WOLLO UNIVERSITY

KOMBOLCHA INSTITUTE OF TECNOLOGY

SCHOOL OF MECHANICAL AND CHEMICAL ENGINEERING
Department of chemical engineering
Stream- Environmental Engineering
Target group 5th Year
Task research methods and project proposal (ChEg 5251

Title treatment of chromium rich tannery solid wastes with hydrated lime
powder

Section –A and B

Group Members ………………………………………………………LD No

1. Ashenafi Belete………………………………………………...0864/10
2. Tizita adeno…………………………………………………....2165/10

3. Adane Bayene …………………………………………………0744/10

4. Haileselassie Aynetu…………………………………………..1383/10

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Submitted to Mr Kider.Y Submitted date 2/10/2014 E.C

Table of Contents
CHAPTER ONE..............................................................................................................................................3
INTRODUCTION...........................................................................................................................................3
1.1Background of the Study....................................................................................................................3
1.2 Statement of the Problem.................................................................................................................4
1.3 Objectives of the Study......................................................................................................................5
1.3.1 General objective........................................................................................................................5
1.3.2 Specific Objective ;......................................................................................................................5
1.4 Significance of the Study....................................................................................................................5
1.5 Scope of the Study.............................................................................................................................6
1.6 Expected out come............................................................................................................................6
CHAPTER TWO.............................................................................................................................................7
LITERATURE REVIEW....................................................................................................................................7
2.1 Description of Leather Processes.......................................................................................................7
2.1.1 Beam House Processes...............................................................................................................7
2.1.2 Tan-yard Processes...................................................................................................................10
2.1.3 Post-Tanning Operations..........................................................................................................12
2.1.4 FINISHING.................................................................................................................................15
2.2 Wastes Generated from a Tannery..................................................................................................17
2.3 Chromium.....................................................................................................................................19

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 2.3.1 Forms of chromium..................................................................................................................19
2.3.2 Role of Chromium in Tanning Process......................................................................................21
2.3.3 Toxicity of Chromium................................................................................................................21
2.4.3 Treatment of Chromium Containing Tannery Solid Wastes......................................................22

CHAPTER ONE
INTRODUCTION
1.1Background of the Study
The principal aim of the leather industry is to transform animal
hides/skins into a physically and chemically stable material by
subjecting them to chemical and mechanical sequential processes, and
therefore to obtain different leather products for meeting various needs
of people. The leather industry generally uses hides and skins as raw
materials, which are the byproducts of meat and meat products industry.
In this respect, the leather industry could have easily been distinguished
as an environmentally friendly industry, since it processes waste
products (by products) from meat Leather industry in Ethiopia plays
significant role for economic growth of the country as a main source of
foreign currency production.
However, most of the tanneries in Ethiopia dispose their liquid and solid
waste to the environment without any treatment mechanisms. The
situation with solid waste by product management is even worse than the
liquid effluent. Because there is no designated site for disposal of huge
solid wastes the tanneries generate every day. Hence tanneries are using
the nearby water ways for dumping their solid waste.
In leather industry; tanning is the main process that protects leather
against some environmental effects such as microbial degradation, heat,
sweat or moisture. About 90% of tanneries in the world use chromium
salts as tanning materials because of the excellent properties of the
chromium compounds in the tanning process. During the tanning
process, chromium forms cross links between the collagen fibers and

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the resulting hides have a good mechanical resistance, an
extraordinary dyeing suitability and a better hydrothermal resistance in
comparison with hides treated with vegetable materials. However, up to
two-thirds of the chromium used to tan hides by a typical tannery never
gets into the finished product.

