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 Volume 99 Page 280

Characterization of Raw Wastewater from Tanneries

MARILIZ GUTTERRES, JAQUELINE BENVENUTI, JULIANA T. FONTOURA
and SANTIAGO ORTIZ-MONSALVE
Federal University of Rio Grande do Sul - UFRGS, Chemical Engineering Department,
Laboratory for Leather and Environmental Studies – LACOURO,
Rua Eng. Luiz Englert, s/n, Zip Code 90040-040 – Porto Alegre – RS, Brazil

Summary
Due to the constantly increasing requirements and supervisory environmental agencies concerning
the release of industrial effluents into receiving waters, industries are looking to properly treat their
effluents and to achieve efficient removal of contaminants. The leather industry is responsible for the
production of liquid effluents with high concentrations of pollutants since most of the process steps are
carried out in an aqueous medium. Due to the changes in leather technologies in recent years, it is
necessary to know and analyze how tannery effluents vary according to the processing steps
performed in different tanneries. This may be used to plan and design unit operations in wastewater
treatment plants. In order to contribute to this purpose, this study presents the characterization of raw
tannery wastewater and provides and discusses an overview of effluent treatment plants and some
particularities of them. The raw effluents were characterized by analysis of pH, turbidity, conductivity,
chromium oxide, chlorides, total hardness, total Kjeldahl nitrogen (TKN), ammonia nitrogen, solids
(total, suspended: fixed and volatile, dissolved: fixed and volatile), five-day biochemical oxygen
demand (BOD5), chemical oxygen demand (COD), phosphorus and total organic carbon (TOC). The
test results of the parameters for contaminants for each type of tannery are related to previous
researches and discussed.

INTRODUCTION
The industrial sector takes up an average of 22% of
the globally used water. Water usage intensity is
significant to all businesses whose sustainability will
depend on its availability, cost and quality.1 According
to the National Water Agency, the Brazilian industry
consumes about 17% of total Brazilian water demand.2
Industrial use of these resources is also responsible
for the disposal of a considerable volume of effluents,
leading to concerns about the treatment and disposal
of effluents and impact related to discharges to the
environment and water quality.
The main constituents to be considered in
wastewater treatment are included in the following
categories: suspended solids, biodegradable organic
pollutants, pathogens, nutrients, priority pollutants,
refractory organic pollutants, heavy metals and
dissolved inorganic solids.3
Physical properties, chemical and biological
characteristics of wastewaters are interrelated, e.g.
physical and chemical characteristics of water bodies
affect the abundance, species composition, stability,
productivity and biological conditions of populations of
aquatic organisms. Regarding physical properties, for
instance, temperature may affect the gases, and, in
some cases, the dissolved inorganic solids. Another
physical property – turbidity – is associated with
suspended solid concentrations.4
The pollution potential of wastewater is directly
proportional to the pollutants concentration. The
tannery wastewater characterization allows
* Paper presented at the Asian International Conference on
Leather Science and Technology (AICLST 2014) Okyama, Japan.
* Corresponding author: E-mail: mariliz@enq.ufrgs.br
establishment of the necessary treatment system to
ensure the quality of treated wastewater effluent.
LEATHER INDUSTRY AND WASTEWATER
In tanneries, the stages of hide preparation
(cleaning and conditioning treatment for tanning), as
well as the transportation and fixation of tanning and
modifying substances into collagen structure are all
carried out in aqueous media. Most of the steps in
these processes are carried out with fresh water, which
is used as a vehicle for the diffusion of chemical
products and the extraction of undesirable materials
from the hide.
Tanneries may process the hide/skin through all
stages and steps of leather production or just some of
them. Among the main specifications for identifying and
characterizing the tannery business, there are two
requirements: the kind of raw material (hide, fell or
skin) and the definition of the tanning system, which
depends on the tanning substance (mineral or organic
nature). Tanneries can be classified, according to the
stages of production, in the following categories:
a) Complete tanneries, which start from raw hide
(green or preserved) to produce finished leather.
b) Beamhouse tanneries, those that start from raw
hide up to the tanning step
c) Wet-end and finishing tanneries, which start from
leather (wet-blue) to produce crust or finished leather.
Tannery effluents are characterized by the high
biological oxygen demand (BOD), high chemical
oxygen demand (COD) and high concentrations of

