Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 78:614 (online: 2002)

DOI: 10.1002/jctb.713

Effect of stream segregation on ozonation for

the removal of significant COD fractions from
textile wastewater
Serdar Dogruel,* Fatos Germirli-Babuna, Isk Kabdasl, Guclu Insel and Derin Orhon
Environmental Engineering Department, Istanbul Technical University, I.T.U. Insaat Fakultesi, 80626 Maslak, Istanbul, Turkey

Abstract: Ozonation was tested on selected streams of cotton finishing textile plant wastewater for
optimizing chemical oxygen demand (COD) removal. For this purpose, significant COD fractions in
the wastewater were experimentally identified and the effect of ozone on these fractions was
investigated. Ozonation experiments were performed with a 1 dm3 sample volume. Ozone treatment of
batches of raw wastewater provided, at a rate of 62 mg min
1 and a gas feeding time of 15 min, achieved
complete colour removal but only 21% COD reduction. Increasing the feeding time to 30 min slightly
increased the COD removal to 32%. At this feeding time, removal of the readily biodegradable COD
was 60%, but soluble inert COD reduction remained at 16%, indicating selective preference of ozone
for simpler compounds. At low concentrations, ozone was mainly influential on soluble COD compounds. Longer feeding times also affected particulate compounds, resulting in the solubilization of
the COD fractions. Pre-ozonation of the dye-house wastewater, as a segregated stream, proved much
more effective in the breakdown of refractory organic compounds, rendering the overall plant effluent
more amenable to biological treatment.
# 2002 Society of Chemical Industry

Keywords: ozonation; textile wastewater; cotton finishing; chemical oxygen demand fractionation; stream
segregation; reactive dyes.

NOTATION

F/M
OUR
SH
SI
SS
SS
ST
VSS
XT
YH

Food/microorganism ratio (g COD (g

VSS)
1)
Oxygen uptake rate (mg O2 dm
3 s
1)
Rapidly hydrolysable COD
(mg COD dm
3)
Soluble inert COD (mg COD dm
3)
Readily biodegradable COD
(mg COD dm
3)
Suspended solids (mg SS dm
3)
Total soluble COD (mg COD dm
3)
Volatile suspended solids (mg VSS dm
3)
Total particulate COD (mg COD dm
3)
Heterotrophic yield coefficient (g COD (g
cell COD)
1)

1 INTRODUCTION

The dyeing process in cotton finishing textile plants,

such as that investigated in this study, mostly involves
reactive dyes. From an environmental impact standpoint, reactive dyes are much more soluble than
others, imparting to the wastewater a strong colour1,2

and organic residues with a significant non-biodegradable fraction, persisting through chemical precipitation and biological treatment.3,4 In fact, chemical
precipitation, although effective for the removal of
colour due to dyes with limited solubility, such as
disperse dyes, remains relatively inefficient for soluble
dyes.5 Regardless of the removal efficiency potential
provided, sludge generation, which requires additional
and costly handling and disposal, is a major drawback
for chemical treatment.5,6 Biological treatment inherently increases the non-biodegradable organic matter,
initially present in the wastewater, through the
generation of soluble residual microbial products.7
Chemical oxidation with ozone, however, is one of the
most suitable chemical oxidation processes for effective colour removal from textile effluents, with
simultaneous interaction and breakdown of refractory
organic matter resistant to biodegradation, without
leading to sludge production.6,8
Ozonation, despite its distinct technical advantages,
may prove costly when applied to the entire wastewater volume. Cotton finishing, however, like other
major textile operations, involves a sequence of welldefined batch operations in terms of chemicals used

. Insaat Fakultesi, 80626

* Correspondence to: Serdar Dogruel, Environmental Engineering Department, Istanbul Technical University, I.T.U
Maslak, Istanbul, Turkey
Contract/grant sponsor: Environmental Biotechnology Center of the Scientific and Research Council of Turkey
Contract/grant sponsor: Volkswagen Stiftung
Contract/grant sponsor: Research and Development Fund of Istanbul Technical University
(Received 14 March 2002; revised version received 3 July 2002; accepted 28 July 2002)

# 2002 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2003/$30.00

Stream segmentation in ozonation removal of COD from textile wastewater

2 MATERIALS AND METHODS

2.1 Description of the textile plant

and quality/quantity of polluted effluents generated.