1.2 Statement of the Problem

Tanneries generate huge amount of CCTSW, such as wet blue shaving
waste, wet blue trimmings, crust and finished leather trimmings, buffing
dust and waste water treatment sludge. Most of these wastes are highly
acidic and contain trivalent chromium. And in acidic medium trivalent
chromium is highly soluble and leachable. Hence when these solid
wastes dispose to the receiving environment or utilized for different
purpose without any treatment, trivalent chromium has the tendency to
leach and oxidized in to hexavalent chromium which is highly toxic
even in a very small amount to all living organisms (ATSDR, 1993;
Mabasa, 2007; Assem and Zhu, 2007). Beside to this the acidity of most
of CCTSW which is around pH 3-4 will lower the pH of the receiving
environment which will disturb the fauna and flora found there
(Ozgunay et al., 2007). Sanitary landfills in countries that have strict
environmental regulation are reluctant to accept CCTSW because of the
possibility of trivalent chromium being leached from CCTSW and
converted to hexavalent chromium in gentle condition in wide range of
pH (both in acidic and alkali media) (Kolomaznik et al., 2009 ). But
most of the tanneries in Ethiopia dispose their CCTSW in the nearby
rivers and water ways (Isayas Taddesse, 2003). And some tanneries like
ELICO-Awash Tannery dispose their CCTSW without any treatment to
landfill called Koshe or Repi which is not secured for such hazardous
waste disposal. This subsequently causes both surface and ground water
pollution and soil contamination with the toxic chromium metal. And
there are a lot of city farms near this land fill site which might create a
possibility for chromium to enter in to the food chain. Chromium is not
biodegradable and tends to bioaccumulate in living organisms causing
serious disease and disorders (Wang et al., 2007; ATSDR, 1993).
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Beside to this chromium (VI) is classified by both international agency
for research on cancer and USEPA as a known carcinogen and it is also
known to have mutagenic potentials (DEFRA, 2002; Assem and Zhu,
2007).
Therefore, it is necessary to treat (to fix the leachable chromium) in
chromium containing tannery solid wastes before disposal or utilization
for different purpose.
1.3 Objectives of the Study
1.3.1 General objective ;
The overall aim of this study is to mitigate the environmental impact of
chromium containing tannery solid wastes by stabilizing chromium
within the solid waste through treatment with hydrated lime powder.
1.3.2 Specific Objective ;
 Determine the type and amount of chromium containing solid
waste generated from ELICO-Awash Tannery.
 Determine chromium (III) and chromium (VI) content of solid
wastes generated from ELICO-Awash Tannery.
 Examine leachablity of chromium from the tannery solid wastes.
 Stabilize chromium in chromium containing tannery solid wastes
to reduce its leachabilty and toxicity in the receiving
environment.
1.4 Significance of the Study
In this study the type and amount of chromium containing tannery solid
wastes generated per hide / skin processed in Awash Tannery will be
determined. This enables to calculate the total amount of chromium
containing solid wastes generated from Awash Tannery and also helps to
estimate the total amount of chromium containing solid wastes generated
from other tanneries in Ethiopia based on their process capacity. This is
important information for tannery solid waste management and for
tannery solid waste utilization program. Beside to this the study provides
baseline information about the environmental impact of chromium
containing tannery solid wastes specially about the conversion of
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chromium(III) that is mainly found in CCTSW in to chromium(VI)
which is a more toxic form of chromium in the receiving environment.
This study also proposes cheap treatment methods for CCTSW which
helps to stabilize (fix) and reduce leachablity of chromium from the
solid wastes. This subsequently reduces the environmental impact of
CCTSW. Finally, this study recommends feasible technologies to utilize
CCTSW for different purpose and also recommends proper and safe
disposal method for these tannery solid wastes as an alternative.
1.5 Scope of the StudyThis study deals mainly with determining the type
and amount of chromium containing tannery solid wastes (CCTSW),
determining the leachabilty of chromium from tannery solid wastes,
stabilizing (fixing) chromium in CCTSW to reduce it leachabilty and
toxicity in the receiving environment and assessing feasible technologies
to utilize CCTSW for different purposes.
1.6 Expected out come
Since different waste materials showed potential of metal removal from
aqueous solutions, therefore, this study expected out come is:

 Sustainable tanneries wastewater treatment for chromium removal,

in order to be reused in the industry or to be discharged in the
environment, using different types of solid wastes.
 The best suitable material for chromium removal.
 The best mixing and operation conditions for the best removal
efficiency of trivalent chromium.
 The efficiency of the treatment technique on real tanning
wastewater samples.
 the efficiency of trivalent chromium recovery using sulfuric

