Water Research 37 (2003) 18681878

Anaerobic treatment of real textile wastewater with a uidized

bed reactor
S.
-
Sen
a
, G.N. Demirer
b,
*
a
Department of Civil and Environmental Engineering, San Diego State University, San Diego, CA 92182, USA
b
Department of Environmental Engineering, Faculty of Engineering, Middle East Technical University, Inonu Bulvari,
Ankara 06531, Turkey
Received 14 September 2001; received in revised form 11 November 2002; accepted 15 November 2002
Abstract
Anaerobic treatability of a real cotton textile wastewater was investigated in a uidized bed reactor (FBR) with
pumice as the support material. The immobilized biomass or attached volatile solids level on the support material was
0.073 g VSS/g support material at the end of the 128-d start-up period. During the operation period, real cotton textile
wastewater was fed to the anaerobic FBR both unsupplemented (in Stages 1 and 2) and supplemented (with synthetic
municipal wastewater in Stage 3 and glucose in Stages 46). The effect of operational conditions such as organic loading
rate (OLR), hydraulic retention time (HRT), inuent glucose concentration as the co-substrate, etc. was investigated to
achieve the maximum color removal efciency in the reactor. Results indicated that anaerobic treatment of textile
wastewater studied was possible with the supplementation of an external carbon source in the form of glucose (about
2 g/l). The corresponding maximum COD, BOD
5
and color removals were found to be around 82%, 94% and 59%,
respectively, for HRT of around 24 h and OLR of 3 kg COD/m
3
/d. Further increase in external carbon source added to
real textile wastewater did not improve the color removal efciency of the anaerobic FBR reactor.
r 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Textile wastewater; Anaerobic; Decolorization; Fluidized bed reactor
1. Introduction
Textile establishments receive and prepare bers;
transform bers into yarn, thread, or webbing; convert
the yarn into fabric or related products; and dye and
nish these materials at various stages of production [1].
Textile manufacturing consumes a considerable amount
of water in its manufacturing processes. The water is
primarily utilized in the dyeing and nishing operations
of the textile establishments. Considering both the
volume generated and the efuent composition, the
textile industry wastewater is rated as the most polluting
among all industrial sectors.
Important pollutants in textile efuent are mainly
recalcitrant organics, color, toxicants and inhibitory
compounds, surfactants, chlorinated compounds
(AOX), pH and salts. Dye is the most difcult
constituent of the textile wastewater to treat. Azo dyes
are the class of dyes most widely used industrially [2]
having a world market share of 6070%. Reactive azo
dyes are becoming more popular in the textile industry,
they are mainly used for cotton dyeing. However,
reactive dyes hydrolyze easily, resulting in a high portion
of unxed (or hydrolyzed) reactive dyes, which have to
be washed off during the dyeing process. As much as
50% of the initial dye load is present in the dye bath
efuent [3].
Physico-chemical methods are applied for the treat-
ment of this kind of wastewaters, achieving high dye
removal efciencies [4]. On the other hand, in recent
*Corresponding author.
E-mail address: goksel@metu.edu.tr (G.N. Demirer).
0043-1354/03/$ - see front matter r 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0043-1354(02)00577-8
years there is a tendency to use biological treatment
systems to treat dye-bearing wastewaters [5]. The
recalcitrant nature of azo dyes, together with their
toxicity to microorganisms, makes aerobic treatment
difcult. On the other hand, a wide range of azo dyes is
decolorized anaerobically [69]. Under anaerobic con-
ditions, azo dyes are readily cleaved via a four-electron
reduction at the azo linkage generating aromatic amines.
The required electrons are provided by electron donat-
ing carbon source such as starch, volatile fatty acids
(VFA) or glucose. In addition, it is known that
methanogenic and acetogenic bacteria in anaerobic
microbial consortium contain unique reduced enzyme
cofactors, such as F
430
and vitamin B
12
that could also
potentially reduce azo bonds [10,11]. These steps remove
color of the dye, however they do not completely
mineralize the aromatic amines generated in the
anaerobic environment [7,12,13] with a few exceptions
