To whom correspondence should be addressed. Fax: 385-1-4667526.

E-mail: zeljko.bajza@zg.tel.hr.
Ecotoxicology and Environmental Safety 50, 15}18 (2001)
Environmental Research, Section B
doi:10.1006/eesa.2001.2085, available online at http://www.idealibrary.com on
Water Quality Analysis of Mixtures Obtained from Tannery
Waste Effluents
Zeljko Bajza* and Ivana Vinkovic Vrcek-
*Faculty of Chemical Engineering and Technology, University of Zagreb, 10000 Zagreb, Marulicev trg 19, Croatia; and -Faculty of Pharmacy and Biochemistry,
University of Zagreb, 10000 Zagreb, A. Kovacica 1, Croatia
Received May 9, 2000
In this study, the mixing of waste solution obtained from
chrome tanning process and waste solution derived from liming
of bovine leather was investigated. The liming process of bovine
leather was performed using calcium carbonate and sodium
sul5de, and the tanning process was performed using alkaline
chromium sulfate. The analyses of waste solutions and sediments
formed during the mixing process include pH values, the concen-
tration of sul5des, the concentration of chromium(III) oxide,
and parameters such as chemical oxygen demand and biochemi-
cal oxygen demand. All measurements were carried out before
and after the mixing process. Results indicate that the mixing of
the corresponding waste solutions yields the mixture e8uents
that are ecologically acceptable. 2001 Academic Press
Key Words: BOD
5
; chromium; COD; liming; sul5des; tanne-
ries; wastewater.
INTRODUCTION
Leather processing is characterized by a large amount of
liquid and solid waste. Wastewaters are very complex and
the most di$cult problem among tannery wastes. Waste-
waters derived from washing/soaking and from liming of
bovine leather makeup 31% of the total amount of waste-
waters, and wastewater derived from the tanning process
makes up 11% of the total amount of wastewaters. The
remaining wastewaters include 25% retanning wastewater,
26% washdown water, and 7% machine water. Typical
combined tannery e%uent, which has not yet been treated, is
characterized by a high oxygen demand and high salt con-
tent (chromium salts, sul"des, chloride ions, etc.) and is
strongly alkaline. Traditional soaking and liming of leather
result in more than 50% of wastewater pollution in tanne-
ries. Lime blended with sodium sul"de is traditionally used
to loosen wool and hair, or to dissolve these into a
pulp. This process is responsible for the major part of the
chemical oxygen demand (COD) and biochemical oxygen
demand (BOD
`
) load from a tannery. The chrome tanning
process also produces a large quantity of wastewaters and
total pollution. Wastewaters derived from washing/soaking
and from liming and wastewater derived from the tanning
process make up less than 50% of all wastewater; however,
their pollution e!ects are the most signi"cant (over 90%).
Thus, 88% of BOD
`
is related to beamhouse waters, and
8% to tanyard waters. Seventy-three percent of COD is
related to beamhouse waters, and 13% to tanyard waters,
while 83% of suspended solids are related to beamhouse
waters, and 11% to tanyard waters (Konrad et al., 2000).
The majority of leathers today are chrome-tanned in drums
for 4 to 24 h. Wastewater characterization of conventional
pollutants for hair pulp/chrome tan/retan}wet "nish sub-
category mean are as follows: BOD
`
, 1600; COD, 4600;
sul"des, 64; total chromium, 76 (UNEP, 1991). Tannery
e%uents consist of di!erent streams, the sul"de-containing
waters, the sul"de-free beamhouse waters, the waters abun-
dant in chrome, and "nally the #oats with only chrome
traces. Every treatment starts with water collection for
a greater or daily charge, mixing, and pH adjustment
(Besserer, 1996).
As tannery e%uents contain several chemical constituents
needed to be treated, a sequence of treatment processes
must be used. A primary treatment includes sul"de removal
from beamhouse e%uents, chrome removal from tanning
e%uents, and physical}chemical treatment for BOD re-
moval and neutralization (UNEP, 1991).
