Desalination 211 (2007) 314–320

Investigation of the relation between COD fractions and the

toxicity in a textile finishing industry wastewater:
Effect of preozonation

Gulen Eremektara, Huseyin Selcukb, Sureyya Mericc*

a
Istanbul Technical University, Environmental Engineering Department, 34469, Maslak, Istanbul, Turkey
b
Pamukkale University, Environmental Engineering Department, Kinikli/Denizli, Turkey
c
Department of Civil Engineering, Environmental Engineering Division, University of Salerno,
84084 Fisciano (SA), Italy
Tel. +39 (089) 96 4016; Fax +39 (089) 96 4100; email: smeric@tin.it, msureyya@unisa.it

Received 15 December 2005; revised 5 February 2006; accepted 9 February 2006

Abstract
Textile industry is one of the most common and essential sectors in the world. On the other hand, high volume
of water consumption and varying wastewater characteristics due to many products such as dyes, biocides, carriers,
detergents, etc. used in the process are the factors that have caused a continuous effort to find appropriate technologies
to treat textile industry wastewater. In the last decade, the use of advanced oxidation processes (AOPs) has gained
importance to degrade, decolorise and detoxicify the textile wastewater. However, the main mechanisms for AOPs
for removing toxicity, thus, any contribution by the reduction of decreased inert factions in the effluent of textile
wastewater are still to be studied. This study aimed to investigate the relation between inert COD fractions (which
are characteristics in part of the influent wastewater, and in part generated in the biological treatment as the common
used treatment process for textile industry) and effluent toxicity in the presence/absence of pre-ozonation. 18.5 mg/
l of ozone dose was applied during 30 min oxidation on two wastewater samples taken from balancing tank of a
textile industry localized in Istanbul, Turkey. A direct assessment method was used to determine inert COD fractions
of the raw and ozonated wastewater samples. The toxicity of raw and treated was tested using newborn (<24 h)
samples of Daphnia magna for 24 h exposure time. The soluble inert COD (SI) decreased significantly while
soluble residual microbial product (SP) increased slightly due to preozonation. The sum of soluble inert fractions

*Corresponding author.

Presented at the 9th Environmental Science and Technology Symposium, September 1–3, 2005, Rhodes, Greece.
Organized by the Global NEST organization and prepared with the editorial help of the University of Aegean,
Mytilene, Greece and the University of Salerno, Fisciano (SA), Italy.

0011-9164/07/$– See front matter © 2007 Published by Elsevier B.V.

doi:10.1016/j.desal.2006.02.096
 G. Eremektar et al. / Desalination 211 (2007) 314–320 315

were found in the order of 17–18% and 20% of total COD for raw and preozonated samples. Preozonation decreased
the toxicity of raw wastewater. This phenomenon was evidenced also by testing the effluents of the inert COD
determination reactors.
Keywords: Textile industry; Acute toxicity; Ozonation; Wastewater treatment; Inert COD fractions; Decolorisation;
Degradation; Detoxification; Daphnia magna