[10,14]. Unfortunately, as suspect mutagens and carci-
nogens, the aromatic amines cannot be regarded as
environmentally safe end products. On the other hand, it
is known that most of the aromatic amines can be
biodegraded under aerobic conditions [8,15,16].
Several high rate anaerobic reactor congurations
have been developed for treating wastewaters at
relatively short hydraulic retention times (HRT). Of
these the anaerobic uidized bed reactor (FBR) has been
one of the technological advances. It has been success-
fully employed in a broad spectrum of wastewaters
including both readily and hardly biodegradable wastes
[1719]. Although, in recent studies dealing with
anaerobic treatment of textile wastewater several high
rate anaerobic reactors such as upow anaerobic sludge
blanket reactors (UASB) and anaerobic bafed reactors
(ABR) were used, no study was reported using FBR in
textile wastewater treatment. Tables 1 and 2 provide
summaries about performance of different anaerobic
systems treating real and synthetic textile wastewater
reported in the literature, respectively.
Cotton manufacturing and dyeing are predominant in
the Turkish textile sector which is one of the most
important industrial sectors in the country both in terms
of its contribution to economy and environmental
emissions. Therefore, the aim of this study was to
investigate the anaerobic treatability of a real cotton
textile wastewater in a FBR. To this purpose, a FBR
with pumice as the support material was operated. The
effect of operational conditions such as OLR, HRT,
inuent glucose concentration as the co-substrate, etc.
was also investigated.
Table 1
Performance of different anaerobic systems treating real textile wastewater
Anaerobic
system
Co-substrate Inuent OLR HRT Removal rates
(%)
Reference
COD
(mg/l)
color COD color
Bafed reactor Sucrose+
peptone+nutrient
(90%v/v)
1000 1.2 g COD/l d 20 h 70 90 [32]
Two stage
UASB
Tapiaco (black line)
500 mg/l 646 155 SU 12 h 74 67 [9]
1000 mg/l 1172 87 71
1500 mg/l 1675 90 69
(red line)
0 408 150 SU 12 h 27 39
200 mg/l 619 40 58
500 mg/l 940 45 57
(blue line)
0 96 150 SU 12 h 13 48
200 mg/l 300 73 52
500 mg/l 602 84 56
GAC amended
UASB+SCAS
No co-substrate 6000 0.8 OD
(500 nm)
3.6 g COD/l d 12 d 80 75 [38]
UASB 1200 500 dil. factor 22.4 g COD/
m
3
d
810 h 60 80 [31]
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1869
Table 2
Performance of different anaerobic systems treating simulated (synthetic) textile wastewater
Dye Dye type Reactor type Dye conc. HRT Color
rem. (%)
Reference
Mordant Blue 13 Mono azo Batch 100 mg/l 42 d 83 [7]
Mordant Black 77
Basic Red 92
Acid Yellow 151 88
Direct Red 7 Diazo 92
Acid Red 114 62
Direct Blue 15 83
Direct Yellow 12 75
Reactive Black 5 81
Acid Blue 113 94
Direct Black 19 Polyazo 51
Direct Black 22 61
Reactive Blue 19 Anthraquinone 70
Acid Blue 80 7
Acid Blue 25 67
Basic Blue 22 62
Direct Yellow 11 Stilbene 53
Reactive Blue 21 Phthalocyanine 36
Basic Blue 3 Oxazine 62
Acid Orange 3 Nitro 62
Basic Yellow 28 Methine 35
MY3 Azo Batch 0.5 mmol/l 72 h 51 [37]
Acid Red 27 37
4-Hydroxyazobenzene-4-
sulphonic acid
43
Acid Yellow 23 6
Acid Yellow 21 98
Reactive Yellow 16 Azo Batch 100 mg/l 6.5 h 8090 [8]
Reactive Red 198 2 h 8590
Reactive Red 141 4.5 h 8590
Reactive Blue 220 1 h 9095
Reactive Yellow 95 0
Reactive Orange 12 23 h 9095
Reactive Red 218 32 h 9095
Reactive Orange 13 50 h 8590
Reactive Red 24 32 h 9097
Reactive Brown 11 23 h 90
Reactive Black 39 5.5 h 7075
Reactive Black 5 Diazo 4.5 h 8085
Reactive Blue 49 Anthraquinone 2 h 710
Blue PB Metal complex Batch 100 mg/l 2 h 98
Black SG 7.5 h 7580
Reactive Blue 38 Phthalocyanine 4.5 h 40
Reactive Blue 21 4.5 h 8590
Reactive Blue 72 50 h 2530
Acid Orange 7 Azo FBR 5 mg/l 24 h 90 [16]
Acid Orange 8 12 h 98
Acid Orange 10 12 h 81
Acid Red 14 24 h 86
Acid Yellow 17 Azo UASB 40 mg/l 820 h 20 [36]
Basic Blue 3 Phenoxazine 72
Basic Red 2 Acridine 78
Remazol Golden Yellow Azo Batch 500 mg/l 24 h 78 [40]
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1870
2. Materials and methods
2.1. Fluidized bed reactor
A 5.2 cm inner diameter, 73 cm long plexiglass tube
was fused to a 15 cm inner diameter, 25 cm long tube to
form the 4 l reactor body (Fig. 1). The enlarged top
section was used as a gassolid separator. The bottom of
the reactor was at with symmetrically placed four pores
through which ow was equally distributed into the
reactor. Five sampling ports were installed on the