Consequently, it lends itself easily to the segregation of
wastewater streams, when required. Stream segregation is often practiced for wastewater recovery and
re-use.911 It is therefore possible to apply ozonation to
a selected portion of the raw wastewater, for the
optimum use of the chemical oxidation potential
provided, both for the overall chemical oxygen
demand (COD) and colour removal, and for the
reduction of soluble non-biodegradable COD fraction, often a major problem in meeting the stringent
effluent quality restrictions.
In this framework, the objective of this study may
primarily be defined as the investigation of the effect of
partial ozonation of selected wastewater streams on the
removal of COD and colour, typical pollutants for
textile effluents. Changes induced by ozonation on
soluble COD components and specifically on the fate
of soluble inert COD fraction were also evaluated
under different operating conditions. For this purpose,
an effluent of dye-house operation, involving dye-bath
and rinsing discharges, was the selected segregated
stream as the major source of colour and nonbiodegradable COD in the overall plant effluent.
Ozonation of this stream, as a technically effective
and economically feasible means of treatment, was
evaluated in terms of COD fractionation, a new
concept for treatability-oriented wastewater characterization.

The plant used in the survey reflects a typical example

of the knit fabric finishing sub-category, involving
batchwise operations such as dyeing, bleaching, etc,
applied to cotton, viscose rayon, polyester, polyamide
knit fabrics and cottonpolyester, polyesterviscose
rayon blend knit fabrics. Table 1 outlines the main
production processes together with the daily production and related wastewater generation.12 According
to the values given in this table, the investigated plant
has a total volumetric wastewater load of 72 m3 (1 t
fabric)
1, which is consistent with the literature.13,14
2.2

Experimental approach
Four processes among a total of 20 were selected for
experimental investigation to represent the plant
effluent as they are all routinely performed on a
regular basis. They also affect the effluent quality to a
great extent and contribute approximately 55% to the
daily total wastewater generation. The selected processes are cotton knit fabric optical brightening, cotton knit
fabric 60 C Remazol 1 dyeing with kiering, cotton knit
fabric 95 C Procion2 dyeing with bleaching and viscose
rayon knit fabric 95 C Procion2 dyeing. It must be kept
in mind that in the typical textile plants some processes
are realized only once in a while. Therefore, such a
selection is an important step in planning the experimental study. The experimental survey is conducted

Table 1. Plant characteristics

Process
Cotton knit fabric
Optical brightening
60 C reactive (Remazol1) dyeing with kiering
Dyeing
1st rinse
2nd rinse
Others
95 C reactive (Procion2) dyeing with bleaching
Dyeing
1st rinse
Others
Other finishing operations
Mercerized cotton knit fabric
Viscose rayon knit fabric
95 C reactive (Procion2) dyeing
Dyeing
1st rinse
Others
Other finishing operations
Polyester viscose rayon knit blend
Polyester knit fabric
Cotton polyester knit blend
Polyamide knit fabric
Sugar bleached, mercerized cotton knit fabric
Total

Average daily
production
(kg fabric day
1)
5300
1700
700

Unit wastewater generation

m3 (t fabric)
1
82.5
40.0
91.4

m3 day
1
437
68
6.4
6.4
6.4
44.8

2300

600
100
900
500

400
800
1700
1200
300
100
10 400

Sample
%

58.2
9.1

0.85
0.85
0.85
5.95










97.0

136.7
50.0
110.0
114.0

105.0
77.5
25.3
68.3
36.7
110.0
72

27.9
27.9
167.2
82
5
99

3.7
3.7
22.3
10.9
0.7
13.2








7.1
7.1
42.8
42
62
43
82
11
11
750

0.95
0.95
5.7
5.6
8.3
5.7
10.9
1.5
1.5
100








Investigated processes.