1. Introduction and acute toxicity [14–16] in textile industry

wastewater.
Textile industry wastewater has been charac-
This paper summarizes the results, as a comple-
terised with its complexity, composed of dyestuff,
mentary stage to acute toxicity and the inert COD
surface-active materials and additives which are
fraction removal by preozonation from textile in-
related to color and effluent toxicity problems
dustry wastewater, of our previous findings [16],
[1,2]. Many reactive, direct dyes have been found
and further presents the identifications of the re-
toxic to aquatic life [3–7]. Therefore, many ad-
lation between inert COD fractions and the acute
vanced oxidation processes (AOPs) such as pho-
toxicity on Daphnia magna which has been used
tocatalytic oxidation [8], Fenton (FO) [4,5,9],
as a standard and reliable biotest to tests many
photo-Fenton [10] and ozone oxidation [11–16]
textile dyes [4–7], auxiliaries and wastewater
have been attempted individually or combined
[1,9,14–16].
with UV or H2O2 oxidants to decolorise, detoxicify
and enhance the biodegradability of textile waste-
water and dyes.
2. Materials and methods
The composition of raw wastewater such as
recalcitrants of biocides, carriers [17], therefore 2.1. Sampling
inert fractions of the wastewater influence heavily
Raw textile wastewater samples (S1 and S2)
the biodegradation of this industry’s wastewater
were taken from the process wastewater balanc-
[13,18]. Therefore, determination of COD frac-
ing tank of a textile industry located in Istanbul
tions gains importance because it provides us more
(Turkey). In the industry, cotton and polyester
information on biological treatability of waste-
fabrics are dyed using reactive, dispersive dyes.
water as well as the extent of complying with the
The wastewater resources are the bleaching and
discharge limits. The COD fractions in wastewa-
dyeing units for cotton processing and dyeing of
ters are defined: initially inert particulate COD
synthetic fabric. Total process wastewater is
(XI), initially inert soluble COD (SI); particulate
around 500 m3/d. The samples were delivered to
residual meatbolic products (XP), soluble residual
the laboratory cooled and kept at 4°C during ex-
metabolic products (Sp); readily biodegradable
perimental study. Toxicity tests were done within
COD (SS) and slowly biodegradable COD (XS)
1 d while chemical analyses were realized in 3 d
[18,20]. SI and XI leave the the traetment system
after collection.
unchanged, however XI is entrapped in the sludge
line. Thus, it becomes important to assess the ef-
2.2. Ozonation
fluent SI value causing a direct impact to aquatic
environment. Preozonation was found to be ef- Ozone was generated from air by ozone gen-
fective to reduce inert COD fractions [12,13,16] erator (PCI model, GL-1). A closed cylindrical
316 G. Eremektar et al. / Desalination 211 (2007) 314–320
Pyrex glass reactor with a diameter of 40 mm and
height of 1100 mm was used in the ozonation ex-
periments [15,16,21]. A tubular cylindrical porous
diffuser was placed at the bottom of the reactor to
transfer input ozone gas into aqueous solution at
the regular intervals. Teflon tubing line was used
for the connection between ozone generator and
reactor.
Optimization experiments of ozonation were
performed at room temperature (25°C) and origi-
nal pH of wastewater using 1 L aqueous solution
[21]. A foam preventer was added into the reactor
to avoid the foam formation during oxidation. 9.5
and 11.2 of ozone doses were applied with an air
flow rate of 0.566 m3/h. The ozone concentrations
in input gas and in off gas were destroyed by two
sequential washing bottles containing 250 mL of
acidified 2% KI solution. Then, a sodium thyo-
sulfite titration procedure in the presence of starch
as the indicator [22] was performed to measure
ozone concentration. Hence, the transferred ozone
(TrO3) was calculated as:
TrO3 (mg/l) = input ozone concentration
(1)
− ozone concentration in off gas
Once optimum ozonation time was determined
for effective toxicity removal to be 30 min, the
raw water sample was ozonated for 30 min and
COD fraction determination reactors were run on
it as explained below.
2.3. Determination of inert COD fractions
Four aerated cylindrical batch reactors, one fed
with the unfiltered raw wastewater (R1, CTO), sec-
ond with raw wastewater (STO) filtered through
0.45 µm filter paper (R2), third fed with pre-
ozonated total wastewater (R3), and the fourth fed
with pre-ozonated filtered wastewater (R4), were
used for each sample. The activated sludge seed
was obtained from a lab-scale fill-draw aerobic
reactor operated under steady-state with the same
wastewater. An initial biomass concentration of
50 mg VSS/L was sustained in all reactors.
Aliquots were removed periodically from the
mixed liquor and analyzed for total and soluble
(filtered) COD. Data were collected until the COD
profiles reached a plateau. Any water loss from
the reactors by evaporation was replaced by add-
ing distilled water before measuring COD. The
experiments were concluded at a point where the
threshold level was established as less than 3–5%
variation between consecutive samples [18–
20,23]. At this stage the supernatant samples were
taken from the reactors to conduct the toxicity tests
after filtering through 45 µm membrane filter
(Millipore) [23].
2.4. Daphnia magna
The toxicity of raw and ozone-treated samples
and the effluent of the biological reactors run for
the COD fraction determination was measured
using 24 h newborn D. magna at different dilu-
tion rates [24] for 24 h exposure time. Daphnids
were grown in the laboratory at 16 h daylight and
8 h dark periods supplying a 3000 lux illumina-
tion. They were fed by Selenastrum capricor-
nutum (300000 cells/ml) and baker’s yeast (Schi-
zosaccharomyces cerevisiae, 200000 cells/ml) [9].
All solutions were prepared in bidistilled water at
pH 8.0. Room temperature was kept at 20±1°C
and minimum 6 mg/l of dissolved oxygen was
supplied by air filtered through activated carbon.
Experiments were carried out quadruplicate and
5 daphnids were used in each test beaker with
50 ml of effective volume. Results were evalu-
ated on the basis of immobilization percentage
obtained by dividing the number of immobilized
animals by total animals.
2.5. Analysis
All chemical parameters were measured ac-
cording to Standard Methods [25] except COD
[26]. The samples were filtered through 0.45 µm
membrane filter (Millipore) for measuring toxic-
ity, COD, color in APHA Pt-Co (HACH-Dr-B
 G. Eremektar et al. / Desalination 211 (2007) 314–320 317

