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Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 359364

Contents lists available at ScienceDirect

Journal of the Taiwan Institute of Chemical Engineers


journal homepage: www.elsevier.com/locate/jtice

Removal of uorescent dissolved organic matter in biologically treated


textile wastewater by ozonation-biological aerated lter
Qian Wu a, Wen-Tao Li a, Wei-Hua Yu b, Yan Li a,, Ai-Min Li a
a
b

State Key Laboratory of Pollution Control and Resources Reuse, School of the Environment, Nanjing University, Nanjing 210023, China
Nanjing University & Yancheng Academy of Environmental Protection Technology and Engineering, Yancheng 224000, China

a r t i c l e

i n f o

Article history:
Received 7 January 2015
Revised 13 August 2015
Accepted 26 August 2015
Available online 29 September 2015
Keywords:
Textile wastewater
Ozone-biological aerated lter
Decoloration
Fluorescence excitationemission matrix
High-performance liquid chromatography
(HPLC)

a b s t r a c t
Ozonation-biological aerated lter (O3 -BAF) has been proven effective for the biologically treated textile
wastewater. However, little information on the behavior of dissolved organic matter in the process was available. In this study, a pilot scale O3 -BAF was set up to treat the biologically treated textile wastewater, and
both uorescent excitationemission-matrix (EEM) and HPLC with multi-excitation/emission uorescence
scan were applied to study the removal characterization of uorescent dissolved organic matter (DOM). The
results showed that with the improvement of biodegradability by ozonation, the combination of ozonation
and BAF could low the COD of the euent below 50 mg/L, meeting the Chinese Discharge Standard. EEM
analysis showed that the removal of the triple-excitation peaks at Em460 was the dominant mechanism of
high removal eciency of color and UV254 during ozonation process. In addition, during the ozonation process, the uorescent DOM species were decomposed in the order of humic substances with Em at 460 nm
(HS-Em460-Ex3), the hydrophobic aniline-like species, humic substances with Em at 430 nm (HS-Em430Ex2) and the hydrophilic aniline-like species. This study provided better understanding on the decoloration
mechanism of ozonation and helps to build automatic optimization systems in advanced treatment of textile
wastewater.
2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Textile industry consumes substantial water and complex chemicals during various textile processing stages, and also generates a
large quantity of hazardous wastewater that is high in color and
toxic chemicals [1]. The direct discharge of such wastewater not only
affects the aesthetic merits of the receiving water bodies, but also
threatens the health of the aquatic systems and human beings by
the possible toxicity and carcinogenicity [24]. Herein various techniques have been applied for the treatment of textile wastewater,
such as biological degradation, adsorption, membrane separation,
chemical coagulation and oxidation [2,5,6]. Due to its robustness,
eco-friendliness and especially the lower costs, biological treatment
is most widely used, in which the typical process is anoxic or anaerobic hydrolysis-acidication in combination with aerobic oxidation
(A/O) [3,5,7]. And its removal mechanism has been clearly elucidated
as anaerobic treatment for the reductive cleavage of azo bonds in
dyestuffs with the following aerobic treatment for further degradation of the produced aromatic amines [3].

Corresponding author at: School of the Environment, Nanjing University, Xianlin


Campus, Nanjing 210023, China. Tel.: +86 25 89680377; fax: +86 25 89680377.
E-mail address: liyan_0921@126.com (Y. Li).