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 CHAPTER TWO

LITERATURE REVIEW
2.1 Description of Leather Processes
Leather technology consists of different process steps and unit
operations to convert raw hide and skin into different finished leather.
Although the technologies used by all tanneries are not the same there
are common operations in leather making activities. These main
operations in leather making process are beam house, tan-yard, post
tanning and finishing operations each comprising a number of sub
operations as described below.
The beam house process is the first process where
2.1.1 Beam House Processes
the raw hide or skin is soaked, washed, limed, un haired, fleshed,
delimed and bated prior to tanning. The raw hide must be kept well
preserved before coming to the tannery in order to retard its putrefaction.
The most common methods of preserving raw hides are; wet-salting,
dry-salting and sun-drying.
The aim in all the three methods being the reduction of moisture there by
making condition unfavorable for bacterial growth.

a) Soaking ; Soaking is carried out to allow hides and skins to re-

absorb any water which may have been lost after flaying, to clean the
hides and skins (removal of dung, blood, dirt etc), and to remove inter
fibrillary material. The soaking methods depend on the state of the hides.
The process is mostly carried out in two steps: pre soak to remove the
salt and dirt and a main soak to re hydrate the raw hide or skin and to
adjust the pH to 8-10. The process is carried out in processing vessels,
such as mixers, drums, paddles, pits, or raceways. The duration of
soaking may range from several hours to a few days. Depending on the
type of raw materials used, soaking additives can be used such as
surfactants, enzyme preparations and bactericides (IPPC, 2003).
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b) Un haring and liming of bovine hides; The function of
liming and un - haring is to remove hair, inter fibrillary components and
epidermis and to open up the fiber structure. Hair removal is performed
by chemical and mechanical means. The keratinous material (hair, roots,
and epidermis) and fat are eliminated from the pelts mainly with
sulphides (NaHS or Na2S) and hydrated lime [Ca (OH 2]. Alternatives
to inorganic sulphides include organic compounds such as mercaptans or
sodium thioglycolate in combination with strong alkali and amino
compounds. Enzymatic preparations are sometimes added to improve
the performance of the process. The process of liming and unhairing can
be carried out in process vessels such as drums, paddles, mixers, or pits
(Sharp house, 1983).

c) Painting & liming of sheep skins; the aim of painting is to

bring about the breakdown of the wool root within the skin so that as
much undamaged wool fiber as possible can be pulled easily from the
pelt. Paint, generally consisting of a mixture of sodium sulphide and
lime, is applied to the flesh side of the skin and left for several hours.
Application of the paint can be through a spraying machine or manually.
After several hours the wool can be ‘pulled’ from the skin, either
manually or mechanically. After pulling the wool, the skins are limed in
process vessels, with the same purpose as the liming of bovine hides.
Wool- on skins are not painted, unhaired or limed.

d) Fleshing; Fleshing is a mechanical scraping off of the excessive

organic material from the hide (connective tissue, fat, etc.). The pelts are
carried through rollers and across rotating spiral blades by the fleshing
machine. Fleshing can be carried out prior to soaking, after soaking,
after liming or after pickling .The process of fleshing is called green
fleshing if the removal is done prior to liming and unhairing. If fleshing
is performed after the liming and unhairing it is called lime fleshing.
Sheep skins maybe fleshed in the pickle stage.

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e) Splitting; By mechanical splitting the thickness of hides and skins
is regulated and they are split horizontally into a grain layer and a flesh
layer. Splitting is carried out on splitting machines, fitted with a band
knife. Splitting can be done in limed condition or in the tanned
condition. The inner part which is called pelt split or wet blue split
considered as byproduct and may be used for glue production or split
leather production. The upper part (the grain part) will be proceeding to
the next leather making processes.