In the majority of tanneries, chemical pretreatment is
performed separately for alkaline wastewaters derived from
washing and liming process and for wastewaters derived
from the chrome tanning process. Alkaline solution is com-
monly treated with Fe
`
(SO
"
)
`
, which precipitates sul"des.
Chromium(III) salts are treated with lime, a basic coagulant
in primary treatment of wastewaters in tanneries (McEdow-
ney, 1993). Preliminary treated solutions are mixed with the
rest of the wastewater in balancing tanks (Besserer, 1996).
Equalization of solutions is performed to improve tanning
15
0147-6513/01 $35.00
Copyright 2001 by Academic Press
All rights of reproduction in any form reserved.
FIG. 1. The time dependency of pH value measured after the mixing of
waste solutions derived from liming and chrome tanning.
e$ciency. Flowbalancing is pretreatment that eases some of
the operational problems involving e%uent variability
(UNEP, 1991).
The generally accepted concentration of sul"des in pol-
luted water from tanneries is 2 mgdm`. Concentration of
chromium(III) salts in untanned wastewater usually comes
to 2}3 gdm`, and the accepted concentration is lower than
1 mgdm` (Besserer, 1996).
End-of-pipe e%uent treatment reduces the environmental
impact of tanneries. In order to exercise e!ective day-to-day
control over the tanning process, and over the treatment of
wastewaters, it is necessary to be able to analyze samples of
process liquors and e%uents on a regular basis (UNEP,
1991).
MATERIALS AND METHODS
Samples of waste solutions were obtained from commer-
cial tanneries. In this study, samples of waste solutions
derived from liming (processing of raw leather with 3%
calcium carbonate and 1.5% sodium sul"de) and tanning of
bovine leather (processing with 7% chromium(III) sulfate,
a technical product containing about 26% Cr
`
O
`
of basic-
ity 33%) were used. In samples of waste solutions obtained
after bovine leather liming pH and concentration of sodium
sul"de were examined, and in those samples derived from
chrome-tanned bovine leather, pH and concentration of
Cr
`
O
`
were analyzed. Waste solutions derived from both
liming and tanning of bovine leather were mixed in the
ratios 1: 9, 3: 7, 5: 5, 7: 3, and 9: 1, respectively.
The concentration of sul"des and chromium dioxide, the
volume of formed sediment, and the mass of suspension
were determined after mixing. Time dependence of pH value
in these solutions was measured over a time interval of
120 min in order to determine a range of time needed for
stabilization of solution properties. pH was measured using
a pH meter with glass and calomel electrodes.
The concentration of sul"des was determined using the
standard titration method with Na
`
S
`
O
`
in the presence of
iodine. The sodium sul"de was precipitated with Fe
`
(SO
"
)
`
,
according to Eq. (1), and the residual Na
`
S was titrated by
a solution of Na
`
S
`
O
`
:
Na
`
S#Fe
`
(SO
"
)
`
PNa
`
SO
"
#Fe
`
S
`
. [1]
Solutions of 1, 5, and 10% Fe
`
(SO
"
)
`
were used, respec-
tively.
Chromium(III) salts were precipitated with Ca(OH)
`
.
Oxidation of chromium(III) was performed with KMnO
"
and HCl according to the following equations:
Cr(OH)
"
#MnO
"
PCrO
"
`#MnO
`
#2H
`
O [2]
2CrO
"
`#2H>PCr
`
O
`
`#H
`
O. [3]
Solutions of 1, 5, and 10% Ca(OH)
`
were used, respec-
tively.
Concentration of chromium(III) was determined by using
the titration method with Na
`
S
`
O
`
in the presence of KI
according to the following equations:
Cr
`
O
`
`#6I#14H>P2Cr`>#3I
`
#7H
`
O [4]
I
`
#2S
`
O
`
`P2I#S
"
O
'
`. [5]
Sediment (mud formed in 2 h) was determined by the
measuring volume of the formed sediment in glass mensura.
