zaborski M (2004) Use of waste collagen
as a filler for rubber compounds. J Soc Leather Technol Chem 88:
223–227
Przepiorkowska A, Prochon M, Zaborski M, Zakowska Z, Piotrowska M
(2005) Biodegradable protein-containing elastomeric vulcanizates.
Rubber Chem Technol 78:868–878
Przepiorkowska A, Chronska K, Prochon M, Zaborski M (2006) New
possibilities for managing the leather industry wastes. Przem Chem
85:971–975

Przepiorkowska A, Chronska K, Zaborski M (2007) Chrome-tanned
leather shavings as a filler of butadiene–acrylonitrile rubber. J
Hazard Mater 141(1):252–257
Qiang X, Feng H (2011) Collagen extracted from chrome shavings using
alkali and Enzyme. RSETE, International Conference June 24-26 pp
5810-5813
Qiang X, Sheng Z, Zhang H (2013) Study on scale inhibition perfor-
mances and interaction mechanism of modified collagen.
Desalination 309:237–242
Rajamani S (1995) Environment management in tanneries, feasible chro-
mium recovery and reuse system. Proc. III International Conference
on appropriate waste management technologies for developing
countries pp 965-973
Ramasami T, Sreeram KJ, Gayatri R (1998) Emerging leather processing
options for waste minimization. UNIDO Report, Regional
Workshop on Cleaner Tanning Technologies
Ramnath V, Sekar S, Sankar S, Sankaranarayanan C, Sastry TP (2012)
Preparation and evaluation of biocomposites as wound dressing
material. J Mater Sci Mater Med 23(12):3083–3095
Rao JR, Thanikaivelan P, Sreeram KJ, Nair BU (2002) Green route
for the utilization of chrome shavings (chromium-containing
solid waste) in tanning industry. Environ Sci Technol 36:1372–
1376
Rao JR, Thanikaivelan P, Sreeram KJ, Nair BU (2004) Tanning
studies with basic chromium sulfate prepared using chrome shav-
ings as a reductant:A call for ‘wealth from waste’ approach to the
tanning industry. J Am Leather Chem Assoc 99:170–176
Reis MAD, Beleza V (1991) Utilization of leather waste: Animal
feedstuff from chrome shavings Part 1: Pilot plant study. J Soc
Leather Technol Chem 75:15–19
Riaz S, Alam SS (2006) Evaluation of nutritive value of different levels of
chrome shaving (hydrolysed) partially replacing animal protein in
the feed on the performance of quail chicks. J Agri Biol Sci 1:1–7
Rose C, Ranganayaki MD, Srinivasan TS, Ramakrishnan S,
Seethalaksmi S, Sastry TP (2007) A process for the preparation of
a parchment like material. India 0300/DEL/2001
Saha N, Kresalkova M, Saha L, Kolomaznik K (2003a) The effect of
anaerobic digestion on chrome sludge: a by-product of tanned
leather waste. J Am Leather Chem Assoc 98:256–262
Saha N, Zatloukal M, Saha P (2003b) Modification of polymers by
protein hydrolysate: a way to biodegradable materials. Polym Adv
Technol 14:854–860
Sangeeth MG, Saravanakumar MP, Porchelvan P (2009) Pollution po-
tential of chrome shaving generated in tanning process. J Appl Sci
EnvironSanit 11:11–15
Sanjuán-Herráez D, Chabaane L, Tahiri S, Pastor A, de la Guardia M
(2012) Preliminary results on the use of leather chrome shavings for
air passive sampling. J Anal Methods Chem 2012:1–6
Santana TJM, Torres AC, Lucero AM (1998) Extrusion and Mechanical
characterization of PVC-leather fiber composites. Polym Compos
19:431–439
Santana TJM, Vega MJA, Lucero AM, Moreno FV (2002) Production of
leather like composites using chemically modified short leather
fibers I: chemical modification by emulsion polymerization.