J Chem Technol Biotechnol 78:614 (online: 2002)

S Dogruel et al

on four different flow proportional composite samples

(where batch wastewater discharges are mixed in
proportion to their respective volumes to form the
sample) originating from the above-mentioned processes: Sample A represents raw wastewater from the
respective processes; Sample B is composed of the
dye-baths and subsequent rinsing streams; Sample C
is defined as the remaining portion of wastewaters after
the segregation of dye-baths and subsequent rinsings;
and Sample D is the flow proportional mixture of the
pre-ozonated dye-baths and subsequent rinsing
streams with the rest of the wastewater streams
(ozonated Sample B Sample C). The contributing
wastewater streams to Samples A, B and C can also be
seen in Table 1. Table 2 summarizes the results of
conventional wastewater characterization for Samples
A, B and C.

ozone on different COD fractions. The soluble inert

COD fraction, SI, was measured according to the
method proposed by Orhon et al. 15 The method
consists of running two aerated batch reactors of the
same volume, one fed with the filtered wastewater and
the other with glucose. Both reactors were started with
the same initial COD concentration and seeded to
secure an initial biomass concentration of around
40 mg VSS dm
3. The seed was obtained from a
laboratory-scale fill and draw aerobic reactor operated
at steady state with a feed composed of a glucose
wastewater mixture with equal COD contributions.
Aliquots removed periodically from the mixed liquor
were analysed for soluble COD. Experiments were
continued until the observation of a stable threshold
COD level coupled with no measurable biomass
activity. SI in the filtered wastewater reactor could be
calculated by taking in the account the accumulation
of soluble residual metabolic products in the glucose
reactor.
As the experimental procedures in this study involve
a sequence of differences in measured COD values,
analytical errors associated with COD measurements
were also investigated. For this purpose, three
different sets of COD experiments were carried out
with the raw wastewater (Sample A) used in the study,
diluted to concentrations of 30, 300 and 600 mg dm
3,
each measured on 30 samples. The standard deviation
was 1 mg dm
3 (3.1%) for 30 mg dm
3, 7 mg dm
3
(2.3%) for 300 mg dm
3 and 13 mg dm
3 (2.2%) for
600 mg dm
3. This evaluation indicated that the
results depicted and discussed in the paper related to
COD differences were significantly higher than what
could be attributed to analytical errors.
Determination of the readily biodegradable COD
fraction, SS, was performed respirometrically as
defined in the method proposed by Ekama et al. 16
The oxygen uptake rate (OUR) measurements were
conducted in samples periodically taken from 2 dm3
aerobic batch reactors where the initial food to
microorganism ratio (F/M) was adjusted to 0.6 g
COD (g VSS)
1. The reactors were seeded with the
biomass obtained from fill and draw reactors acclimatized to wastewater, operated at a sludge age of 10
days. The heterotrophic yield coefficient, YH, was
assumed to be 0.67 g COD (g cell COD)
1 in accordance with the data reported in the literature.13,17
OUR measurements were performed in a Manotherm
RA-1000 continuous respirometer connected to a PC.
The pH of the biological reactors was kept in the range
7.08.0 and continuous aeration was supplied to

2.3 Experimental and analytical methods

Ozone was produced from dry air by a PCI GL1

laboratory ozone generator. The rated concentration
of ozone was 2% by weight on air. Ozonation
experiments were conducted at 15 psi (103.45 kPa)
pressure by a feed gas flow-rate of 1.42 dm3 min
1
using a bubbling vessel with a total height of 120 cm,
an inner diameter of 4.5 cm and a volume of 1.5 dm3 as
an ozone reactor, and a semi-batch bubbled gas
washing bottle reactor with an effective depth of
23 cm. Ozone gas was supplied at the bottom of the
reactor through a sintered-glass plate diffuser. All
pieces in contact with ozone were stainless steel, glass
or Teflon1 and stable in the presence of ozone. Two
gas washing bottles containing 2% (w/w) potassium
iodide solution were connected to the reactor in series
in order to determine the output ozone gas passing
through the reactor. Wastewater samples of 1 dm3
volume were used in the ozonation experiments. It
should be noted that physical constraints such as bypassing of gas, vessel height, etc, may affect the
effectiveness of the ozonation reaction. In this respect,
results obtained in a laboratory-scale system such as
that used in the study, although providing a relative
evaluation on process parameters, may not be directly
indicative of industrial practice of ozonewater contact.
Experimental studies related to biological treatability involved the identification of significant soluble
COD fractions, namely the readily biodegradable
COD (SS), the rapidly hydrolysable COD (SH) and
the soluble inert COD (SI). This was a necessary
experimental step of the evaluation of the impact of