280
suspended solids, organic nitrogen, sulphide and
chromium.5 Currently, aqueous streams of each bath
of a tanning process are mixed together in an
equalization tank.6 This mixture of many compounds
may complicate the wastewater treatment. Acids,
alkalis, chromium salts, tannins (natural or synthetic),
solvents, sulphides, dyes, surfactants, auxiliaries and
many other compounds which are used to transform a
hide to leather, are not completely fixed to the collagen
fibres and the surface of the product, thus remaining
free in the effluent. In addition, for each end product,
the tanning process and chemicals used are different,
and the kind and amount of waste produced may vary
over a wide range.7-10 Besides, variations were reported
that may occur under the same operating conditions of
manufacture due to the quality of raw hides/skins
processed.11
In Table I are shown some researches by other
authors who also characterized the composition of
tannery wastewater and showed the efficiency of some
treatments.
BRAZILIAN LEATHER INDUSTRY AND
WASTEWATER TREATMENT PLANTS
With 210 million head of cattle, or 14.23% of the
worldwide total, Brazil has the largest commercial herd
in the world. Brazilian leather industry processes
around 47.5 million animal hides in 310 tanning plants.
Finished leather consists of 60.6% and wet-blue leather
38.9% of exports of bovine hides. Brazil is considered
the eighth largest footwear exporter in the world.12,13
In Brazil, a unified treatment plant for wastewater
both municipal and industrial effluents is inaccessible.
Therefore, the effluent treatment plants are designed
and commonly installed for the treatment of specific
industrial effluents. The presence of certain industrial
pollutants creates a limiting factor in the treatment, as
these could reduce the capacity of a communal
wastewater treatment facility.
Tannery wastewater treatment is being implemented
with the water reuse before final treatment, with the aim
of reducing the water consumption and the high costs
of the treatment process. Process waters from
liming/dehairing and tanning operations are often
reused as input for the same operations in the industry.
The recycling of residual baths from dehairing and
liming consists of the recovery of the residual bath from
a batch of hides and using it in the dehairing process of
the next batch, replacing the amount of water and
chemical inputs needed to complete the formulation.
The tanning baths can be recycled after fine sieving or
chromium precipitation. It is possible to recycle the
tanning baths directly, passing them through a sieve,
analyzing chromium in solution and replenishing the
chromium salt and other chemical inputs required for
the process. The indirect re-use of the tanning bath
through chemical precipitation consists basically of four
steps: chromium precipitation with alkalis; chromium
hydroxide separation by sedimentation, filtration or
centrifugation and dissolution of chromium hydroxide
with sulphuric acid for its reuse.
In wastewater treatment plants, physical unit
operations are first used in order to remove solids,
sand, grit, fibres, oil and grease, floating substances
and other materials or compounds in which
transformation is carried out through the application of
physical forces. The unit operations include screening,
grit removal, sedimentation, flow equalization, aeration
and flotation. These treatments avoid obstructions and
enhance the performance of the subsequent treatment
stages.
After the preliminary treatment, the effluents go to
physic-chemical treatment by coagulation and
flocculation. Chemical coagulants such as aluminum
sulphate or ferric chloride are added to interact with the
solids in order to de-stabilize suspended colloidal
particles to form flocs. Flocculants, typically organic
chemicals like anionic polyelectrolytes, enhance the

TABLE I
Review of research about composition and treatment efficiency of tannery wastewater

Research Authors

Wastewater characterization by steps process
Raw wastewater characterization
Efficiency analysis of each treatment step
Efficiency analysis of total treatment process
Cassano et al. (2001)6, Collivignarelli and Barducci (1984)14,
Cooman et al. (2002)15, Gutterres et al. (2005, 2010, 2011)16–18,
Rao et al. (2003)19, Rivela et al. (2004)20, Sathish et al. (2013)21,
Suresh et al. (2001)7, Wang et al. (2014)22.
Bhattacharya et al. (2013)23, Di Iaconi et al. (2002)24,
El-Sheikh et al. (2011)25; Floqi et al. (2007)26; Kurt et al. (2007)11,
Mandal et al. (2010)27; Munz et al. (2008)28, Orhon et al. (1999)29,
Preethi et al. (2009)30, Ram et al. (1999)31,
Haydar and Aziz (2009a)9, Song et al. (2000, 2004)32,33.
Coagulation-flocculation: Aber et al. (2010)34, Gao et al. (2004)35,
Rossini et al.(1999)36, Haydar and Aziz (2009b)37.
Biological treatment: Leta et al. (2004)8.
Bhattacharya et al. (2013)23, Kurt et al. (2007)11,
Mandal et al. (2010)27, Preethi et al. (2009)30.