Polym Compos 23:49–60
Saravanabhavan S, Sreeram KJ, Rao JR, Nair BU (2004) The three pot
solution for chromium, tannins and solid wastes: recovery and reuse
technique for spent semi-chrome liquor and chrome shavings. J Soc
Leather Technol Chem 88:202–207
Saravanabhavan S, Sreeram KJ, Rao JR, Nair BU (2005) The three pot
solution for chromium, tannins and solid wastes: recovery and reuse
technique for spent semi chrome liquor and chrome shaving. J Soc
Leather Technol Chem 89:111–114
Saravanabhavan S, Sreeram KJ, Rao JR, Nair BU (2007) The use of toxic
solid waste for the adsorption of dyes from waste streams. J Chem
Technol Biotechnol 82:407–413
Environ Sci Pollut Res
Sastry TP, Ranganayaki MD, Rose C, Rajini R (1999) Extraction of
gelatin from chrome shavings using pancreatic enzymes. Proc.
XXV IULTCS Congress,held in Chennai, Waste Manage Technol
513-519
Sastry TP, Sehgal RK, Ramasami T (2005) Value added eco-friendly
products from tannery solid wastes. J Environ Sci Eng 47(4):250–254
Sedliacik J, Matyasovsky J, Smidriakova M, Sedliacikova M, Jurkovic P
(2011) Application of Collagen Extracted from Chrome Shavings
for Innovative Polycondensation Adhesives. J Am Leather Chem
Assoc 106:332–340
Sekaran G, Swarnalatha S, Srinivasulu T (2007) Solid waste management
in leather sector. J Des Manuf Technol 1:47–52
Senthil Kumar P, Sounderraj L, Sivakumar K, Rajakumar S (2012)
Enzymatic hydrolyses of chrome shaving waste from tannery
through Aspergillus tamerii. J Biol Environ Sci 6(18):285–292
Sethuraman A, Srinivas K, Sekaran G (2013) Double pyrolysis of chrome
tanned leather solid waste for safe disposal and products recovery.
Int J Sci Eng Res 4(11):61–67
Shanthi C, Shelly DC (2003) Immobilization of degradative enzyme on to
collagen hydrolysate films. J Am Leather Chem Assoc 98:6–12
Shanthi C, Banerjee P, Chandra Babu N, Rajakumar G (2013) Recovery
and characterization of protein hydrolysate from chrome shavings
by microbial degradation. J Am Leather Chem Assoc 108:231–239
Sharaf SAA, Gasmeleed GA, Musa AE (2013) Reduction of Hexavalent
Chromium from Chrome Shavings. Int J Adv Ind Eng 1:24–27
Shin EC, Lee SC, Kim WJ, Heo JS (2007) Development of regenerated
protein fibers from a collagen-polyvinyl alcohol complex. J Am
Leather Chem Assoc 102:315–321
Sirbu C, Cioroianu T, Dumitru M, Dorneanu A et al (2008) New struc-
tures of biofertilizers with chelate proteinic substances with role of
biostimulator and protection for sustainable agriculture. Seria
Agronomie 51(2):189–194
Sirbu C, Cioroianu T, Dumitrascu M (2009) New fertilizers with protein
structure with fitostimulator role. Seria Agronomie 52:473–478
Sivaparvathy M, Suseela K, Nanda SC (1986) Hydrolytic action of
Pseudomonas aeruginosa on chrome shavings. Leather Sci 33(1):8–11
Skrypski-Mantele S, Bridle TR (1995) Environmentally sound disposal
of tannery sludge. Water Res 29(4):1033–1039
Smith LR, Donovan RG (1982) Preparation of high quality gelatin with
low chromium content from chrome-tanned stock. J Am Leather
Chem Assoc 77:301–306
Sreeram KJ, Saravanabhavan S, Rao JR, Nair BU (2004) Use of
chromium-collagen wastes for the removal of tannins from waste-
waters. Ind Eng Chem Res 43:5310–5317
Sreeram K, Rao J, Nair B (2011) Chromium (III) Pigments: Use of leather
wastes as alternative starting material. J Am Leather Chem Assoc
106:219–225
Stein K, Schwedt G (1994) Chromium speciation in the wastewater from
a tannery. Fresen J Anal Chem 350:38–41
Stockman G (1996) Practical considerations of the production scale
hydrolysis of blue shavings. J Am Leather Chem Assoc 91:190–193