reactor wall to obtain solid samples. The efuent was
collected by gravity through a loop connected to a port
on the top section of the reactor. The recycle ow was
Table 2 (continued)
Dye Dye type Reactor type Dye conc. HRT Color
rem. (%)
Reference
Remazol Navy Blue GG Diazo 80
Remazol Red RB 89
Remazol Blue B 76
Remazol Black B 67
Cibracon Orange CG 79
Cibracon Red C-2G 88
Disperse Navy D2GR 68
Remazol Turquoise Blue G113 Phthalocyanine 8
Remazol Black B Diazo UAF 500 mg/l 48 h >95 [41]
Mordant Orange 1 Azo UASB 100 mg/l 8 h 95 [33]
Mordant Orange 1 (MO1) UASB 100 mg/l 8 h >99 [5]
Azodisalicylate (ADS) 75 mg/l 8 h 98.8
Azodisalicylate 75 mg/l 24 h 88.9
Acid Orange 7 Azo Batch 100 mg/l 28 d 97 [15]
Acid Yellow 36 7 d 97
Acid dye 28 d 100
Acid Red 114 7 d 100
Acid Blue 25 21 d 100
Acid Yellow 27 56 d 57
Acid Yellow 151 14 d >90
Acid Back 24 14 d 100
Direct Red 7 28 d 98
Direct Blue 14 7 d >90
Direct Blue 15 7 d 100
Direct Yellow 12 7 d 100
Direct Yellow 50 35 d 100
Mordant Black 11 7 d 99
Mordant Black 9 7 d 100
Remazol Brilliant Violet 5R Reactive Sequencing
batch reactor
90 mg/l 15 d 90 [39]
Maxilon red BL-N Basic Anaerobic lter
reactor
200 mg/l 68.6 h >99 [34]
Acid Yellow 17 Acid 25 mg/l No rem.
Pricion Red H-E7B Azo UASB 150450 mg/
l
16 h 5577 [35]
Remazol Black B Reactive anthraquinone
oxazine
Sequencing
batch reactor
20 mg/l 18 h 61 [42]
Remazol Blue R 57
Cibacron Blue CR 67
Pricon Blue H-EGN 44
Azodisalicylate (ADS) UASB 25 mg/l 0.33 d 91 [5]
95
Acid Yellow 17 UASB 40 mg/l 20 [31]
Basic Blue 3 72
Basic Red 2 78
Orange II Azo Semi-
continuous
100 mg/l >99 [28]
Black 3HN >99
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1871
drawn from the top section (5 cm below the free liquid
surface) using a peristaltic pump and then fed upward
into the reactor. Gas produced in the reactor was
transferred through water trap to prevent the intake of
oxygen from the atmosphere. Reactor was placed in a
temperature-controlled room at 35721C. Pumice
(HESS Pumice Products, Inc., Malan, Idaho, USA),
with a diameter of 0.251.4 mm and particle density of
1764 kg/m
3
was used as support material in the FBR.
The start-up and operation periods of the anaerobic
FBR are described below.
2.2. Start-up period
The aim of the start-up period was to acquire biolm
formation on the support material. Mixed anaerobic
cultures with mixed liquor suspended solids (MLSS) and
mixed liquor volatile suspended solids (MLVSS) con-
centrations of 72.776.8 and 26.0371.37 g/l, respec-
tively, was obtained from the anaerobic sludge digesters
of the Ankara wastewater treatment plant. The feed
contained methanol, glucose and yeast extract as well as
basal medium (BM) during the start-up period. BM
contained all the necessary micro- and macro-nutrients
for an optimum anaerobic microbial growth [20]. The
composition of the BM was as follows (concentrations
of the constituents are given in brackets as mg/l): NH
4
Cl
(1200), MgSO
4
7H
2
O (400), KCl (400), Na
2
S 9H
2
O
(300), CaCl
2
2H
2
O (50), (NH
4
)
2
HPO
4
(80),
FeCl
2
4H
2
0 (40), CoCl
2
6H
2
0 (10), KI (10),
MnCl
2
4H
2
0 (0.5), CuCl
2
2H
2
0 (0.5), ZnCl
2
(0.5),
AlCl
3
6H
2
0 (0.5), NaMoO
4
2H
2
O (0.5), H
3
BO
3
(0.5),
NiCl
2
6H
2
0 (0.5), NaWO
4
2H
2
O (0.5), Na
2
SeO
3
(0.5),
cysteine (10) and NaHCO
3
(3000).
During the start-up period the COD loading was
gradually raised by increasing the feed rate while
keeping the inuent COD constant at around 5000 mg/
l. The yeast extract concentration in the feed was 20 mg/l
and the remaining COD was supplied by methanol and
glucose at different ratios (Table 3). Methanol which
provided 50% of the total inuent COD (5000 mg/l)
initially encouraged the growth of methanosarcina [21].
The contribution of methanol in the total inuent COD
was decreased to 25%, 12.5%, and 0% on days 25, 38,
and 46, respectively, by replacing it with glucose.
Moreover, NH
4
Cl concentration was gradually in-
creased to its value in BM (1200 mg/l) to obtain high
initial C/N ratios during the start-up period to
encourage extracellular polymer production, which aids
bacterial attachment on solid surface (Table 3).
2.3. Operation period
In the operation period, the reactor was fed with the
real textile wastewater obtained from dye bath efuent
of a dye house in Ankara, Turkey. Wastewater
characterization was done for wastewater in each
different container that was used for experimental
practice (Table 4). In the dye house, reactive dyes