The sediment was weighed after drying on "lter paper at
temperature of 1053C for 2 h. COD was determined using
the colorimetric method with a DR100 colorimeter in
HACHcuvettes, and in the presence of potassium bicarbon-
ate and sulfuric acid (UNEP, 1991). BOD
`
was determined
using a standard method (5210B) (Aloy and Buljan, 1994).
The sample was incubated at 203C in the dark for 5 days.
The amount of dissolved oxygen was measured. The con-
sumption of oxygen after a period of 5 days in the sample
was calculated from the di!erence between the initial and
the "nal concentration of oxygen.
RESULTS
The pH value of waste solution after liming at a temper-
ature of 17.53C was found to be 12.5, that of waste solution
after chrome tanning at the same temperature was 3.9. The
time dependency of pH value measured after the mixing of
waste solutions derived from liming and chrome tanning is
presented in Fig. 1, and the variation of volume of the
formed sediments after the mixing process is presented in
Fig. 2. Table 1 presents concentrations of sodium sul"de
and chromium(III) oxide, COD and BOD
`
parameters in
waste solutions after liming and chrome tanning of bovine
16 BAJZA AND VRCEK
FIG. 2. The variation of volume after the mixing of waste solutions
derived from liming and chrome tanning.
TABLE 1
Results for the Concentration of Sul5des, the Concentration of Chromium(III) Oxide, CODand BOD
5
in Waste Solution Derived
from Liming of Bovine Leather, Waste Solution Obtained from Chrome Tanning Process, and Solutions Obtained by Mixing These
to Waste Solutions in Di4erent Ratios
Liming waste solution: Chrome tanning waste solution
Liming waste Chrome tanning
solution waste solution 1: 9 3: 7 5: 5 7: 3 9: 1
pH 12.5 3.9 6.61 9.11 10.03 11.53 12.13
(Na
`
S), mgdm` 8,020 0 31 1,249 2,748 1,232 8,328
4,122 (1%)
406 (5%)?
(1 (10%)?
(Cr
`
O
`
), mgdm` 0 561 302 188 66 (1 (1
36 (1%)`
(1 (5%)@
(1 (10%)@
COD, mgdm` 22,510 6,400 6,700 10,380 17,775 19,550 27,125
BOD
`
, mgdm` 7,030 2,500 2,200 2,300 2,830 4,300 6,500
Volume of sediment, mL * * 4.0 19 18 18 7
Total solids, mgdm` 13,500 10,000 1,885 8,220 8,120 10,280 8,330
?Concentration of Fe
`
(SO
"
)
`
used for the precipitation process of sul"des in liming waste solution.
@Concentration of Ca(OH)
`
used for the precipitation process of chromium(III) salts in chrome tanning waste solution.
leather, and the concentrations of solutions obtained by
mixing these two solutions in di!erent ratios.
DISCUSSION
Ca(OH)
`
and Na
`
S with water form a high concentration
of OH ions. This resulted in a pH value of 12.5 for waste
solution obtained after the liming process. The molar con-
centration of sul"des was 8020 mgdm`, which is in agree-
ment with common values (6000}10,000 mgdm`) (Barabas
and Huszar, 1986). Precipitation of sul"des with 10%
Fe
`
(SO
"
)
`
decreases the concentration for Na
`
S below
2 mgdm`. This value is within the safety standards
(Besserer, 1996).
In the waste solution obtained after the chrome tanning
process the concentration of Cr
`
O
`
was 561 mgdm`, and
after precipitation with 1% Ca(OH)
`
it was 36 mgdm`.
Precipitation of Cr
`
O
`
using 5 and 10% Ca(OH)
`
reduced
the concentration of Cr
`
O
`
below 1 mgdm`, which is
lower than the values de"ned by safety regulations (Be-
sserer, 1996).
pH value of the resulting mixture was relatively stable
during the 120 min of the mixing process. The mixture
composed of liming waste solution and tanning waste solu-
tion in the ratio 1: 9, respectively, had the lowest pH value,
6.34. In 120 min this value increased by 0.27. With the
relative increase of liming waste solution fraction, the pH
value of the mixture increased. Thus, the mixture composed
of liming waste solution and tanning waste solution in the
ratio 9: 1, respectively, had pH value of 12.13.