Wastewater volume
Sample

Table 2. Conventional wastewater

characterization

A
B
C

m3 day
1

pH

412
89
323

100
22
78

9.68
10.09
7.77

Total COD Soluble COD

(mg dm
3)
(mg dm
3)
955
865
985

675
550
710

Colour
(PtCo unit)

TSS
(mg dm
3)

540
1580
275

105
190
80

J Chem Technol Biotechnol 78:614 (online: 2002)

Stream segmentation in ozonation removal of COD from textile wastewater

maintain a dissolved oxygen concentration of above

6 mg dm
3. SS was calculated from the area under the
OUR curve as described by the proposed method.
Conventional characterization yields the total COD
(CT) of the selected sample. The total soluble COD
(ST) was the measured COD in the filtrate. The
remaining soluble COD fraction, namely rapidly
hydrolysable COD (SH), was calculated from the
following mass balance equation:18
SH ST
SS
SI

COD measurements were performed as defined in

ISO 6060.19 All other analyses for conventional
characterization were conducted in accordance with
the APHA.20 The colour measurements were performed by the platinumcobalt method after filtering
the samples through a 0.45 mm membrane filter-paper.
Soluble fractions were defined as filtrates of the
samples subjected to vacuum filtration using also
0.45 mm membrane filters. Whatman GF/C glass-fibre
filter-papers having a pore size of approximately
1.2 mm were used for suspended solids (SS) and
volatile suspended solids (VSS) measurements. Each
data point in the study was calculated as the mean of
three replicate measurements.

3 RESULTS AND DISCUSSION

3.1 Ozonation experiments

Ozonation involves at least three major process

parameters, namely ozone flow-rate (mg O3 min
1),
contact/feeding time (min) and utilized ozone (mg
O3). All have a significant impact on the efficiency of
chemical oxidation. In this part of the study, the raw
wastewater sample (Sample A) and the sample
representing the dye-baths and subsequent rinsing
streams (Sample B) were subjected to ozonation

experiments in two consecutive steps. In the first step,

the feeding time was set as 5 min for a wide range of
ozone flow-rates ranging from 7 to 68 mg min
1. The
results obtained are outlined in Table 3. For Sample
A, a gradual improvement in colour removal was
observed, starting from 25% at 7 mg O3 min
1 and
reaching 86% at 68 mg O3 min
1. The corresponding
COD reduction was almost negligible for the majority
of tests, with a single significant increase from 6 to
12% for 62 mg O3 min
1. COD removal remained
limited to 14% at 68 mg O3 min
1.
Experiments on the dye-baths and subsequent
rinsing streams were conducted for a limited ozone
flow-rate range of 5670 mg min
1. The results
obtained could be characterized, as shown in Table
3, with a much narrower but higher colour removal
range of 9496%, coupled with a lower COD removal
efficiency of 58%. A value of around 6062 mg O3
min
1 was selected as the optimum ozone flow-rate,
mainly based on results associated with the raw
wastewater, but also in view of the fact that it
corresponds to the same level of ozone utilization of
around 125 mg for both samples. In this way, the
selected O3 value provides a means of comparison for
the two samples tested, on the basis of equal ozone
utilization values.
Following the preliminary experiments, Samples A
and B were ozonated for four different feeding periods
of 5, 10, 15 and 30 min at the selected optimum ozone
flow-rate. The results obtained are given in Table 4. As
shown, the COD reduction efficiency was improved to
32% for the raw wastewater, with a parallel increase in
colour reduction from 83 to 94%. A similar trend was
also observed for the dye-baths and subsequent rinsing
streams with an almost total colour removal and a
limited COD reduction of 19%. It should be noted
that raw wastewater and the dye-baths with subse-

Table 3. Results of preliminary ozonation experiments

Sample a
A

Utilized
Ozone flow-rate Ozone feeding
time (min)
ozone (mg)
(mg min
1)

7
14
18
29
38
44
48
57
62
65
68

56
61
67
70

5
5
5
5
5
5
5
5
5
5
5

5
5
5
5

30
55
60
75
85
100
105
115
125
130
145

120
125
145
155

pH
9.68
9.60
9.47
9.52
9.44
9.49
9.50
9.46
9.53
9.40
9.45
9.39
10.09
10.06
10.04
10.00
9.94