namely Remazol, Everzol and Levax types of dyes are
commonly used. FBR was operated under 6 different
operational conditions. These conditions are tabulated
in Table 5.
2.4. Analytical methods
pH measurements were performed with a pH meter
(Model 2906, Jenway Ltd., UK) and a pH probe (G-
05992-55, Cole Parmer Instrument Co., USA). COD of
samples were measured by Hach spectrophotometer
(Model no P/N 45600-02) and vials for 01500 mg/l
COD. Suspended solids and volatile suspended solids
were measured as described in Standard Methods 2540
D, E. Total phosphorus and total Khjeldahl nitrogen
concentrations were also determined by Standard
Methods 4500-P-E and 4500-N
org
, respectively [22]. To
measure the immobilized biomass, sample from the
expanded bed material was collected in a ceramic dish
through a sampling port (510 ml). Suspended biomass
Recycling
pump
Inlet
structure
Sampling ports
Feed solution
Water trap
Effluent
collection
Feeding
pump
Magnetic stirrer
Fig. 1. Schematic diagram of the anaerobic uidized bed
reactor (FBR) system.
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1872
in the mixed liquor was removed by gentle wash then, it
was dried at 1051C for 24 h. The dried sample was then
mufed at 6001C for 1 h. The difference between two
dried weights would yield the weight of immobilized
biomass as attached volatile solids (AVS).
Color was measured by UVVis spectrophotometer
(Varian Cary 100 Conc, Australia) at peak absorption
wavelength of real textile wastewater (669 nm). Before
analysis, samples were ltered through 0.45 mm lters to
remove suspended matters.
3. Results and discussion
Start-up period was completed in 128 d. The AVS
concentration (0.0732 g VSS/g support) attained at the
end of the start-up period was within the typical range
reported in the literature such as 0.0740.11 [23], 0.039
[43], 0.05 [24], and 0.03750.429 g VSS/g support [25].
Table 6 shows operational parameters obtained at the
end of start-up period. The bed expansion was 19%
during the start-up period. It was increased to and kept
between 35% and 40% in the operation period which is
in the typical range reported in the literature [26,27].
After the start-up period, the real textile wastewater
was fed to the reactor. The corresponding organic
loading rate (OLR), HRT, efuent pH, VFA and
alkalinity values, inuent and efuent COD and BOD
5
values, COD and BOD
5
removal, inuent and efuent
color and color removal are depicted in Fig. 2. As seen
in Table 5, the FBR was operated under 6 different
operating conditions (stages) with the aim of increasing
the color removal efciency in the reactor for a 118-d
period.
Table 3
Organic load and percentage of methanol and ammonium chloride during the start-up
Time (days) COD loading (kg COD/m
3
d) Methanol (% of total COD) Glucose+yeast (% of total COD) NH
4
Cl
a
024 03.75 50 50 50
2537 3.7510 25 75 75
3845 1015 12.5 87.5 100
46128 1522 0 100 100
a
% of its value at the end of the start-up.
Table 4
Characteristics of real textile wastewater
Parameters Container 1 Container 2 Container 3 Container 4
pH 9.91 9.9 8.9 8.9
BOD
5
(mg/l) 170714.14 162.570 90721 97.573.5
COD (mg/l) 1029767.4 1157.57100 1062.67760.7 1018711.3
SS (mg/l) 180716 11079 13075 180784.8
TKN (mg/l) 22.5172.05 20.7870.55 57.0674.51 55.8170.5
PO
4
3
(mg/l) 2.3970.09 2.1670.08 1.4270.07 0.9270.07
SO
4
2
(mg/l) 2.3670.38 1.9470.33 4.2370.06 6.4370.14
Cl
1
(mg/l) 609.8 594.8728.3 557.33710.6 569.877.07
Color (at 669 nm) 0.21 0.18 0.16 0.15
Table 5
Different operational conditions applied to the FBR
Container no and on
which day it was used
Stage Operation days OLR (kg COD/
m
3
d)
HRT
(h)
Feed composition Inuent COD
conc. (mg/l)
1-114 1 146 1 24 TW 1030
2-1546 2 4762 0.5 50 TW 1162
3-4786 3 6377 0.38 50 TW: SMW (3:1) 850
4-87118 4 7891 1.3 24 TW+glucose 1500
5 92105 3 24 TW+glucose 3000
6 106118 5 24 TW+glucose 6000
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1873
3.1. Stage 1 (days 146)
In this stage, real textile wastewater was fed to the
reactor without any additional carbon and nutrient
source, only alkalinity was added (with different con-
centrations, see Fig. 2e) prior to feeding. Average COD
concentration of real textile wastewater was 1100 mg/l.
During Stage 1, OLR was kept at around 1 kg COD/
m
3
d. HRT applied to the reactor was around 24 h
(Fig. 2b). pHof the efuent was around 9 (Fig. 2c), which
did not vary much during the operation period. The