Figure 2.1 Flow Diagram of the Beam House Operation

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2.1.2 Tan-yard Processes
a) Deliming;the aim of deliming is to remove residual lime from the
pelts and to take the pelts to the optimum condition for bating. This
involves a gradual lowering of the pH up to 8.2 - 8.8 (by means of
washing and addition of deliming chemicals), an increase in temperature
and the removal of residual chemicals and degraded skin component.
Generally, deliming is performed in a processing vessel such as drum,
mixer or paddle.
b) Bating; Bating is a partial degradation of non-collagenic protein
achieved by enzymes to improve grain of hide and the subsequent run
and stretch of leather. In this process the rest of the unwanted hair roots
and scud can be removed. Bating is processed in the same deliming float
by using pancreatic enzyme.
c) Degreasing; Excess grease must be eliminated from fatty skins
(sheep, pig) to prevent the formation of insoluble chrome-soaps or
prevent the formation of fat spues at a later stage. Degreasing is most
relevant in processing sheepskins, where the natural fat content is about
10 % - 20 % on dry weight. The nature of this fat makes it difficult to
remove because of the presence of cerides and a high melting
temperature (IPPC, 2003). The three different methods commonly used
for degreasing are degreasing in aqueous medium with organic solvent
and non-ionic surfactant, degreasing in aqueous medium with non-ionic
surfactant and degreasing in solvent medium.
d) Pickling; Pickling is carried out to reduce the pH of the pelt prior to
mineral tanning and some organic tannages (e.g. chrome tanning,
zirconium tanning gluter dialdehyde tanning, and vegetable tanning).
The choice of the exact pickling parameters depends on the subsequent
tanning step. Very often tanning is carried out in the pickle liquor;
however, pickled pelts, e.g. sheepskins, can be traded. Pickled pelt
sheepskins must contain fungicides to protect them from mould growth
during storage.
e) Tanning; In the tanning process the collagen fibre is stabilized by the
tanning agents such that the hide or skin is no longer susceptible to
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putrefaction or rotting. In this process the collagen fibers are stabilized
by the cross-linking action of the tanning agents. Furthermore, their
dimension stability, resistance to mechanical action and heat increase
after tanning process (IPPC, 2003). The various tanning agents can be
categorized in three main groups: Mineral tannages like chromium
tannage, Vegetable tannages and alternative tanning agents, which
includes syntans, aldehydes and oil tannage.
f) Sammying and Setting; After tanning, the leathers are drained, rinsed
and either horsed up to age, or unloaded in boxes and subsequently
sammed to reduce the moisture content prior to further mechanical
action, such as splitting and shaving. The setting out operation can be
carried out to stretch out the leather. Machines exist which combine the
sammying and setting action. After sammying and setting, hides and
skins can be sorted into different grades after which they are processed
further or sold on the market.
g) Shaving; the shaving process is carried out to achieve an even
thickness throughout the skin/hide, and it can be carried out on tanned or
crusted stage of the leather. Shaving is carried out where splitting is not
possible or where minor adjustments to the thickness are required.
h)Trimming; Trimming is the process of removing the un wanted part
(rags or flags) from the skin or hide to reduce the damage by different
machines in the next leather making operations and to maintain the
shape of the leather.

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 Figure 2 .2 Flow diagram of tan-yard operation
2.1.3 Post-Tanning Operations
Post-tanning involves neutralization and washing, followed by
retanning, dyeing , fat liquoring and fixation mostly done in a single
processing vessel. At this stage of the process, specialist operations may
also be carried out to add certain properties to the leather such as water
repellence or resistance, gas permeability, flame retarding, abrasion, anti
electrostatics etc. This done by using some chemicals in this process that
can bring the above mentioned characterstics.

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a) Neutralization; Neutralization is the process by which the tanned
hides are brought to a pH suitable for the process of retanning, dyeing
and fat liquoring. During neutralization the pH should be raised up to
4.8-6.5 based on the type of the product. There are neutralization agents
like sodium formate, sodium carbonate and neutralization syntans.
b) Bleaching; Vegetable tanned skins and leathers with wool or hair
may need to be bleached in order to remove stains, or to reduce the
coloring in the hair, wool, or leather prior to retanning and dyeing. In
leather making process bleaching agent like sodium bi sulphite is
commonly used. There are also some syntans that have bleaching power
in leather making processes.
c) Retanning; The retanning process can be carried out to improve the
feel and handle of the leathers and to fill the looser and softer parts of
the leather in order to produce leathers of more uniform. A wide variety
of chemicals can be used for the retannage of leather such as vegetable
tanning extracts, syntans, aldehydes, mineral tanning agents like
chromium meatals and resins.
d) Dyeing; the dyeing process is carried out to produce level colors over
the whole surface of each hide and skin and exact matching between
hides in a commercial pack. Typical dyestuffs are water based acid dyes.
Basic and reactive dyes are less commonly used. Sometimes ammonia
solution will be added during dyeing process to open up the fiber of the
leather and help the dyestuffs to penetrate through the leather. This is
mostly done during dyeing process of thick leathers like cow and buffalo
leather.
e) Fat liquoring; Leathers must be lubricated to achieve product
specific characteristics and to reestablish the fat content lost in the
previous procedures. The oils used may be of animal or vegetable origin,
or might be synthetics based on mineral oils. Stuffing is an old technique
used mainly for heavier vegetable tanned leather (commonly known as
sole leather). The sammed leather is treated in a drum with a mixture of
molten fat.