Total COD Total COD Soluble COD

Colour
Colour
(mg dm
3) removal (%) (mg dm
3) (PtCo unit) removal (%)
955
920
915
915
910
905
905
905
900
845
830
825
865
820
815
805
795

4
4
4
5
5
5
5
6
12
13
14

5
6
7
8

675
700
685
620
720
710
645
615
600
605
565
555
550
560
585
615
640

540
405
340
270
200
150
130
115
100
90
80
75
1580
100
90
80
70

25
37
50
63
72
76
79
81
83
85
86

94
94
95
96

Ozonation experiments were performed with a 1 dm3 sample volume.

J Chem Technol Biotechnol 78:614 (online: 2002)

S Dogruel et al
Table 4. Results of ozonation experiments at optimum ozone flow-rate

Sample a
A

Utilized
Ozone flow-rate Ozone feeding
time (min)
ozone (mg)
(mg min
1)

62
62
62
62

62
62
62
62

5
10
15
30

5
10
15
30

130
235
465
1385

130
250
440
1360

Total COD Total COD Soluble COD

Colour
Colour
(mg dm
3) removal (%) (mg dm
3) (PtCo unit) removal (%)

pH
9.68
9.35
8.85
8.69
8.08
10.09
10.05
9.90
9.83
9.72

955
850
775
750
650
865
815
790
760
700

11
19
21
32

6
9
12
19

675
580
545
525
480
550
580
605
610
625

540
90
45
35
30
1580
80
50
40
20

83
92
94
94

95
97
97
99

Ozonation experiments were performed with a 1 dm3 sample volume.

3.2 Effect of ozonation on soluble inert COD

fraction

Figure 1. Relationship between utilized ozone and soluble inert COD

removal for an ozone flow-rate of 60 mg min
1 (1 dm3 sample volume).

quent rinsing streams have practically the same total

COD content of around 900 mg dm
3 and yet they
respond differently to chemical oxidation, in terms of
the respective COD and colour removals achieved.
This observation may be justified on the basis of
substrate (organic matter) selectivity of ozone. The
results also indicated that changing the ozone contact
time from 10 to 15 min did not appreciably affect the
efficiency of chemical oxidation. A contact time of
30 min is an extreme level, not often encountered in
practice. It was tested in this study as an upper
threshold value, mainly to evaluate its impact on COD
fractions and especially on the soluble inert COD
fraction.

The soluble inert COD, SI, is perhaps the most

significant COD fraction, as it by-passes biological
treatment and accounts for the majority of the effluent
COD. Therefore, the merit of chemical oxidation by
ozone may best be evaluated through its impact on SI.
In this context, the effect of ozonation on soluble inert
COD was investigated on samples A and D, as
illustrated in Fig 1, using three feeding periods of 5,
10 and 30 min and an ozone flow-rate of 6061 mg O3
min
1. For the soluble inert COD fraction (SI)
experiments, as previously explained, Sample A
represents raw wastewater and Sample D is a flow
proportional mixture of the pre-ozonated dye-baths
and subsequent rinsing streams with the rest of the
wastewater streams. The SI values determined experimentally for samples A and D, together with corresponding total soluble COD (ST) and colour levels are
outlined in Table 5. Review and evaluation of results
in Tables 4 and 5 indicate the following.
SI in the raw wastewater sample was 320 mg dm
3,
corresponding to 47% of the total soluble COD (ST)
and to 34% of the total COD (CT), a level significantly
higher than the soluble inert COD content experimentally ascertained for similar textile effluents.13,14,18,2123 This difference may be explained
by the fact that Sample A was prepared to emphasize

Table 5. Results of inert COD experiments and colour levels at optimum ozone flow-rate

Sample a
A

Ozone flow-rate
(mg min
1)

Ozone feeding
time (min)

Utilized
ozone (mg)

ST
(mg dm
3)

SI
(mg dm
3)

SI
removal (%)

Colour
(PtCo unit)

Colour
removal (%)

61
61
61

60
60
60

5
10
30

5
10
30

130
245
1395

125
245
1320

675
580
545
480
675
680
685
690

320
300
295
270
320
285
275
240

6
8
16

11
14
25

540
90
45
30
540
235
225
220

83
92
94

56
58
59

Ozonation experiments were performed with a 1 dm3 sample volume.