model spectrophotometer) unit [21,23]. All chemi- 3.2. Ozone treatment

cals used were of analytical grade. KI solution
According to raw wastewater toxicity removal
used for residual ozone titration was prepared
at 50 and 75% dilutions the ozone oxidation con-
daily. Twice distilled water was used to prepare
ditions were optimized as summarized in Table 2.
the solutions.
The details of ozone oxidation optimization are
given elsewhere [16]. The difference between the
transferred ozone doses and concentrations for the
3. Results and discussion samples can be explained due to wastewater com-
position and the color intensity [16]. High toxic-
3.1. General
ity removal (90%) obtained at higher dilution
The characteristics of the raw wastewater (75%) indicates that the composition of oxidized
samples are given in Table 1. The high conduc- wastewater is affecting the toxicity test. However,
tivity (9400 and 12500 µS/cm for S1 and S2, re- testing samples at 75% dilution was indicative to
spectively) of both samples was toxic to D. ma- evaluate the changes occurring in the wastewater
gna without dilution (effluent becomes toxic over composition. Thus, more than toxicity removal it
10000 µS/cm [1]). The ammonia concentration was useful to define the ozonation condition for
of S1 (40 mg/l) was higher than 25 mg/l that was investigating the soluble inert COD fractions.
recorded 50% toxic to D. magna [9]. However,
both samples resulted in 100% toxic even at 80% 3.2. Inert COD fractions
dilution when the conductivity and ammonia pa-
The experimental conditions of inert COD
rameters were below the toxic limits. Thus, the
fractions for raw wastewater and ozone-treated
ozone oxidation was applied for removing the
samples are presented elsewhere [16]. Table 3 pre-
toxic component in the samples as well as affect-
sents the ratios of the inert COD fractions in total
ing the inert COD fractions of wastewater.
COD. The influent soluble inert COD fractions
of raw S1 and S2 were determined to be 280 mg/l
and 255 mg/l, respectively while the values of SP
(soluble residual COD generated as metabolic
Table 1
products) were found to be low as 10 mg/l for
Raw wastewater characteristics of the textile industry
both samples. The soluble residual COD
Parameter Sample 1 (S1) Sample 2 (S2)
COD, mg/l 1700 1685 Table 2
Soluble COD, mg/l 950 1000 Optimum removal conditions of ozone oxidation applied
BOD5, mg/l 150 170
for COD fractionation experiments
TSS, mg/l 750 250
VSS, mg/l 330 190
TKN, mg/l 70 16 Sample # S1 S2
NH3-N, mg/l 45 5 Ozonation time, min 20 30
Total-P, mg/l 30 14 COD removal, % 57 64
Conductivity, mS/cm 9400 12500 Filtered COD removal, % 33 39
Chloride, mg/l 1650 1750 Color removal, % 96 86
Sulphate, mg/l 525 590 TrO3, mg/l 200 129
Alkalinity, mg/l — 470 TrO3 rate, mg/L-min 9.5 4.3
Color, Pt-Co 3300 1000 Toxicity removal (%) 80 90
pH 8.8 8.6 at 75% dilution
318 G. Eremektar et al. / Desalination 211 (2007) 314–320