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The retanned, dyed, and fat liquored leather is usually fixed with formic
acid to avoide bleeding of the dyes and fat liquors and washed before
being piled on a 'horse' to age (let the fat migrate from the surface to the
inside of the leather).
f) Drying; The objective of drying is to dry the leather whilst
optimizing the quality and area yield. There is a wide range of drying
techniques and some may be used in combination. Each technique has a
specific influence on the characteristics of the leather. Drying techniques
include samming, setting, centrifuging, hang drying, vacuum drying,
toggle drying and paste drying. Generally samming and setting are used
to reduce the moisture content mechanically before another drying
technique is used to dry the leather further. After drying, the leather may
be referred to as crust which is a tradable intermediate product.

Figure 2 .3 Flow diagram of post tanning processes

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2.1.4 FINISHING
The overall objective of finishing is to enhance the appearance of the
leather and to provide the performance characteristics expected of the
finished leather with respect to:
Color, gloss, handle, flex, adhesion, rub fastness, as well as other
properties including extensibility, break, light and perspiration fastness,
water vapor permeability and water resistance as required for the end
use. Generally, finishing operations can be divided into mechanical
finishing processes and surface coat finishing process.
a) Mechanical Finishing Processes; A wide range of mechanical
finishing operations may be carried out to improve the appearance and
the feel of the leather. The following operations are commonly used
mechanical finishing operations. However, the list is not exhaustive and
many other operations exist for special leathers such as sole leathers and
special effects leathers: Staking (softening and stretching of leather),
Buffing and dedusting (abrading of the leather surface and removing the
resulting dust from the leather surface), Dry milling (mechanical
softening), Polishing and Plating or embossing (flattening or printing a
pattern into the leather).
b) Surface Coat Finishing; There are a wide range of surface coat
application methods each of which has its advantages and disadvantages.
A combination of methods can be used to achieve the desired effect on
the finished product. Commonly used surface coating systems are roller
coating, spraying and paddling. The purposes of applying a surface coat
are:
 To provide protection from contaminants (water, oil, soiling)
 To provide color (to even the color) or to disguise defects.
 To provide modifications to handle and gloss performance
 To provide attractive fashion or fancy effects

There are commonly two types of finished leathers; aniline finished

leather which is slightly sprayed with some finishing chemicals like wax
15
& oils and pigment finished leathers that have open defects and to cover
these defects some finishing chemicals like pigments, filers and binders
will be coated by spray machines or roller coater machines .