281
flocculation process. The settleable part (sludge) is
separated from the clarified effluent in sedimentation
tanks.
The biological treatment processes aim at the
removal of the organic load from the effluents in
colloidal and/or suspended form. The most frequently
used biological treatment is the suspended growth
aerobic process, named activated-sludge, where the
microorganisms responsible for treatment are
maintained in liquid suspension by appropriate mixing
methods. The system consists of a tank provided with
aeration, which works as a biological reactor, followed
by a secondary sedimentation tank and a pump that
performs partial recycling of the biological (activated)
sludge in the tank in order to increase the microbial
mass and keep it alive. Excess biomass produced as
floc particles is removed by gravity settling in the
sedimentation tank.
To remove moisture from the sludge, drying beds
and mechanical dewatering systems such as
centrifuges, filter presses and dewatering belt presses
are employed. The chromium-containing sludge must
be disposed in hazardous-waste landfill while sludges
not containing chromium can be used in agriculture or
go to non-hazardous landfill.
The present concerns about the efficiency of
treatment wastewater plants are in regard to the
nutrient removal (essentially nitrogen in case of
tanneries) and monitoring methods, analyses and
control of residual toxicity, thus, biological nutrient
removal (BNR) systems have become part of
conventional wastewater treatment and advanced
treatments are being adopted in order to meet emission
standards and non-toxicity requirements before
discharging the effluents into rivers and water bodies.
Tertiary treatment includes operations aimed at the
removal of specific pollutants that did not reach the
requirements of emission standards and/or increasing
the efficiency of the processes used in the treatment of
effluents. Treatment systems such as sand filtration, ion
exchange, adsorption, disinfection, advanced oxidation
processes, membrane filtration, reverse osmosis and
advanced oxidation are being investigated widely for
tannery wastewater treatment38 and are gaining
importance with respect to being adopted by the industry.
This paper presents a review of the characterization
of raw tannery wastewater available in the literature
and analyses and discusses the pollutant parameters
of raw wastewater collected from six different tanneries
with their respective categorisation.
MATERIALS AND METHODS
Tanneries and sampling
The wastewater samples analyzed were obtained
from six tanneries located in the State of Rio Grande do
Sul (Southern Brazil). Three of the factories were
complete tanneries and the other three were wet
end/finishing tanneries. Table II summarizes the main
characteristics of the operation of each company.
282
The wastewater treatments most employed by these
companies include a grit and solids removal
(screening), equalization basin, coagulants and
flocculant addition, primary settling, biological
treatment, secondary settling and, in some instances,
an additional treatment by another physical-chemical
step (coagulants/flocculants followed by settling or
flotation) before the discharge to the receiving body.
Wastewater characterization
Wastewater samples were collected from the
equalization tank in polyethylene bottles and preserved
by acidification to pH≤2 using sulphuric acid when
necessary. The collected samples were stored at 4°C
for subsequent use. Samples were analyzed for pH,
conductivity, turbidity, solids, total hardness, chlorides,
chromium oxide, biochemical oxygen demand after five
days (BOD5), chemical oxygen demand (COD), total
organic carbon (TOC), phosphorus (P), ammonia
nitrogen and total Kjeldahl nitrogen (TKN). The
concentrations of chromium oxide,39 solids40,41 and total
hardness42 in the wastewater were measured
according to Brazilian standards. Other parameters
were analyzed using test procedures outlined in
Standard Methods.43 Total organic carbon was
analyzed in TOC analyzer, Shimadzu.
RESULTS AND DISCUSSION
The characterization data of tannery effluents
available in the literature are shown in Table III, where
the COD, solids, pH, BOD, chlorides and other more
specific parameters are analyzed by the authors.
The physical-chemical characteristic parameters of
the tannery wastewater samples analyzed in this work
are summarized in Table IV. The values of BOD, TOC
and TKN in wastewater detected in this work appears
to be higher than the values found in the cited
references but overall the values are of the same order
of magnitude.
The results for four of the tanneries accessed in this
work, which do not separate the tanning or re-tanning
streams, some parameters of the wastewater collected
are charted in Figure 1 for discussion. It is evident that
the big contribution to wastewater contamination is
made by complete tanneries I and II in comparison with
wet end/finishing tanneries IV and VI. This is explained
by the removal of undesirable substances (dirt,
degraded proteins) of the hide during the beamhouse
operations in tanneries I and II, which contributes to
high levels of the pollution parameters, especially
providing higher values of TKN, as shown in Table IV.
All tanneries I, II, IV and VI, showed the parameter
DQO to be higher than DBO due to chemicals used in
leather processing this indicates the non-biodegradable
or slowly biodegradable portion of organic matter in
tanneries wastewater although; some of this portion
may be removed by WWTP (Wastewater Treatment
Plant) using suitable coagulants, flocculants and
primary sedimentation. Total fixed solids are associated
with DQO and total volatile solids are more associated
with DBO and TOC.
 TABLE II
Description of the tanneries accessed