However, the textile wastewater contains different types of


dyestuffs, which might have very low biodegradability and then result in the uctuation of euent quality [8,9]. Also, the biologically
treated textile euents containing large amounts of dissolved organic matter (DOM) still have deep color and high UV absorbance at
254 nm (UV254 ), which can cause the light attenuation of the receiving water bodies [10,11]. Another important problem with the biological treatment is the residual aromatic amines in euents, which
could be more toxic and carcinogenic than their parent dyestuffs [12].
With the more stringent discharge standard, advanced treatment is
quite necessary to achieve adequate level of decoloration and detoxication as well as chemical oxygen demand (COD) removal.
At present, advanced oxidation processes (AOPs) such as Fenton and ozonation seem to be the most desirable for the advanced
treatment of biologically treated textile euents [2,13]. As a kind of
sludge-free AOPs, ozonation is increasingly promising because of the
limited space and high expense for disposal of sludge [14]. Other merits of ozonation treatment are the improvement of biodegradability,
reduction of aromatic compounds and also partially decrease of COD
[1517]. Typically, ozonation rarely causes complete mineralization
of organic matter, but leads to partial oxidation products such as organic acids, aldehydes and ketones [14]. The biological aerated lter (BAF) is an alternative to the traditional activated sludge process,

http://dx.doi.org/10.1016/j.jtice.2015.08.015
1876-1070/ 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

360

Q. Wu et al. / Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 359364

Table 1
Characterization of textile wastewater after coagulation and sedimentation.
pH

Color (times)

UV254 (abs units)

COD (mg/L)

BOD (mg/L)

8.59

130200

1.01.5

70100

510

which is very effective in removing organic matter from wastewater


that features relatively low levels of COD [18]. Ozonation in tandem
with biological aerated lter (O3 -BAF) has been observed as one of
the most economical and effective techniques for treatment of textile
wastewater [1821].
However, the previous works mainly use bulky characteristics like
COD, biological oxygen demand (BOD), color, and UV254 to investigate the removal of DOM during ozonation treatment of textile
wastewater [1823]. Fluorescent excitationemission-matrix (EEM)
has been extensively applied for characterization of DOM in both natural and engineered water systems [24,25]. Recently, we rstly introduced HPLC/HPSEC with multi-excitation/emission uorescence scan
for DOM characterization and EEM interpretation [26,27]. For the textile wastewater, due to the electron-donating effect of amine groups,
aromatic amines like derivatives of aniline or naphthylamine will exhibit strong uorescence [28]; while ozone molecule preferentially
attacks the unsaturated bonds of chromophores [15]. With the development of the eld-portable uorometer [29], it is very possible
to realize the automatic optimization of ozone dosage. Herein it is
meaningful to study the behavior of uorescent DOM during the O3 BAF treatment of textile wastewater, which can guide the selection of
excitation and emission wavelengths for online monitoring.
In this work, the treatment eciency of a pilot O3 -BAF for advanced treatment of textile euents was studied. The EEM and HPLC
with multi-excitation/emission uorescence scan were further applied to investigate the behavior of uorescent DOM during the O3 BAF treatment. The results of this study help to understand the decoloration mechanism of ozonation and build automatic optimization
systems in the advanced treatment of textile wastewater.

The ozonation reactor consisted of ozonizer, ozone-online detector, contact reactor and off-gas absorption device. The ozonizer
used compressed oxygen as the gas source with the gas ow rate of
0.6 m3 /h. Different ozone concentrations could be obtained by adjusting the voltage. Ozonation was performed in 6 series of polyvinyl
chloride tubes (inner diameter 0.13 m, height 5 m), which is designed
to improve utilization rate of ozone. After ozonation, the wastewater was aerated for about 10 min to eliminate residual ozone which
might damage the microorganism in the BAF.
The upow BAF reactor was made of carbon steel with an epoxy
anticorrosive coat and the size of the reactor was 1.2 1.2 4.0 m3
(a b h) with the volume of empty bed of 3.6 m3 . BAF reactor was
packed with ceramsite balls ranging from 3 to 5 mm in diameter. Oxygen was introduced via compressed air through porous tubes located
at the bottom of the BAF.
The BAF reactor was inoculated with activated sludge from the
aerobic tank of wastewater treatment process in the textile mill. After a start-up stage of 20 days, the surface of ceramsite balls were
attached with biolm and microorganisms, and meanwhile, the COD
removal increased to a steady level. Under the condition of hydraulic
retention time 2.4 h and airwater ratio 5:1, the lter reactor was
backwashed with gaswater once 2 weeks to remove the accumulated suspended solid and the excess biomass to keep the system
operating eciently and steadily. The schematic diagram and photograph of the pilot O3 -BAF is provided in Figs. S1 and S2 of the Supplementary Material (SM).
2.3. The kinetic experiment of ozonation