The largest amount of sediment was formed during the
mixing process of liming waste solution and tanning waste
solution in the ratio 7: 3, respectively. The mass of the
sediment was 10,280 mg/Liter of the mixture. A high quanti-
ty of sediment was also formed in ratios of 5: 5 and 7: 3. The
largest decrease in the sediment volume, from 16.5 to 7 mL
over the 120-min mixing process, was observed in the mix-
ture composed of liming waste solution and tanning waste
solution in the ratio 1: 9, respectively.
The largest concentration of Na
`
S (6401 mgdm`) was in
the mixture of liming waste solution and tanning waste
solution in the ratio 9: 1, respectively, while the largest
concentration of chromium was found in the corresponding
mixture of ratio 1: 9, respectively. With the increase of lim-
ing waste solution fraction in the mixture, the COD value
increased from 6700 to 27,125 mgdm`, while the BOD
`
WATER QUALITY ANALYSIS OF TANNERY WASTE EFFLUENTS 17
value increased from 2200 to 6500 mgdm`. The smallest
value for both COD and BOD
`
parameters was observed in
the ratio 1: 9, respectively. According to these results
a greater quantity of organic material was found in the
liming waste solution.
CONCLUSION
This study indicates that the mixing of waste solutions
derived from liming process and chrome tanning process in
di!erent ratios results in signi"cant changes in pH values,
concentration of sul"des, concentration of chromium(III)
oxide, COD and BOD
`
values, and mass of the formed
sediment.
Ecological parameters resulting from waste e%uents in
the majority of the tanneries today are not as acceptable as
they should be. The results of this work indicate that the
fraction of wastewaters derived from washing/soaking and
liming processes should be mixed together in a speci"c ratio
with wastewaters derived from tanning processes. This
should be performed before the equalization process is car-
ried out in order to obtain the most acceptable ecological
parameters. In that case, pretreatment procedure of waste-
waters derived from tanning processes and pretreatment
procedure of wastewater fractions derived from wash-
ing/soaking and liming processes could be omitted.
Pretreatment of the rest of wastewaters derived from
washing/soaking and liming processes should be performed.
The proposed procedure would reduce the cost of materials
that are necessary for neutralization of wastewaters. The
physico-chemical treatment of wastewaters was made more
e$cient and resulted in more acceptable ecological para-
meters. This investigation may help in designing new
methods for monitoring waste e%uents from tanneries.
REFERENCES
Aloy, M., and Buljan, J. (1994). &&Selection of Equipment for Labaratories
Monitoring Pollution in the Tanning Industry,'' pp. 11}29. United
Nations Industrial Development Organization, Wien.
Barabas, A., and Huszar, L. (1986). Chromarme und Chromfreie Gerbver-
fahren. In &&Congress on the Leather Industry, Budapest,'' I/A/1,
pp. 37}47.
Besserer, D. (1996). Betriebliche Erfahrungen bei der Reinigung von Ger-
berei-Abwasser nach gesetzlichen Au#agen und gesamtheitlicher
Betrachtung. Das eder 47, 243}253.
Heidemann, E. (1993). &&Fundamentals of Leather Manufacturing,''
pp. 269}290. Eduard Roether KG, Darmstadt.
Konrad, C., Bichler, B., Lorer, K., and Marquez, F. (2000). J. Soc. Leather
Technologist Chemists 84, 223}226.
McEdowney, S., Hardman, D. J., and Warte, S. (1993). &&Pollution: Ecology
and Biotreatment.'' Wiley, New York.
United Nations Environment Program (UNEP), Industry and Environ-
ment O$ce (IEO) (1991). &&Tanneries and the Environment,'' 1st ed.
UNEP, Paris.
18 BAJZA AND VRCEK