Table 3
Partition of the inert COD components for each sample before and after ozonation (initially inert particulate COD (XI),
initially inert soluble COD (SI); particulate residual meatbolic products (XP), soluble residual metabolic products (Sp);
readily biodegradable COD (SS) and slowly biodegradable COD (XS))

(mg/l KOI)/ Sample type SI/CTO XI/CTO CSO/CTO SP/CSO XP/CSO (SI + SP)/CTO
(mg/l KOI)
S1 RW 0.17 0.05 0.78 0.008 0.06 0.18
O3 treated 0.19 0.06 0.76 0.03 0.07 0.20
S2 RW 0.16 0.005 0.83 0.007 0.06 0.17
O3 treated 0.18 0.05 0.76 0.02 0.02 0.20

(SR = SI + SP) were calculated in the raw wastewa-
ter samples as 18–19% of the total COD. These
results were found at the same order with the pre-
vious studies on textile wastewater [12,13]. Pre-
ozone oxidation decreased SI component in both
samples significantly while soluble metabolic pro-
duct (SP) increased to 23 and 15 mg/l levels for
the same samples.
3.3. Toxicity–inert COD fractions relations
As seen in Table 4, there was significant evi-
dence that the supernants of pre-ozonated samples
(R3, R4) filtered through 0.45 µm pore size filter
displayed lesser toxicity than both total (R1) amd
filtered (R2) raw wastewater reactors when they
were tested at the same dilutions. However, the
toxicity levels were different between the samples.
Ozonated S2 displayed lesser toxicity than S1
even when it was tested without diluted. Lesser
toxic supernatant of the filtered S2 (R2) evidenced
that toxicity observed should be originated from
the soluble inert fractions (at 25% dilution) be-
cause any contribution by particular inert frac-
tions was already removed by filtering the sample
when the reactor was set initially, so no effect

Table 4
D. magna toxicity test results on the effluents of the biological wastewater characterization reactors (R1: raw wastewater
fed reactor; R2: filtered raw wastewater fed reactor; R3: ozonated total wastewater fed reactor; R4: filtered ozonated
wastewater fed reactor)

Sample # Dilution of Raw Immobilization (%)