Figure 2.4 Flow diagram of finishing processes

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2.2 Wastes Generated from a Tannery
The environmental impacts of tanneries originate from liquid, solid and
gaseous waste streams and from the consumption of raw materials such
as raw hides, energy, chemicals and water. Only 20 % of the weight of
the raw hide is processed to finished leather. The rest of the weight plus
the chemicals input ends up as either waste or by-products. The main
releases to wastewater originate from wet processing in the beam house,
the tan yard, and the post tanning operations. The main releases to air are
due to the dry finishing processes, although gaseous emissions may also
arise in all other parts of the tannery. The main sources of solid wastes
originate from fleshing, splitting and shaving. A further potential source
of solid waste is the sludge from the effluent treatment plant, but this is
not an onsite activity in all tanneries (IPPC, 2003). The next figure
indicates the type and amount of wastes generated during processing 1
ton of raw hide.
a) Waste Water; Water is used as the carrier for chemicals to render the
cleaning of raw hides and skins. The water after completion of the
process is drained out in the same quantity as it was used in the process.
Normally water consumption of 50 liter / kg is recommended for
tanneries but it is found that tanneries generally consume more water
and in some cases it is found to be as high as 150 liter / kg.the most
commonly monitored parameters for setting the requirements for waste
water effluents are chemical oxygen demand (COD), biochemical
oxygen demand (BOD5), suspended solids (SS), total nitrogen (N-tot,
TKN), ammonium nitrogen (NH4-N), sulphide (S2-), chrome(total),
grease and fat content, pH and temperature. Salt as chloride and/or
sulphate (Cl-, SO42-), total dissolved solids (TDS), phosphorous (P
total), absorbable organic halogenated compounds (AOX), surfactants,
pesticides, phenols and fish toxicity are not as common.
The composition of wastewater effluents varies greatly between
tanneries (IPPC, 2003; UNIDO, 2000; Bukahari et al., 2012).
b) Solid Wastes; Quantities of solid waste produced by tanneries
depend on the type of leather processed, the source of hides and skins

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and the techniques applied (Technologies used by individual tanneries).
The major solid wastes consist of dusted curing salt, wet trimmings, dry
trimmings, wet shaving, buffing dust and wastewater treatment sludge
(Kanagaraj et al., 2006). During handling of raw skins, adhered dusted
salt, which is contaminated with blood, hair, dirt and certain type of
bacteria is removed and dumped. Trimmings are cuttings of edges of
raw skins. Fleshing is the flesh material of the limed skins generated
during fleshing operation. Chrome wet shavings and trimmings are
produced when skins / hides are shaved for proper thickness (uniform
thickness) after chrome tanning (Chattaha and Shaukat, 2000; IPPC,
2003).
c) Air Emissions; In tanneries air emissions are produced from the
stacks of boilers and generators and during the processing of leather.
Emissions from the stacks are well within the limits and pose no serious
environmental impact. But hydrogen Sulphide and ammonia gases
which are emitted during different processes are a health hazard for the
workers (Chattaha and Shaukat, 2000). Common air emissions from
tanneries are: sulphides from the beam house and from waste water
treatment plant, ammonia from the beam house, tanning and post-
tanning operations, sulphur dioxide from post tanning operations, dust or
total particulate from various operations, such as storage and handling of
powdery chemicals, dry shaving, buffing, dust removal from machines,
milling drums and staking machines (IPPC, 2003).

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2.3 Chromium
Chromium was discovered in 1780 by French chemist Nicolas Louis
Vauquelin in Paris. He discovered the element in a mineral sample of
‘Siberian red lead’- now known as crocoite or lead chromate (Santos et
al., 2012). One of the most interesting characteristics of this metal is its
hardness and high resistance to corrosion and discoloration. The
importance of these proprieties resulted among others in the usage of
this metal in the development of stainless steel, which together with
chrome plating and leather tanning, are the most important applications
of this element and also the main sources of chromium pollution of the
environment. Chromium is a transition metal of Group VIB of the
Periodic Table and it is one of the heavy metals that need strong
regulation and management because of its toxicity (Bewley, 2007).
2.3.1 Forms of chromium
Chromium can exist in several chemical forms displaying oxidation
numbers from 0 to VI. The three most common forms of chromium are
the zero or elemental state [Cr (0)], the trivalent state [Chromium (III)]
and hexavalent state [Chromium (VI)]. Elemental chromium does not
occur naturally and is highly resistant to chemical attack. Both the
trivalent and hexavalent forms exist in the environment, the latter being
largely anthropogenic in origin (Bewley, 2007; Mwinyihija, 2010).
Under reducing conditions, Cr (VI) converts to Cr (III) that is insoluble,
but this form is strongly absorbed onto the surface of soil particles. On
the other hand chromium (III) converts to chromium (VI) spontaneously
in an oxidizing condition both in acidic and alkaline media
(Kolomaznik, 2009). The properties of chromium and its compounds,
which determine toxicity and impact on the environment, depend on the
valency state. Only hexavalent chromium compounds are biologically
active and known as skin irritant, mutagenic and carcinogenic. Metallic
chromium and the trivalent compounds, have no such toxic properties
(Mabasa, 2007).
a) Trivalent Chromium; Trivalent chromium is the form of chromium
naturally found in the environment. It is used for brick lining for high-