2. Material and methods

The kinetic experiment of ozonation was conducted in laboratory


with sample from the same sedimentation tank. Ozone was generated from dry air using a laboratory model ozone generator with an
ozone production of 2.5 mg/min. The ozonation was conducted in a
1 L cylindric glass reactor and samples were drawn at 0, 1, 2, 4, 6, 8,
10, 15, 20 min for analysis. The ozone dosage was determined by the
reaction time. After ozonation, the wastewater was aerated for 5 min
with air to eliminate the inuences on the subsequent measurements
from residual ozone.

2.1. Chemicals and materials

2.4. Analytical methods

Acetonitrile was of HPLC grade and purchased from Merck (Shanghai, China). Pure water from a Millipore system (Millipore, Bedford,
MA, USA) was used in HPLC array. All other chemicals are of analytical grade and purchased from Sinopharm Chemical Reagent Co., Ltd
(Shanghai, China). All reagents were used without further purication. Ceramsite balls are purchased from an environmental protection
company in Henan Province, China.

COD was analyzed by the standard method of potassium dichromate oxidation. Color was measured by the dilution multiple method
and values are expressed as x (0 indicates that the sample is as
clear as pure water). The UV254 absorbance was measured with a Shimadzu UV-1800 ultravioletvisible (UVvis) spectrophotometer. Removal rate of color, UV254 and COD were calculated as:

2.2. Pilot O3 -BAF system


In this study, the pilot-scale O3 -BAF experiment was conducted
in a textile mill located at Nantong city, Jiangsu Province, China. The
textile mill engages in spinning, dyeing, weaving, nishing and so
on. Many dyes, both azo dyes and non-azo dyes, such as reactive,
disperse and acid dyes are utilized in the production process. The
textile mill produces two streams of textile wastewaer. One is highconcentration wastwater with COD of 8000 mg/L and the ow of
1000 t/d and the other is low-concentration wastwater with COD
of 800 mg/L and the ow 19000 t/d. High-concentration wastwater is mixed with low-concentration wastwater after up-ow anaerobic sludge bed (UASB) process. The mixed textile wastewater was
treated by the typical A/O process in tandem with coagulation
sedimentation. The feeding stream for the pilot O3 -BAF system was
from the euent of coagulationsedimentation. Table 1 lists the characteristics of the wastewater fed to O3 -BAF process.

Removal rate(%) =

C0 C
100%
C0

where C0 and C are the initial and nal values of color, UV254 and COD,
respectively.
The EEM analysis was conducted on a Hitachi F-7000 spectrouorometer. The slit widths of excitation and emission were both set
at 5 nm. Excitation (Ex) wavelengths were conducted from 200 to
400 nm at 5 nm intervals and emission (Em) wavelengths were conducted every 1 nm from 280 to 550 nm with the scanning speed of
2400 nm/min.
After ltering with 0.45 m membrane, samples were further
analyzed by Agilent 1200 LC systems coupled with UV absorbance
and uorescence detectors (FLD) [28]. For the reverse-phase HPLC,
an Eclipse XDB-C18 column (150 4.6 mm, 5 m) was applied. The
mobile phase was a mixture of acetonitrile and pure water, and the
gradient elution procedure was set as shown in Table 2. According to
results of EEM, FLD parameters were set as Em = 340/Ex = 220300
or Em = 460/Ex = 220400 for multi-excitation scan of protein-like

Q. Wu et al. / Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 359364

361

Table 2
The HPLC elution procedure.
Time (min)

Solvent B (%)a

Solvent D (%)b

Flow rate (mL/min)

0.00
3.00
5.00

20.0
40.0
60.0

80.0
60.0
40.0

1
1
1

Solvent B: acetonitrile.
Solvent D: pure water. Among each sample injection, there were 3 min
of post-operation time for re-equilibration of mobile phase.
b