10

J Chem Technol Biotechnol 78:614 (online: 2002)

Stream segmentation in ozonation removal of COD from textile wastewater

the impact of dyeing and finishing most frequently

used in the plant and therefore may not provide an
accurate indication of the expected quality. It underlines, however, the crucial importance of the SI
fraction and the need for optimizing the efficiency of
chemical oxidation in meeting stringent effluent
limitations.
Ozonation induced an SI reduction of only 8% with
a contact time of 10 min. When the latter was extended
to 30 min, SI was brought down to 270 mg dm
3,
corresponding to a reduction efficiency of 16%,
together with a colour removal of 94%. The same
ozonation set-up was observed to provide an almost
twice-higher removal efficiency for the total soluble
COD, lowering ST to 480 mg dm
3. This observation
reflects the selective preference of ozone for simpler
organics and in this respect, potential competition of
chemical oxidation with biological treatment for biodegradable COD.
The experimental data related to Sample D identified the dye-baths and subsequent rinsing streams as
the major source of the soluble inert COD fraction,
presumably composed of dye residues, with little
contribution, if any, from the rest of the wastewater
streams. Pre-ozonation of the dye-baths and subsequent rinsing streams proved much more effective for
the breakdown of these complex organics at source,
lowering SI in sample D from 320 to 240 mg dm
3, as
shown in Fig 1 and Table 5. The total soluble COD
level, however, remained practically unchanged at
around 675690 mg dm
3 and the colour removal
efficiency below 60% owing to addition of the
untreated wastewater streams after pre-ozonation.
These results should be evaluated based on specific
effluent requirements. If COD removal is the prime
concern, stream segregation is effective, as preozonation of the most polluted stream renders the
wastewater more amenable to subsequent biological
treatment, with a final SI of 240 mg dm
3 and a
corresponding SI/ST ratio of 0.35, compared with
ozonation of the entire wastewater. Furthermore, the
selected dye-house effluent is only 22% of the total
wastewater volume. Therefore, stream segregation
also proves attractive from an economical standpoint,
involving only 22% of the ozone applied at the same

ozone flow-rate and contact time, yet providing a

lower SI level. If colour removal is desired, however,
stream segregation does not appear suitable, as 78% of
the plant effluent is not subjected to ozonation. It
should be noted that colour removal from textile
effluents is not a requirement in most countries.
3.3

Effect of ozonation on different COD fractions

The experimental observations so far outlined give a
clear indication of the limitations associated with
overall substrate parameters, such as COD, in providing scientific explanations on the fate of organics after
ozonation. COD fractionation, introduced and experimentally defined as part of the new modeling
concepts,7,24 is a suitable tool for this purpose. It was
used in this study to identify, aside from total soluble
(ST) and particulate (XT) COD components, the
readily biodegradable (SS), the rapidly hydrolysable
(SH) and inert (SI) fractions of the soluble COD
fraction. The effect of ozonation on the fate of
different COD fractions was investigated for experimental set-ups previously used in the study. Removal
efficiencies obtained for individual COD fractions are
given in Table 6 and the relative magnitudes of these
fractions as percentage of the total COD after each
ozonation experiment in Table 7.
Review of the results obtained primarily underlines
the significant impact of ozone contact time on the fate
of COD fractions. Evaluation of the experimental data
can best be made first on the overall particulate and
soluble COD components. The effect of ozone is
mainly observed on soluble components at low contact
times. At higher contact times, however, the breakdown of the particulate compounds becomes more
pronounced, resulting in the breakdown of particulate
COD into smaller sized, soluble COD compounds. In
fact, inspection of the data for Sample A shows that a
5 min contact time induced a total COD reduction of
11%, due to a 14% decrease in the soluble fraction but
only 4% in the particulate fraction. At a contact time of
30 min, however, the particulate COD reduction was
significantly increased to 39%, with a lower reduction
of 29% for the soluble counterpart and averaging 32%
for the total COD. For the same sample, the same
argument may also be put forward on the basis of