19
temperature industrial furnaces and for making alloys, chrome plating,
dye manufacture, leather tanning and wood
preserving. Chromium (III) is required for the body to utilize sugars,
proteins and fat properly. Insufficient levels of chromium (III) may
cause weight loss, impact growth, cause diabetes-like conditions and
affect the nervous system. Chromium (III) appears to enhance sensitivity
to insulin by facilitating the interaction of insulin with its receptor site
(Mabasa, 2007). The main concern with the exposure to chromium (III)
appears to be allergic reactions causing skin rashes as well as redness
and swelling of the skin in sensitive people (Mwinyihija, 2010). In the
presence of strong oxidizing agents such as Hydrogen per oxide (H2O2),
Sodium per oxide (Na2O2), Chlorine (Cl2), Bromine (Br2), and
Potassium permanganate (KMnO4), chromium (III) can converted in to
chromium (VI) which is one of the carcinogenic substance. Conversion
of chromium (III) to chromium (VI) can also take place by atmospheric
oxygen at higher temperature (Mabasa, 2007; Kolomaznik, 2009).
b) Hexavalent Chromium; Hexavalent chromium or chromium (VI) is
released into the environment primarily as a result of industrial activity.
Chromium (VI) is a potent, extremely toxic carcinogen and may cause
animals and humans to die if ingested in large doses (Mabasa, 2007).
The main cause for concern with chromium (VI) is induction of lung
cancer after long-term exposure to this toxicant. Chromium (VI) is
usually present in complexes with halide (chromyl chloride) and oxygen
ligands (chromium trioxide, chromate, and dichromate). There are
numerous chromium (VI) compounds. Some examples are potassium
chromate, dichromate, sodium chromate, chromium trioxide, and lead
chromate (Campbell, 2009).
Hexavalent chromium can easily absorbed by gut or body walls (such as
shells, gills, and mantle) because of its higher solubility. At higher
concentrations, chromium (VI) is associated with abnormal enzyme
activities, altered blood chemistry, lowered resistance to pathogenic
organics, behavioral modifications, and disrupted feeding,
histopathology, osmo regularatory upset, alterations in population

20
structure and species diversity indices, and inhibition of photosynthesis
(Irwin et al., 1997). Because of these properties of chromium (VI), EPA,
WHO, and IARC have all recognized it as a human carcinogen (YU, D.,
2008).Table 2.2 indicates different species of chromium with different
oxidation states and their environmental behaviors.
2.3.2 Role of Chromium in Tanning Process
The discovery of leather tanning with plant and organic materials may
have been accidental and started in ancient time. With increasing
demand for aesthetic appeal and softer types of leathers as well as the
need for reduction in process time, alternative tanning methods and post
tanning operations have been developed. The discovery of chromium
tanning in 1858 is a landmark in leather processing. Although many
alternative mineral tanning materials have been explored, chromium
based tanning methods in the manufacture of light and softer types of
leathers have stood the test of time (Sereeram, 2003).
Chromium (III) salts, especially chrome alum and chromium (III)
sulfate, are used in the tanning of leather. Chromium (III) stabilizes
leather by cross linking the collagen fibers. Reaction sites for chrome
tanning are the ionized carboxyl groups on side chains of the collagen
found in the skin or hide (Sharp house, 1983). Most commercial chrome
tanning products are used in powder form; they contain about 25 %
Cr2O3 of 33 % basicity. Basic chrome sulphate (BCS) liquors are also
used for leather tanning process (Sereeram, 2003). These liquors are
prepared by reducing the sodium or potassium dichromates in the
presence of sulphuric acid.
2.3.3 Toxicity of Chromium
The utilization of chromium in tanning procedures accelerates the
mobility and transport rates of chromium, which by far exceed the rates
of natural cycle processes, resulting in serious problems in countries
involved with the tanning industry (Katisfas et al., 2004).Chromium is
not biodegradable and tends to accumulate in living organisms, causing
serious diseases and disorders (Wang et al., 2007). Chromium (III) is
toxic only at high concentrations, whereas Chromium (VI) is toxic to