100

COD
UV254
color

Removal rate (%)

80

60

40

20

0
0

10

20

30

40

ozone dose (mg/L)


Fig. 1. Effect of ozone dose on COD, UV254 and color removal eciency by O3 -BAF
(conditions: pH 89; temperature 2535 C).

or humic-like uorophores, respectively. HPLC multi-emission scan


was set as Ex = 230/Em = 300500 nm. The UV absorbance spectra
from 200 to 300 nm were also taken in tandem with the uorescence
scan for each sample.
3. Results and discussion
3.1. Optimal ozone dosage
Ozone concentration varying from 0 mg/L to 40 mg/L was conducted to nd out the optimal ozone dosage in the pilot O3 -BAF
process. Each ozone dosage ran for a week, and during each stage,
color, UV254 and COD of the inuent and euent were daily analyzed. As shown in Fig. 1, it is obvious that increasing the ozone
dosage of per volume textile wastewater, the removal eciencies of
color, UV254 and COD steadily increased, and the variation of these
three indices were the order of color > UV254 > COD. For instance,
when the ozone dosage increased from 10 to 40 mg/L, the removal
of color, UV254 and COD increased from 67.5%, 41%, 18.3% to 96.2%,
62.6% and 43.8%, respectively. Especially, the removal eciency of
color suddenly went to nearly 70% when the ozone dosage increased
from 0 mg/L to 10 mg/L. It has been clearly elucidated that ozonation prefers to cleave the conjugated bonds of chromophores [4,15],
resulting in the signicant removal of color and UV254 . There were
some refractory organic compounds that cannot be thoroughly decomposed by ozonation. However, the steadily increasing removal
rate of COD further suggests that ozonation improved the biodegradability of textile wastewater from A/Ocoagulation process. Similar
phenomena were also observed in previous study [4,20]. In terms of
economics and eciency, the optimal ozone dosage was in the range
of 3040 mg/L for this study.
3.2. Running performance of the pilot O3 -BAF
The pilot O3 -BAF was operated with an ozone dosage of 35 mg/L
for 17 days. The pH values maintained in the range of 89 without signicant uctuation during the operation period. Samples were
daily taken from the inuent (i.e., the euent from coagulation
sedimentation process), euent of ozonation and BAF, respectively.

Fig. 2. The performance of the pilot-scale O3 -BAF system: (a) color, (b) UV254 and
(c) COD.

The performance of the pilot O3 -BAF in terms of color, UV254 and


COD removal are shown in Fig. 2. Fig. 2a shows that the O3 -BAF was
ecient for decoloration with the color removal higher than 90%.
Similarly, the O3 -BAF also stably reduced the UV254 absorbance of
the wastewater, and most of the values were lower than 0.7, under
the conditions in spite of the signicant uctuation of inuent UV254
(Fig. 2b). Further from Fig. 2a and b, the ozonation process rather than
BAF process mainly contributed to the total removal eciencies of
color and UV254 .
Fig. 2c shows that the ozonation process partially mineralize organic matter with the COD removal eciency in the range of 1015%;
while the following BAF removed another 2035% of COD. Ozone is
known as a kind of powerful oxidant and when it was dissolved in the
euent from coagulationsedimentation process, ozone could oxidize compounds including the residual dyes and other organic matter through direct oxidation and indirect reaction with free radical
species such as hydroxyl radical [15,30], and thus the biodegradability of the wastewater was considerable improved. Consequently, BAF
process accomplished a favorable operation. From this aspect, the
combination of ozonation and BAF process is effective on the advanced treatment of the biological treatment textile wastewater. After the O3 -BAF process, the euent COD was stably below 50 mg/L,
which meets the Chinese Discharge Standard.
However, the high uctuation of the inuent quality had signicant impacts on the removal eciency, when ozone is xed at
an optimal dosage. If the ozone dosage could coordinate with the

362

Q. Wu et al. / Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 359364

Fig. 3. EEM spectra of samples from O3 -BAF process: (a) feeding wastewater, (b) ozonation euent and (c) BAF euent.