wastewater (%) wastewater R1 R2 R3 R4
1 50 100 100 100 100 100
60 100 100 100 100 60±5
75 100 100 100 100 20±5
80 100 100 100 100 0
2 0 100 100 100 80 60±5
25 100 100 100 40 20±5
50 100 40±5 40 0 0
60 100 20±5 0 0 0
75 100 20±5 0 0 0
80 100 0 0 0 0
 G. Eremektar et al. / Desalination 211 (2007) 314–320
shoud be contributed by XI and XP fractions. The
much lower toxic results for all reactors for the
S2 sample indicated that wastewater complex mix-
ture should be origin of this beahviour although
its ammonia concentration was much lower than
S1, the conductivity was significantly higher than
S1. However, the colour unit of S2 was signifi-
cantly lesser than the S1 one. This point raised
the hypothesis that the relation between color
(dyes) and toxicity parameters which was strongly
evidenced in our previous studies [4,5,9,15,16],
as well as influencing the soluble COD fractions.
Furthermore, the recent studies have shown that
the toxicity of many additives used textile indus-
try such as biocides [2,17] are also influencing
factors the toxicity in whole sample. This point
should be detailed by analytical measurements as
it was demonstrated that textile industry waste-
water is composed of many organic consitutents
[27].
4. Conclusion
This study aimed to evaluate the effect of ozo-
nation on textile industry wastewater COD frac-
tions and acute toxicity, and investigation of their
relation which was the innovative approach of it.
The main findings obtained can be outlined as
follows:
• The different transfer ozone (TrO3) doses for
S1 and S2 can be explained by wastewater
composition and the color intensity and also
other varying ozone initiators, promoters and
scavengers in textile industry wastewater.
• Ozonation decreased the soluble inert COD
fraction of wastewater, thus, the sum of soluble
residual COD (sum of soluble inert and re-
sidual metabolic COD at the effluents) de-
creased below the discharge limits (250 mg/
L).
• Ozone is effective for removing acute toxicity
from the textile wastewater.
319
• Acute toxicity of raw and pre-ozonated
samples monitored using Daphnia magna was
related to the COD fractions.
Acknowledgements
This work was partly supported by Scientific
Research Council of Turkey (TUBITAK, IÇTAG-
Ç035) and ITU Research Development Center.
The technical support by Arda Yildiz and Volkan
Enç is appreciated.
References
[1] A. Villegas-Navarro, M.C. Rodriguez Santiago, E.
Rosas Lopez, R. Domunguez Aguilar and W.
Sachetin Marcal, Evaluation of Daphnia magna as
an indicator of toxicity and treatment efficacy of
textile wastewater. Environ. Int., 25 (1999) 619–624.
[2] C. Wang, A. Yediler, D. Lienert, Z. Wang and A.
Kettrup, Toxicity evaluation of reactive dyestuff,
auxiliaries and selected effluents in textile finishing
industry to luminescent bacteria Vibrio fisheri.
Chemosphere, 46 (2002) 339–344.
[3] A. Gottlieb, C. Shaw, C. Smith, A. Wheatley and S.
Forsythe, The toxicity of textile reactive azo dyes
after hydrolysis and decolourisation. J Biotechnol.,
101 (2003) 49–56.
[4] S. Meriç, D. Kaptan and T. Ölmez, Color and COD
removal from wastewater containing Reactive Black
5 using Fenton’s oxidation process. Chemosphere,
54(3) (2004) 435–441.
[5] S. Meriç, H. Selcuk, M. Gallo and V. Belgiorno,
Decolourisation and detoxicifying of Remazol Red
dye and its mixture using Fenton’s reagent. Desali-
nation, 173 (2005) 239–248.
[6] J.S. Bae and H.S. Freeman, Aquatic toxicity evalu-
ation of copper-complexed direct dyes to the Daph-
nia magna. Dyes and Pigments, (in press).
[7] J.S. Bae and H.S. Freeman, Aquatic toxicity evalu-
ation of new direct dyes to the Daphnia magna. Dyes
and Pigments, (in press).
[8] S.G. de Moraes, R.S. Freire and N. Duran, Degra-