Tannery Tannery process Wastewater treatment plant (WWTP) Water Water flow Leather
sources rate production

I* Complete tannery: from
beamhouse to finishing
Segregation and pre-treatment of Local river 300m3/day 2400kg of
chromium tanning baths (I-Cr and I). wet-blue/day
The wastewater streams are mixed to
be treated in the own wastewater
treatment plant (WWTP)

II Complete tannery: from Segregation and pre-treatment of Well and rainwater 950m3/day 34000 leather/month
beamhouse to finishing chromium tanning baths. The wastewater
streams are mixed to be treated in the
own wastewater treatment plant (WWTP)

III Complete tannery: from Segregation and pre-treatment of Local river 320m3/day 54000 m2/month
beamhouse to finishing chromium tanning baths. The wastewater wet-blue
streams are mixed to be treated in the 46000 m2/month
own wastewater treatment plant (WWTP) finished leather

IV Wet-end and finishing All wastewater streams are mixed to be treated Rainwater and 360 m3/day 1500-2000
in the own wastewater treatment plant (WWTP) wastewater reuse leathers/day

V** Wet-end and finishing Segregation of wastewater containing Well 160 m3/day 2200 leathers/day
chromium and vegetable tannins (V-Cr and V-tan).
Chromium tanning wastewaters are treated in
the own wastewater treatment plant (WWTP)

VI Wet-end and finishing All wastewater streams are mixed to be treated Local river 4200-4400 2200 leathers/day
in the own wastewater treatment plant (WWTP) m3/month

* Tannery I: I-Cr are streams from chromium tanning baths; I are streams of all others chromium free baths.
** Tannery V: V-Cr are streams from wet-end with chromium; V-Tan are streams from wet-end with vegetable tannins.

283
 TABLE III

284
Parameters of raw tannery wastewater from the literature

pH Cond. COD BOD Solids Cl- S2- NH4-N P Cr TOC TKN Reference

8.0-8.5 34,000-38,000 3500-4000 200-2400 TSS: 1500-2500 6000-7000 – 200-300 – – 700 -800 300 -500 Di Iaconi et al.(2002)24
VSS: 1000-1500

7.2 19,950 2810 910 TSS: 1520 6400 89 130 – 62 – – Kurt et al. (2007)11

8.5 1342 5680 759 TSS: 1690 6580 185 – – 521 514 2.87 Bhattacharya
TS: 10,140 et al. (2013). 23

7.9-9.2 20,042 2533 977 TSS: 1244 6528 860 118 62 258 – –
TDS: 21,620 Mandal et al. (2010)27

7.5-9.6 – 740-2040 390 -1320 TSS: 568 - 2132

SS: 20 - 88 1000-4549 – – – 22.9 -122.4 – – Haydar and Aziz (2009a)9

8.4 – 5000 – TSS: 4200

TDS: 10,000 – – – – – – – Preethi et al. (2009)30

7.79 – 2155 - VSS: 578 7008 35.8 168 6.3 50.9 – 228 Orhon et al. (2000)29
SS: 915

7.5-9.0 – 5000-10,000 1500-2000 TSS: 500 - 4000 – – – – 100 – – Song et al. (2000)32
TS: 29,000-45,000

9.2 ± 0.2 – 3300-150 – TSS: 260 ± 45 – – – – 16.8 ± 2.3 – – Song et al. (2000)33
TS: 15,000 ± 550

– – 13,000-14,000 – TSS: 900-1200 – 55-190 750-1500 – – – – El-Sheikh et al. (2011)25

9.3-11.0 – 4237-11,032 832-2564 TSS: 1264-9984 – 21-380 14.7-104 – 4.75-77 – – Floqi et al. (2007)26

5.8-7.5 6300-12,100 1280-5680 – TSS: 160-1840 3690-7410 3-80 102-324 – – – 190-420 Munz et al. (2008)28

9.6-11.5 – 2000-3560 700-1410 TSS: 655-2136 4500-12,100 40.0-72.0 18.0 -56.0 – 56.0-125.0 – – Ram et al. (1999)31
TS: 12,144-22,096
VSS: 11,324-19,920