Table 6. Individual removal rates of COD fractions after ozonation experiments

Ozone Utilized
CT
XT
ST
SS
SH
SI
feeding ozone
CT
Removal
XT
Removal
ST
Removal
SS
Removal
SH
Removal
SI
Removal
Sample a time (min) (mg) (mg dm
3) (%)
(mg dm
3) (%)
(mg dm
3) (%)
(mg dm
3) (%)
(mg dm
3) (%)
(mg dm
3) (%)

a
b

5
10
30

5
10
30

130
245
1395

125
245
1320

955
850
775
650
955
950
945
925

11
19
32

<1
1
3

280
270
230
170
280
270
260
235

4
18
39

4
7
16

675
580
545
480
675
680
685
690

14
19
29

1b
1b
2b

110
40
50
45
110
75
65
100

64
55
59

32
41
9

245
240
200
165
245
320
345
350

2
18
33

31b
41b
43b

320
300
295
270
320
285
275
240

6
8
16

11
14
25

Ozonation experiments were performed with a 1 dm3 sample volume.

Increase.

J Chem Technol Biotechnol 78:614 (online: 2002)

11

S Dogruel et al
Table 7. Effect of ozonation on COD ratios

Sample a
A

Ozone
ST
SS
SH
SI
XT
feeding
Utilized
CT
XT
ST
SS
SH
SI
time (min) ozone (mg) (mg dm
3) (mg dm
3) CT (mg dm
3) CT (mg dm
3) CT (mg dm
3) CT (mg dm
3) CT

5
10
30

5
10
30

130
245
1395

125
245
1320

955
850
775
650
955
950
945
925

280
270
230
170
280
270
260
235

29
32
30
26
29
28
28
25

675
580
545
480
675
680
685
690

71
68
70
74
71
72
72
75

110
40
50
45
110
75
65
100

11
5
6
7
11
8
7
11

245
240
200
165
245
320
345
350

26
28
26
25
26
34
36
38

320
300
295
270
320
285
275
240

34
35
38
42
34
30
29
26

Ozonation experiments were performed with a 1 dm3 sample volume.

COD fractionation displayed in Table 7. The sample

was initially composed of 29% particulate COD and
71% soluble COD, fairly typical of textile wastewater.
Ozonation for 5 min was observed to change this ratio
to 32:68%; continued ozonation for 30 min reversed
the ratio, this time in favour of the soluble COD
fraction reaching 74%, a level 3% higher than the
initial value associated with the untreated wastewater.
It should be noted that the relative impact of ozone
on particulate and soluble COD components was
observed to depend on the nature of the wastewater.
For the dye-baths and subsequent rinsing streams,
mainly composed of complex and non-biodegradable
organics, ozone was mainly effective on the partial
oxidation of the particulate COD fraction, presumably
owing to the lack of available simpler organics. As
clearly visualized by the data presented in Table 4, the
soluble COD concentration (Sample B) increased
from its initial value of 550 to 625 mg dm
3, indicating
that ST generation through particulate COD breakdown apparently exceeded ST removal by total
oxidation when ozone was applied for 30 min.
A similar trend of oxidation was also observed for
soluble COD fractions, where readily biodegradable
COD (SS), rapidly hydrolysable COD (SH) and inert
COD (SI) are conveniently used to differentiate and
group organics from simpler to more complex compounds, on the basis of biodegradability. For a short
contact time, ozone preferentially attacks SS; at higher
contact times, a gradual increase occurs in SH and SI
removal levels and a balance is established between SS
generation through SH and SI breakdown and direct SS
oxidation. Review of the data for Sample A in Table 6
reveals that a 5 min contact time was found to inflict an
SS reduction of 64%, compared with 2% for SH and
6% for SI. A contact time of 30 min, however, leveled
SS and SH reductions at around 59 and 33%,
respectively, together with only a 16% decrease in SI
concentration, which always remained the least
vulnerable soluble COD component to ozone oxidation. The relative magnitude of different COD
fractions provided the same overall picture, where
ozone basically lowered the SS fraction, maintained the
SH fraction at the same level and increased the SI
fraction, through a gradual breakdown of the more
12