optimum reactor operation conditions were achieved in
anaerobic systems when pH and alkalinity values are
greater than 6.5 and 800 mg/l (as CaCO
3
), respectively
and when VFA concentration is lower than 250 mg/l.
Efuent alkalinity concentration was between 580 and
750 mg/l (as CaCO
3
) (Fig. 2e) and VFA concentration in
the efuent was lower than 100mg/l during the operation
period (Fig. 2e). Both VFA and alkalinity data supported
that the reactor was operating properly.
As seen in Fig. 2g, COD removal in the reactor during
Stage 1 varied over time. COD removal efciency
decreased from 59% to 27% between day 10 and 18,
possibly due to the toxic effect of real textile wastewater.
After acclimation of anaerobic microorganisms to real
textile wastewater, a gradual increase in the COD
removal rate was recorded. On day 33, COD removal
rate reached to 68% and from that point on it did not
change much. Fig. 2h and i depict that BOD
5
removal
rate in Stage 1 showed the same pattern with COD
removal. On day 10, BOD
5
removal was 98%, however
it decreased to 45% in 7 d. After the cultures were
acclimated to the feed, the BOD
5
removal increased to
84% on day 25 and did not vary considerably for the
rest of this stage.
During the rst 24 d, no color removal was observed
in the efuent (Fig. 2j and k). This period was
considered as the acclimation period after which the
onset of color removal was observed with the increase in
COD removal rate (Fig. 2g and k). The color removal
rate was 37% on day 41.
Providing an optimum growth condition for metha-
nogens is critical for color removal. It is known that
methanogenic and acetogenic bacteria in anaerobic
cultures contain unique reduced enzyme cofactors, such
as F
430
and vitamin B
12
that could also potentially
reduce azo bonds. It is therefore, not surprising that azo
reduction rates are sensitive to the amount of available
substrate in an anaerobic system as well as the loading
rate, since catabolism of these substrate is responsible
for the production of reduced enzyme cofactor [5]. As a
result, low color removal with low COD removal
performance was an expected outcome.
3.2. Stage 2 (days 4762)
In Stage 2, HRT applied to the reactor was increased
from 24 to about 50 h (Table 5) to observe the effect of
this increase on the color removal efciency of the
system. Since the inuent COD concentration was the
same (around 1100 mg/l), the OLR decreased to 0.5 kg
COD/m
3
d with the increase in HRT.
With the increase in HRT from 24 to 50 h, the COD
and BOD removal rates decreased to about half of their
values at the end of Stage 1. In other words, COD and
BOD
5
removal rates dropped to 35% and 39%,
respectively. As seen from Fig. 2j and k the color
removal rate also decreased to 19% during Stage 2 (day
61). Decrease in COD, BOD
5
and color removal
performances with the decrease in OLR is understand-
able due to low synthesis of unique reduced enzyme
cofactors (F
430
and vitamin B
12
) responsible for color
reduction under anaerobic conditions. Therefore, it can
be stated that an increase in HRT alone did not result in
the increased color removal.
3.3. Stage 3 (days 6377)
Combined treatment of textile and municipal waste-
water was simulated in this stage. This practice is
advantageous wherever applicable. Because many treat-
ment problems such as ow, alkalinity, temperature
extremes and uctuations are solved by treating textile
and municipal wastewater together. Furthermore, mu-
nicipal wastewater may supply the necessary nutrients
for the biological growth. In this period, textile waste-
water was mixed with synthetic municipal wastewater
(SMW) at 3:1 ratio. The composition of the SMW
solution was 500 mg/l glucose, 27 mg/l urea, 22 mg/l
KH
2
PO
4
and 1000 mg/l Na
2
CO
3
. COD and BOD of the
mixture were between 800900 and 90 mg/l, respectively.
HRT was kept constant at about 50 h (Fig. 2b), OLR
decreased to about 0.38 kg COD/m
3
d.
Upon this change in the feed composition, the BOD
5
removal rate increased to 90% while COD removal rate
remained around 40% in this stage.
Table 6
Operational parameters at the end of start-up period for FBR
Operational parameters FBR
OLR (kg COD/m
3
d) 23
HRT (h) 5.7
Upow velocity (m/h) 19
Q
recycle
=Q
feed
295
Expansion (%) 19
Volume of expanded bed (cm
3
) 700
M
support
(g) 620
g VSS/g support 0.0732
Total VSS (g) 45.4
g VSS/l expanded bed 64.8
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1874