dation and toxicity reduction of textile effluent by
combined photocatalytic and ozonation processes.
Chemosphere, 40 (2000) 369–373.
320 G. Eremektar et al. / Desalination 211 (2007) 314–320
[9] S. Meriç, H. Selçuk and V. Belgiorno, Acute toxic-
ity removal in textile finishing wastewater by
Fenton’s oxidation, ozone and coagulation-floccu-
lation processes. Water Res., 39 (2005) 1147–1153.
[10] M. Rodriguez, V. Sarria, S. Esplugas and C.
Pulgarin, Photo-Fenton treatment of a bio-recalci-
trant wastewater generated in textile activities: bio-
degradability of the photo-treated solution. J.
Photochem. Photobiol. A: Chemistry, 151 (2002)
129–135.
[11] S. Ledakowicz, M. Solecka and R. Zylla, Biodeg-
radation, decolourisation and detoxification of tex-
tile wastewater enhanced by advanced oxidation
processes. J. Biotechnol., 89 (2001) 175–184.
[12] D. Orhon, H. Dulkadiroglu, S. Dogruel, I. Kabdasli,
S. Sozen and F. Germirli Babuna, Ozonatian appli-
cation in activated sludge systems for a textile mill
effluent. Water Sci. Tech., 45(12) (2002) 305–313.
[13] O. Karahan, H. Dulkadiroglu, I. Kabdasli, S. Sozen,
F. Germirli Babuna and D. Orhon, Effect of ozona-
tion on the biological treatability of a textile mill
effluent. Envrion. Technol., 23 (2002) 1325–1336.
[14] H. Selcuk, Decolourization and detoxicification of
textile wastewater by ozonation and coagulation
process. Dyes and Pigments, 64 (2005) 217–222.
[15] H. Selcuk and S. Meric, Ozone pre-oxidation of a
textile industry wastewater for acute toxicity re-
moval. Global Nest: Int. J., 8(2) (2006) 7–14.
[16] H. Selcuk, G. Eremektar and S. Meriç, The effect of
pre-ozone oxidation on acute toxicity and inert
soluble COD fractions of a textile finishing indus-
try wastewater. J Hazard. Mat., 137(1) (2006) 254–
260.
[17] I. Arslan Alaton, G. Insel, G. Eremektar, F. Germirli-
Babuna and D. Orhon, Effect of textile auxiliaries
on the biodegradation of dyehouse effluent in the
activated sludge. Chemosphere, 62(9) (2006) 1549–
1557.
[18] D. Orhon, N. Artan and Y. Cimsit, The concept of
soluble residual product formation in the modelling
of activated sludge. Water Sci. Tech., 21(4–5) (1989)
339–350.
[19] G. Eremektar, A. Yildiz and S. Meriç, Determina-
tion of inert COD fractions in a textile industry
wastewater. Fresenius Envir. Bull., 13(10) (2004)
1061–1065.
[20] F. Germirli, D. Orhon, N. Artan, E. Ubay and E.
Gorgun, Effect of two- stage treatment on the bio-
logical treatability of strong industrial wastes. Wa-
ter Sci. Tech., 28(2) (1993) 145–154.
[21] V. Enç, Toxicity reduction in textile industry using
ozone. M.Sc. Thesis, Istanbul Technical University,
Institute of Sciences, 2003, p. 71 (in Turkish).
[22] IOA, Iodometric method for ozone measurement.
Standardization Committee-Europe, 001/87 (F),
Brussel, 1987.
[23] A. Yildiz, Investigation of the relation between in-
ert COD fractions and effluent toxicity in textile
industry wastewater, MSc. Thesis, Istanbul Techni-
cal University, Institute of Sciences, 2003, p. 85.
[24] ISO (International Organisation for Standardisation,
Geneva, Switzerland), Water quality-determination
of the inhibition of the mobility of Daphnia magna
Starus (cladocera, Crustacea) — acute toxicity test.
ISO 6341, 1996.
[25] APHA, AWWA, WEF, Standard methods for the
examination of water and wastewater, 20th ed.,
American Public Health Association/American
Water Works Association/Water Environment Fed-
eration, Washington DC, USA, 1998.
[26] ISO (International Organisation for Standardisation,
Geneva, Switzerland), Water quality-determination
of the chemical oxygen demand. ISO 6060, 1986.
[27] E. Chamarro, A. Marco and S. Esplugas, Use of
Fenton reagent to improve organic chemical biode-
gradability. Water Res., 35(4) (2001) 1047–1051.