Sudha PN (2010) Are we eating chrome chicken?????? The Socioscan
2(3–4):69–71
Sudha PN, Latha S, Bharghavi VLN (2011) Towards chrome free chick-
en—a pilot scale study to remove chromium from leather waste, a
source for poultry feed manufacture. Environ Sci :An Indian J 6(3):
1–6
Sun D, Liao X, Shi B (2003) Oxidative dechroming of leather shavings
under ultra sound. J Soc Leather Technol Chem 87:103–106
Swarnalatha S, Ganesh Kumar A, Tandaiah S, Sekaran G (2009) Efficient
and safe disposal of chrome shavings discharged from leather in-
dustry using thermal combustion. J Chem Technol Biotechnol 84:
751–760
Sykes G (1997) Leather board manufacture. World Leather 10:60–61
Tahiri S, Azzi M, Albizane A, Messaoudi A, Bouhria M, Sibari A (2001a)
Processing of chrome tanned solid waste generated in the leather
Environ Sci Pollut Res
industry: recovery of proteins and synthesis of a pigment for paint. J
Am Leather Chem Assoc 96:1–8
Tahiri S, Azzi M, Albizane A, Messaoudi A, Bouhria M, Younssi SA,
Mourid A, Amrhar J (2001b) Study of quality of a pigment prepared
by complexation of chromates recovered from treated chrome shav-
ings and tanned splits. J Am Leather Chem Assoc 96:426–436
Tahiri S, Azzi M, Messaoudi A, Albizane A, Bouhria M, Younssi SA,
Mabrour J (2002) Removal of methylene blue from aqueous solu-
tions by adsorption on tanned solid wastes. J Am Leather Chem
Assoc 97:261–266
Tahiri S, Messaoudi A, Albizane A, Azzi M, Bouhria M, Younssi SA,
Ben-nazha J, Mabrour J (2003) Removal of dyes from aqueous
solutions by adsorption on chrome tanned solid wastes generated
in the leather industry. Water Qual Res J Canada 38:393–411
Tahiri S, Bouhria M, Albizane A, Messaoudi A, Azzi M, Younssi SA,
Mabrour J (2004) Extraction of proteins from chrome shavings with
sodium hydroxide and reuse of chromium in the tanning process. J
Am Leather Chem Assoc 99:16–25
Tahiri S, Albizane A, Abargues MR, Guardia MDL (2006) Recovery
of proteinaceous materials from tanned solid wastes: yields and
characterization of isolated products. J Solid Waste Technol
Manag 32:138–148
Tahiri S, Albizane A, Messaoudi A, Azzi M, Bennazha J, Younssi SA,
Bouhria M (2007) Thermal behaviour of chrome shavings and of
sludges recovered after digestion of tanned solid wastes with calci-
um hydroxide. Waste Manag 27:89–95
Tang K, Zheng X, Li W, Shelly DC, Casadonte DJ (2010) Modification of
polyurethane finishing agent using collagen hydrolysate from
chrome shavings. J Am Leather Chem Assoc 105:25–31
Taylor MM, Diefendorf ES, Na GC (1990) Enzymic treatment of chrome
shavings. J Am Leather Chem Assoc 85:264–275
Taylor MM, Diefendorf EJ, Marmer WN (1991) Efficiency of
enzymic solubilization of chrome shavings as influenced by
choice of alkalinity-inducing agents. J Am Leather Chem
Assoc 86:199–208
Taylor MM, Diefendorf EJ, Brown EM, Marmer WN (1992)
Characterization of products isolated by enzyme treatment of chro-
mium containing leather waste. J Am Leather Chem Assoc 87:380–
389
Taylor MM, Diefendorf EJ, Marmer WN, Brown EM (1994) Effect
of various alkalinity inducing agents on chemical and physical
properties of protein products isolated from chromium containing
leather waste. J Am Leather Chem Assoc 89:221–228
Taylor MM, Diefendorf EJ, Marmer WN, Brown EM (1995) Effect
of deionization on physical properties of gelable protein products
recovered from solid tannery waste. J Am Leather Chem Assoc 90:
365–374
Taylor MM, Cabeza LF, Marmer WN, Brown EM (1997a)
Computer-assisted method to measure the adhesive properties