O
L
R

(
k
g

C
O
D
/
m
3
.
d
)
0
2
4
6
H
R
T

(
h
r
)
20
40
60
p
H
8
9
10
C
O
D
(
m
g
/
L
)
2000
4000
6000
Effluent
Influent
C
O
D

r
e
m
o
v
a
l









(
%
)
20
40
60
80
100
120

V
F
A

(
m
g
/
L
)
0
50
100
150
200
A
l
k
a
l
i
n
i
t
y

(
m
g

C
a
C
O
3
/
L
)
0
500
1000
1500
A
b
s
o
r
b
a
n
c
e
@

6
6
9

n
m
0.00
0.05
0.10
0.15
0.20
0.25
0 10 20 30 40 50 60 70 80 90 100 110 120

C
o
l
o
r

r
e
m
o
v
a
l

(
a
s

a
b
s
o
r
b
a
n
c
e
)
0
20
40
60
80
B
O
D
5

(
m
g
/
L
)
2000
4000
6000



B
O
D
5

r
e
m
o
v
a
l

(
%
)
20
40
60
80
100
Stage 1 Stage 2 Stage 3
Time (days)
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
Stage 4 Stage 5
OLR=1 (kg COD/m
3
.d)
HRT= 1 d
OLR=0.5
HRT= 50 h
TW : SMW
(3:1)
TW+glucose
(1500 mg/L
COD)
TW+glucose
(3000 mg/L
COD)
Stage 6
TW+glucose
(6000 mg/L
COD)
Influent alkalinity
Fig. 2. Operation period for FBR treating real textile wastewater.
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1875
As seen from Fig. 2j and k, color removal decreased
sharply to zero, then increased to 12% (day 76) as the
maximum value in this stage. It is evident that color
removal performance of the reactor was adversely
effected from this change in the inuent composition.
Combined treatment of textile and municipal wastewater
did not result in any gain in terms of color removal over
the treatment of textile wastewater alone (Stage 2).
3.4. Stage 4 (days 7891)
In Stage 4, an external carbon source was added to the
textile wastewater in the form of glucose at a concentra-
tion of about 500 mg/l yielding an inuent COD
concentration of about 1500 mg/l (Table 5). At the same
time the HRT of the reactor was decreased from 50
to about 24 h which resulted in an OLR of 1.3 kg COD/
m
3
d.
With the addition of 500 mg/l of glucose as the
external carbon source and corresponding increase in
the inuent COD concentration, BOD
5
and COD
removals increased to 94% and 6266%, respectively.
While the color removal increased to 4044% (Fig. 2k).
A signicant increase in the color removal performance
of the FBR is noteworthy in this stage. This improve-
ment was due to the addition of external carbon source,
which helps to ascertain a reducing environment and
possibly increase the concentration of enzyme cofactors,
such as F
430
and vitamin B
12
in the reactor that could
also potentially reduce azo bonds [5] and hence resulting
in better color removal.
3.5. Stage 5 (days 92105)
After observing the stimulative effect of the addition
of 500 mg/l of glucose as the external carbon source
in Stage 4, glucose concentration was increased to
about 2 g/l to observe the effect of increasing the
concentration of the external carbon source. With this
increase in the glucose concentration, the inuent COD
concentration and OLR applied to the reactor increased
to about 3000 mg/l and 3 kg COD/m
3
d, respectively
(Table 5).
COD and color removal rates increased to 7882%
and 5459% from earlier values of 6266% and 40
44%, respectively (Fig. 2g and k). While the BOD
5
removal rate in the reactor was around 94%. From these
gures it was clear that increasing the glucose concen-
tration from 500 to 2000 mg/l resulted in signicantly
better performance of the FBR both in terms of organics
and color removal.
3.6. Stage 6 (days 106118)
In Stage 6, the concentration of glucose as the external
carbon source was increased further to about 5000 mg/l
to observe any additional improvement in the perfor-
mance of the FBR. As seen in Table 5, this change in the
glucose concentration increased the inuent COD
concentration to around 6000 mg/l and the OLR to
5 kg COD/m
3
d. In this stage although the COD and
BOD
5
removal rates increased to 89% and 99%,
respectively, color removal did not increase signicantly
and stayed around 62% (Fig. 2j and k).
As a result, it was observed that further increase in the
glucose, thus inuent COD concentration did not
improve the color removal efciency of the system
considerably. Therefore, Stage 5 (textile wastewater with
2 g/l glucose addition) represented the optimum condi-
tion for maximum color removal in the real textile
wastewater investigated in this study.
4. Conclusions
Apart from the aesthetic deterioration and obstruc-
tion for penetration of dissolved oxygen into the natural
water bodies caused by the presence of color, some of
the dyes, dye precursors and the dye degradation
products are carcinogenic and mutagenic in nature
[28]. Existing physico-chemical methods for decoloriza-
tion such as advanced oxidation processes like the use of
Fentons reagent (H
2
O
2
+Fe
2+
), hydrogen peroxide,
ozonation are costly in terms of operation costs and
produce problematic sludge. Coagulationocculation
produce high amounts of sludge which pose handling
and disposal problems. Activated carbon adsorption,