Cond.: Conductivity; COD: Chemical Oxygen Demand; BOD: Biochemical Oxygen Demand; TSS: Total Suspended Solids; TS: Total Solids; VSS: Volatile Suspended Solids;
SS: Suspended Solids; TDS: Total Dissolved Solids; Cl-: Chloride; S2-: Sulphide; P: Phosphorous; Cr: Chromium; TOC: Total Organic Carbon; TKN: Total Kjeldahl Nitrogen.
*All parameters are expressed in mg l-1 except for pH, conductibility (µS/cm) and Turbidity (NTU).
 Figure 2 shows how total hardness and chloride
concentration affect the conductivity, increasing the
value of this parameter in the six tanneries accessed.
Alkalinity and hardness can help in the formation of
flocs when coagulants are used in WWTP. The High
turbidity detected is related to total suspended solids
(Table IV) and pH variations depend on the steps of
leather processing.
The chromium remaining in the wastewater denotes
the importance of segregation in streams containing
chromium, this will facilitate recovery of the metal and
prevent contamination of the sludge.
The low phosphorus concentration compared to the
nitrogen levels (TKN and NH4-N) suggests that P is the
limiting nutrient parameter for the biological treatment
of the wastewater.

TABLE IV
Results for parameters of raw tannery wastewater collected

Parameter Tanneries

I-Cr I II III IV V-Cr V-tan VI

pH 4.79 8.99 5.78 8.85 6.89 6.73 3.96 5.49

Cond. 34,500 24,940 28,680 23,400 12,290 4,430 17,990 3,760
Turbid. 1500 1900 >4000 2800 2500 2000 2000 500
COD 5178 3884 8523 4590 4315 6081 54,336 2579
BOD5 2834 1769 4073 2117 2089 3137 27,038 1327
TOC 1152 1324 1040 874 928 1393 8367 658
TS 37,378 21,246 20,800 13,199 12,969 7379 23,536 3709
TFS 34,378 19,229 10,762 9592 9248 4171 15,208 1850
TVS 9019 4135 4992 3206 3879 3580 3578 1408
TSS 3291 1591 3325 2497 2826 1706 510 957
VSS 2977 957 2785 1779 2452 1480 400 899
TDS 40,106 21,773 12,429 8109 10,301 6045 24,543 2301
VDS 6042 3178 2207 1427 1427 2100 3178 509
Cl- 7342 10,011 5224 3456 2979 996 5002 1056
TKN 1852 2487 7382 12,912 609 2064 12,992 265
NH4-N 728 762 185 288 212 24 42 54
P 60 39 83 15 69 18 68 42
Cr2O3 166 – 212 106 44 – – 56
Hardness 5422 2142 1733 1230 1187 487 657 258

Cond.: Conductivity; Turbid; COD: Chemical Oxygen Demand; BOD5: Biochemical Oxygen Demand after 5th day;
TSS: Total Suspended Solids; TS:Total Solids; SS: Suspended Solids ; VSS: Volatile Suspended Solids;
VDS: Volatile Dissolved Solids; TDS: Total Dissolved Solids; TOC: Total Organic Carbon; TKN: Total Kjeldahl Nitrogen;
Hardness: Total Hardness; NH4: Ammonium Nitrogen; Cr2O3: Chromium Oxide; P: Phosphorous.
*All parameters are expressed in mg l-1 except for pH, conductibility (µS/cm 25°C) and Turbidity (NTU).

Figure 1. COD, BOD, TOC, TKN and solids of the raw tannery wastewater collected.

285
Figure 2. Hardness, chloride and conductivity of the solids of the raw tannery wastewater collected.
CONCLUSIONS
The values of the characteristic parameters of
tannery wastewater vary widely and depend on the raw
materials and chemical products used as well as the
leather processing steps.
The beamhouse operations are the major source for
the organic matter in wastewater.
For all different tanneries studied, the parameters of
wastewater pollution obey the same pattern and are
similarly associated, which suggests and shows a
common guideline for tannery wastewater treatment
systems.
Due to growing environmental concerns and
worldwide fresh water shortage, clean technologies and
water re-use, nitrogen removal and advanced
treatment systems are being developed and adopted
in order to avoid water contamination and to meet
requirements prior to discharge of tannery the effluent
to surface waters.
ACKNOWLEDGEMENTS
We wish to acknowledge the financial support from
MCTI/FINEP CT-HIDRO 01/2013 and offer our
appreciation to the tanneries for the technical
information and collected samples.
(Received November 2014,
revised December 2014)
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