of hydrolysis products from collagen. J Am Leather Chem
Assoc 92:28–37
Taylor MM, Diefendorf EJ, Thompson CJ, Brown EM, Marmer WN,
Cabeza LF (1997b) Extraction of value added byproducts from the
treatment of chromium containing collagenous leather industry
waste. J Soc Leather Technol Chem 81:5–13
Taylor MM, Cabeza LF, DiMaio GL, Brown EM, Marmer WN, Carrio R,
Celma PJ, Cot J (1998) Processing of leather waste: pilot scale
studies on chrome shavings. Part, I. Isolation and characterization
of protein products and separation of chrome cake. J Am Leather
Chem Assoc 93:61–82
Taylor MM, CabezaLF BEM, Marmer WN (1999) Chemical modifica-
tion of protein products isolated from chromium-containing solid
tannery waste and resultant influence on physical and functional
properties. J Am Leather Chem Assoc 94:171–175
Taylor MM, Cabeza LF, Marmer WN, Brown EM (2000) Use of tryptec
enzyme preparations in treatment of chrome shavings. J Am Leather
Chem Assoc 95:243–52
Taylor MM, Cabeza LF, Marmer WN, Brown EM (2001) Enzymatic
modification of hydrolysis products from collagen using a microbial
transglutaminase. I. Physical properties. J Am Leather Chem Assoc
96:319–332
Taylor MM, Liu CK, Latona N, Marmer WN, Brown EM (2002)
Enzymatic modification of hydrolysis products from collagen using
a microbial transglutaminase. II. Preparation of films. J Am Leather
Chem Assoc 97:225–234
Taylor MM, Liu CK, Marmer WN, Brown EM (2003) Enzymatic mod-
ification of hydrolysis products from collagen using a microbial
transglutaminase III. Preparation of films with improved mechanical
properties. J Am Leather Chem Assoc 98:435–444
Taylor MM, Marmer WN, Brown EM (2005) Characterization of
biopolymers prepared from gelatin and sodium caseinate for
potential use in leather processing. J Am Leather Chem
Assoc 100:149–159
Trezza MA, Scian AN (2007) Waste with chrome in the Portland cement
clinker production. J Hazard Mater 147:188–196
USEPA (2004) National Priorities List (NPL) Sites with fiscal year 1982–
2003, Records of Decision (RODs). USEPA-June 2003, Office of
Emergency and Remedial Response, OERCLIS
Vedaraman N, Rangasamy T, Muralidharan C, Rao PG (2002) A
process for preparation of leather like sheet and the sheet prepared
there by. India 752/Del/2002
Veeger L (1993) Ecological procedure to solve the tannery waste prob-
lems. J Am Leather Chem Assoc 88:326–329
Walawska B, Kowalski Z (2001) Environmental evaluation of the effects
of using chromic waste in the production of chromium compounds.
J Clean Prod 9:219–226
Williams PT (1990) A review of pollution from waste incineration. Water
Environ J 4:26–34
Wojciech L, Mieczyslzw G, Urszula M, et al (1998) Process for the
removal of chromium from leathers and/or leather wastes, both
tanned with chromium compounds, and/or different substances con-
taining chromium compounds, in particular wastes of the
collageneous origin. WO1998003685
Wojciech L, Mieczyslzw G, Urszula M, et al (1998) Leather treatment to
remove chromium. PCT 9803685
World Bank, Pollution Prevention and Abatement-Hand Book (1999)
Washington, DC, USA
Yilmaz O, Kantarli CI, Yuksel M, Saglam M, Yanik J (2007) Conversion
of leather wastes to useful products. Resour Conserv Recycl 49:
436–448
Zahid ZR, Al-Hakkak ZS, Kadhim AHH, Elias EA, Al-Jumaily IS (1989)
Comparative effects of trivalent and hexavalent chromium on sper-
matogenesis of the mouse. Toxicol Environ Chem 25:131–136
Zhao S, Zhang M, Li G, Liu W (2009) Preparation and characterization
of alkali-soluble collagen from pigskin shavings. J Am Leather
Chem Assoc 104:344–351