membrane ltration, ion exchange, irradiation, and
electrokinetic coagulation are also uneconomical and/
or not very established [4,28,29].
Biological treatment methods, on the other hand,
provide efcient and low cost means of textile waste-
water treatment [6,30]. Conventional aerobic treatment
systems are not efcient [4,5,31]. Decolorization of dyes
using pure (algal, fungal, and bacterial) cultures is
impractical as most of the isolated cultures are dye
specic [28]. However, decolorization of dyes and/or
treatment of textile wastewaters under strict anaerobic
conditions is well documented [5,79,15,28,30,32,33].
Because the textile sector in Turkey is one of the most
important industrial sectors both in terms of its
contribution to economy and environmental emissions,
efcient and cost-effective treatment methods are
needed. Therefore, anaerobic treatability of a real cotton
textile wastewater was investigated in a FBR with
pumice as the support material. The results indicated
that the anaerobic treatability of the textile wastewater
studied was found to be optimal upon the addition of an
external carbon source in the form of 2 g/l glucose (with
the inuent COD concentration of 3000 mg/l). COD,
BOD
5
and color removals achieved were around 82%,
94% and 59%, respectively. The observed improvement
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1876
in the color removal with the addition of 2 g/l of glucose
is in agreement with the literature which underline the
importance of external carbon source supplementation
to anaerobic reactors treating dyes/textile wastewater
[5,9,31,32,34,35]. Further increase in external carbon
source adding to textile wastewater did not improve the
color removal efciency of the system.
Finally, the requirement of glucose addition as the
external carbon source to the textile wastewater with a
concentration of 2 g/l might be a concern in terms of the
practical applicability of anaerobic treatment. However,
it should be kept in mind that anaerobic treatment
compared to physico-chemical treatment methods still
offers a viable option in terms of cost.
Acknowledgements
This study was funded by the State Planning
Organization of the Republic of Turkey. Dr. Metin M.
Duran of Villanova University is deeply appreciated for
his valuable suggestions and help in obtaining the
support material used in the FBRs.
References
[1] EPA Ofce of Compliance Sector Notebook Project:
Prole of the Textile Industry, EAA/310-R-97-009,
September 1997.
[2] Fitzgerald SW, Bishop PL. Two-stage anaerobic/aerobic
treatment of sulfonated azo dyes. J Environ Sci Health A
1995;30:125176.
[3] Shore J. Dyeing with reactive dyes. In: Cellulosics Dyeing.
Oxford, Manchester, UK: The Alden Press, 1995.
[4] Vandevivere PC, Bianchi R, Verstraete W. Treatment and
reuse of wastewater from the textile wet-processing
industry: Review of emerging technologies. J Chem
Technol Biotech 1998;72:289302.
[5] Razo-Flores E, Luijten M, Donlon B, Lettinga G, Field J.
Biodegradation of selected azo dyes under methanogenic
conditions. Water Sci Technol 1997;36:6572.
[6] Banat IM, Nigam P, Singh D, Marchant R. Microbial
decolorization of textile-dye-containing efuents: a review.
Biores Technol 1996;58:21727.
[7] Brown D, Laboureur P. The degradation of dyestuffs: 1.
Primary biodegradation under anaerobic conditions.
Chemosphere 1983;12:397404.
[8] Carliell CM, Barclay SJ, Naidoo N, Buckley CA, Mulhol-
land DA, Senior E. Microbial decolorization of a reactive
azo-dye under anaerobic conditions. Water SA 1995;
21:619.
[9] Chinwekitvanich S, Tuntoolvest M, Panswad T. Anaero-
bic decolorization of reactive dyebath efuents by a two-
stage UASB system with tapioca as a co-substrate. Water
Res 2000;34:222332.
[10] Razo-Flores E, Donlon B, Field J, Lettinga G. Biodegrad-
ability of N-substituted aromatics and alkylphenols under
methanogenic conditions using granular sludge. Water Sci
Technol 1996;33:4757.
[11] Zaoyan Y, Ke S, Guangliang S, Fan Y, Jinshan D,
Huanian M. Anaerobic-aerobic treatment of a dye waste-
water by combination of RBC with activated sludge.
Water Sci Technol 1992;26:20936.
[12] Kool HJ. Inuence of microbial biomass on the biode-
gradability of organic compounds. Chemosphere 1984;
13:75161.
[13] Zeyer J, Wasserfallen A, Timmis KN. Microbial miner-
alization of ring-substituted anilines through an orto-
cleavage pathway. Appl Environ Microbiol 1985;50:
44753.
[14] OConnor OA, Young LY. Effect of nitrogen limitation on
the biodegradability and toxicity of nitrophenol and
aminophenol isomers to methanogenesis. Arch Environ
Contam Toxicol 1993;25:28591.
[15] Brown D, Hamburger B. The degradation of dye stuffs: 3
Investigations of their ultimate degradability. Chemo-
sphere 1987;16:153953.
[16] Seshadri S, Bishop PL, Agha AM. Anaerobic/aerobic