complex organics prior to total oxidation of the simple

compounds, as presented in Table 7. The same
observation is illustrated in Figs 2 and 3, which
indicate for Samples A and D, respectively, incremental concentration changes in mg dm
3 for each
COD fraction induced by different ozone feeding
times. Ozonation for 5 min was found to oxidize a total
COD concentration of 105 mg dm
3, only 10 mg
dm
3 from the particulate and 95 mg dm
3 from the
soluble portions, the last mainly due to 70 mg dm
3 SS
removal. Prolonged ozone application for 30 min
increased the oxidized total COD concentration to
305 mg dm
3, with a much more significant contribution of 110 mg dm
3 from the particulate COD
fraction; the SS removal was observed to remain at
practically the same level because of the generation/

Figure 2. Removal of COD fractions of sample A by ozonation: (a) removal

of CT, XT and ST and (b) removal of SS, SH and SI (1 dm3 sample volume).

J Chem Technol Biotechnol 78:614 (online: 2002)

Stream segmentation in ozonation removal of COD from textile wastewater

Figure 3. Removal of COD fractions of sample D by ozonation: (a) removal

of CT, XT and ST and (b) removal of SS, SH and SI (1 dm3 sample volume).

oxidation balance previously mentioned and the

relative magnitude of SH and SI removals increased,
as potential sources of SS generation through chemical
oxidation. A more pronounced solubility could be
associated with Sample D, as shown in Table 6, with
the combined effect of pre-ozonation of the segregated
dye-house effluent and dilution due to mixing with the
remaining wastewater volume.

soluble inert COD fraction due to complex dye

residues, was selected as the segregated wastewater
stream for chemical oxidation. Pre-ozonation of the
dye-house effluent, prior to mixing with the rest of the
wastewater flow, proved much more effective for the
breakdown of these complex organics at source,
achieving an SI removal of 25%. The total soluble
COD level, however, remained practically unchanged
and the colour removal efficiency below 60%, owing to
addition of the untreated wastewater streams after preozonation. Since the selected dye-house effluent
constituted only 22% of the total wastewater volume,
stream segregation also proved attractive from an
economical standpoint, involving only 22% of the
ozone applied at the same ozone flow-rate and contact
time, yet providing a lower SI, if the objective of
chemical oxidation by ozone is to render the wastewater more amenable to biological treatment. If colour
removal is the prime concern, however, stream
segregation does not appear suitable, as 78% of the
plant effluent is not ozonated.
The concept of COD fractionation was introduced
and experimentally tested to understand better and
evaluate the impact of ozonation on different COD
fractions. For the raw wastewater, ozone was mainly
influential on soluble components at low contact
times. At higher contact times however, the breakdown of particulate compounds became more pronounced, yielding smaller sized, soluble organic
compounds. For the dye-house effluent mainly composed of complex and non-biodegradable organics,
ozone was mainly effective on the partial oxidation of
the particulate COD fraction, presumably owing to the
lack of available simpler organics. The fate of soluble
biodegradable COD compounds was observed to
depend on the complex balance between generation
through particulate COD breakdown and removal by
total oxidation.

4 CONCLUSIONS

The effluent of a knit fabric textile plant using reactive

dyes was studied by means of a composite sample
representing the most frequently used processes in the
plant. The wastewater was found to contain, as
expected, high levels of colour and soluble inert
COD, emphasizing the need for optimizing the
efficiency of chemical oxidation by ozone in meeting
stringent effluent limitations.
Ozonation efficiency was tested both in terms of
ozone flow-rate and contact time; a level of around
60 mg min
1 was determined as the optimum ozone
flow-rate, providing almost complete colour removal.
Total COD reduction, however, could not be improved beyond 32%, even for extended contact times.
Removal of the soluble inert COD fraction was found
to remain at a much lower level of 16%. The results
indicated a selective preference of ozone for simpler
organic compounds, especially at limited contact
times.
The dye-house effluent, the major source of the
J Chem Technol Biotechnol 78:614 (online: 2002)

ACKNOWLEDGEMENTS

This study was conducted as part of the sponsored

research activities of the Environmental Biotechnology
Center of the Scientific and Research Council of
Turkey. It was also jointly supported by the Volkswagen Stiftung Fund and the Research and Development Fund of Istanbul Technical University.

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