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mammals even at low concentrations, with a potential carcinogenic
effect (ATSDR, 1993; Mabasa, 2007; Assem and Zhu, 2007). Chromium
used for tanning process is in trivalent state and it is normally nontoxic
in the trivalent state, but a recent study indicates oxidation of the
trivalent chromium to the hexavalent state occurs under alkaline
conditions and in the presence of manganese oxide (Jones, 1979; Wang
et al., 2007). Beside to this the study by Kolomaznik et al, 2009 indicate
that chromium(III) in tannery solid waste can spontaneously oxidized in
to chromium (VI) both in acidic and alkaline conditions.
The overall toxicity of trivalent chromium is relatively low. Indeed,
chromium (III) is an essential element in human metabolism (IUE, 2001;
Mabasa, 2007). Hexavalent chromium on the other hand is of significant
toxicity. It is classified by both the International Agency for Research on
Cancer (IARC) and US Environmental Protection Agency (USEPA) as a
known human carcinogen and hexavalent chromium compounds are also
known to have mutagenic potential (Assem and Zhu,2007). Toxicity
arising from chromium (VI) may occur via inhalation, ingestion or
dermal exposure. It has an irritating and corrosive effect on skin and
mucous membranes resulting in ulceration and dermatitis. It may also
result in skin sensitization, causing skin allergies to occur in affected
individuals (ATSDR, 1993).
2.4.3 Treatment of Chromium Containing Tannery Solid Wastes
All leather producing countries have introduced specific pollution
control regulations for leather sector. Most of the standards are based on
European/ American standards. However enforcement level varies from
country to country and region to region. Currently, there is a new
regulation targeted by NGO’s to control or eliminate chromium in
tanning processes (Rajamani, 2013). The production of chromium
containing solid waste in tanneries has been recognized as a problem for
many years, and increasing pressure from environmental authorities has
demanded a solution of such a problem. Historically, shavings,
trimmings, and splits from the chromium tanning of hides and skins
have been disposed of in landfills. According to the study by Mandal et
al., 2011 there is a possibility of chromium percolation into the ground
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water, which may lead to many health hazards and disturb the
surrounding livelihoods. Also, the dumping of tannery sludge in an open
land is not safe.for ecosystem due to degradation with time under normal
environmental conditions. Currently, increasing local restrictions on land
disposal and the high costs of incineration have stimulated the search for
alternative treatments. Hence many scientific groups have oriented their
research to find a solution for these wastes (Lima et al., 2010).The major
solid wastes generated at the post-tanning operations of leather
processing or chromium containing leather waste (CCLW), has the
potential to generate value added leather chemicals. Various alkali and
enzymatic hydrolysis were compared, and calcium oxide was found to
be important for effective hydrolysis. On the basis of the results, a novel
three step CCLW treatment process is proposed. The gelatin extracted in
the first step is chemically modified to produce leather finishing agents.
The collagen hydrolysates isolated in the second step are used as
Proteinic retanning agents by chemical modification. The remaining
chrome cake is further hydrolyzed with acids in the third step, and the
obtained chromium containing protein hydrolysates could be used for
the preparation of chromium-containing retanning agents for leather
industry. The proposed three step process provides a feasible zero
discharge process for the treatment of CCLW and can help the leather
industry in solving the difficult CCLW disposal problem and obtain
economic benefits (Mu et al., 2003).Chromium containing tannery solid
waste like tannery sludge is disposed of in landfills, ocean dumping and
incineration or solidification. Landfills and ocean dumping of tannery
sludge are under increasing pressure in many countries because of
environmental consideration. When the sludge was incinerated, the
gases and soluble toxic chemicals were generated which can cause
serious environmental problems such as air, soil and water pollution plus
the high cost. Beside to this chromium (III) can convert to its more
soluble hexavalent form in the air atmosphere. Chemical and
microbiological methods have been investigated to leach chromium and
other metals from tannery sludge and other wastes. Compared to the
mineral acids consuming chemical approach, the sulfur oxidizing

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bacteria using microbiological method have the distinct advantages
(Wang et al., 2007).

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