treatment of selected azo dyes in wastewater. Waste
Manage 1994;14:12737.
[17] Denac M, Dunn IJ. Packed-bed and uidized bed biolm
reactor performance for anaerobic wastewater treatment.
Biotech Bioeng 1988;32:15973.
[18] Henze M, Harremoes P. Anaerobic treatment of waste-
water in xed lm reactors - a literature review. Water Sci
Technol 1983;15:1101.
[19] Hickey RF, Owens RW. Methane generation from high
strength industrial wastes with the anaerobic biological
uidized bed, Biotech. Bioeng Suppl 1981;11:399413.
[20] Demirer GN, Speece RE. Toxicity of acrylic acid to
acetate-enriched methanosarcina cultures. J Environ Eng
Div ASCE 1998;124:34552.
[21] Boone DR, Bryant MP. Propionate-degrading bacteria
from methanogenic ecosystems. 80th General Meeting of
the American Society for Microbiology. Miami Beach, FL,
USA: American Society for Microbiology, 1980.
[22] Standard Methods for the Examination of Water and
Wastewater. 20th ed. Washington, DC: APHA, AWWA,
WEF, 1997.
[23] Farhan MH, ChinHong PH, Keenan JD, Shieh WK.
Performance of anaerobic reactors during pseudo-
steady-state operation. J Chem Technol Biotech 1997;
69:4557.
[24] Garcia-Bernet D, Bufere P, Elmaleh S, Moletta R.
Application of the down-ow uidized bed to the
anaerobic treatment of wine distillery wastewater. Water
Sci Technol 1998;38:3939.
[25] Perez M, Romero LI, Sales D. Anaerobic thermophilic
uidized-bed treatment of industrial wastewatereffect of
F-M relationship. Chemosphere 1999;38:344361.
[26] Balaguer MD, Vicent MT, Paris JM. Utilization of pumice
stone as support for the anaerobic treatment of vinasse
with a uidized-bed reactor. Environ Technol 1991;12:
116773.
[27] Stronach SM, Diazbaez MC, Rudd T, Lester JN. Factors
affecting biomass attachment during startup and operation
of anaerobic uidized-beds. Biotech Bioeng 1987;30:
61120.
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1877
[28] Manu B, Chaudhari S. Anaerobic decolorisation of
simulated textile wastewater containing azo dyes. Biores
Technol 2002;82:22531.
[29] Robinson T, McMullan G, Marchant R, Nigam P.
Remediation of dyes in textile efuent: a critical review
on current treatment technologies with a proposed
alternative. Biores Technol 2001;77:24755.
[30] Beydilli MI, Pavlostathis SG, Tincher WC. Decolorization
and toxicity screening of selected reactive azo dyes under
methanogenic conditions. Water Sci Technol 1998;38:22532.
[31] Huren A, Yi Q, Xiasheng G. A way for water pollution
control in dye manufacturing industry. 49th Purdue
Industrial Waste Conference Proceedings, Chelsea, MI,
USA: Lewis Publishers, 1994.
[32] Bell J, Plumb JJ, Buckley CA, Stuckey DC. Treatment and
decolorization of dyes in an anaerobic bafed reactor.
J Environ Eng Div ASCE 2000;126:102632.
[33] Donlon B, Razo-Flores E, Luijten M, Swarts H, Lettinga
G, Field J. Detoxication and partial mineralization of the
azo dye mordant orange 1 in a continuous upow
anaerobic sludge-blanket reactor. Appl Microbiol Biotech
1997;47:8390.
[34] Basib. uy. uk M, Forster CF. The use of sequential anaero-
bic/aerobic processes for the biotreatment of a simulated
dyeing wastewater. Environ Technol 1997;18:8438.
[35] ONeill C, Hawkes FR, Hawkes DL, Esteves S, Wilcox SJ.
Anaerobic-aerobic biotreatment of simulated textile efu-
ent containing varied ratios of starch and azo dye. Water
Res 2000;34:235561.
[36] An H, Qian Y, Gu XS, Tang WZ. Biological treatment of
dye wastewaters using an anaerobic-oxic system. Chemo-
sphere 1996;33:253342.
[37] Haug W, Schmidt A, Nortemann B, Hempel DC, Stolz A,
Knackmuss HJ. Mineralization of the sulfonated azo dye
mordant yellow-3 by a 6-aminonaphthalene-2-sulfonate-
degrading bacterial consortium. Appl Environ Microbiol
1991;57:31449.
[38] Kuai L, De Vreese I, Vandevivere P, Verstraete W. GAC-
amended UASB reactor for the stable treatment of toxic
textile wastewater. Environ Technol 1998;19:11117.
[39] Louren- co ND, Novais JM, Pinheiro HM. Reactive textile
dye color removal in a sequencing batch reactor. Water Sci
Technol 2000;42:3218.
[40] Nigam P, Banat IM, Singh D, Marchant R. Microbial
process for the decolorization of textile efuent containing
azo, diazo and reactive dyes. Process Biochem 1996;
31:43542.
[41] Oxspring DA, McMullan G, Smyth WF, Marchant R.
Decolourisation and metabolism of the reactive textile dye,
remazol black B, by an immobilized microbial consortium.
Biotech Lett 1996;18:52730.
[42] Panswad T, Luangdilok W. Decolorization of re-
active dyes with different molecular structures under
different environmental conditions. Water Res 2000;
34:417784.
[43] Meraz M, Monroy O, Noyola A, Ilangovan K. Studies on
the dynamics of immobilization of anaerobic bacteria on a
plastic support. Water Sci Technol 1995;32:24350.
S. - Sen, G.N. Demirer / Water Research 37 (2003) 18681878 1878