uctuation of inuent characteristics, then it is expected the win-win


between operation eciency and costs can be achieved. In addition,
after the treatment of A/O in tanderm coagulationsedimentation
process in this textile mill, the COD of the wastwater decreaed from
1000 mg/L to 70100 mg/L. The residual COD made the biologically
treated textile euent, i.e., the inuent of pilot-scale O3 -BAF system, show brown color (Fig. S3 in SM), which was in agree with
the observation in previous study that the biologically treated textile wastewater was always in brown color whatever dyestuffs the
raw textile wastewater contained [28]. The brown color was not like
from any kind of dyestuffs, suggesting that decoloration mechanism
in this study could not be simply explained as oxidation of the residual dyestuffs.
3.3. EEM spectra in O3 -BAF process
The presence of aromatic amines in textile euents is a major
concern, because aerobic systems are not able to degrade all aromatic amines resulting from anaerobic process. Due to the electron donating effects of amine groups, aromatic amines like aniline or naphthylamine have intensive uorescence [28]. Herein EEM
spectra were measured to investigate the behavior of such uorescent DOM during the O3 -BAF process. Fig. 3a shows the typical EEM
spectra of the feeding wastewater. Obviously, there were ve uorescence peaks, which have been identied as the typical characteristics of biologically treated textile euents. The left two peaks
roughly located at Ex230/Em340 and Ex280/Em325 nm are generally dened as protein-like uorescence, but for textile euents, they
are mainly ascribed to the aromatic amines, especially some derivatives of aniline. The right three peaks at Ex250/Em460, Ex310/Em460
and Ex365/Em460 nm are attributed to a special humic-like substance (HS-Em460-Ex3) containing the critical uorescence structure 1-amino-2-naphthol, originated from the biodegradation of azo
dyes [28].
After ozonation and BAF treatment, the EEM spectra of the
wastewater signicantly changed. Fig. 3b and c shows EEM spectra
of euents from ozonation and BAF, respectively, both of which have
similar uorescence peaks roughly at Ex230/Em340, Ex280/Em325,
Ex240/Em430 and Ex350/Em430 nm. Similarly, the left two peaks
mainly originated from aniline derivatives, and the right two peaks
were similar to the widely observed humic-like uorescence (HSEm430-Ex2). Actually, the HS-Em430-Ex2 also existed in the inuent
of the pilot O3 -BAF. However, it was overwhelmed by the more intensive HS-Em460-Ex3.
The component HS-Em460-Ex3 has been identied as the major
contributor to the color and UV254 in most biologically treated textile
euents [28]. After ozonation, the triple-excitation peaks at Em460
have been substantially removed, and hence it explains the high removal eciency of color and UV254 during ozonation process.

Fig. 4. HPLC uorescence excitation-time-maps at Em 340 nm (a) and 460 nm (b).

3.4. Behavior of uorescent DOM in ozonation


In order to gure out the removal priority of uorescent DOM in
ozonation process, the kinetic experiment was conducted, and HPLC
with multi-excitation/emission scan was applied for quantitative
analysis. Fig. 4a shows the HPLC excitation-time-map at Em 340 nm
of the inuent, which represents the left two peaks in EEM, i.e.
aniline-like uorescence. With C-18 column, the earlier it is eluted,
the more hydrophilic it is. The derivatives of aniline were separated
into two clusters, designated as Peak A (the hydrophilic aniline-like
species) and Peak B (the hydrophobic aniline-like species) for integration, respectively. Fig. 4b shows the HPLC excitation-time-map
at Em 460 nm of the inuent, which represents the special component HS-Em460-Ex3. The chromatography peak here is designated as
Peak C.
As shown in Fig. 5, Peak C suddenly dropped at the rst 1 min
with the removal eciency up to 90%. It should be noted that during this period, the critical uorescence structure of HS-Em460-Ex3
was completely decomposed, because the HPLC excitation-time-map
showed that there were no triple excitation peaks any more (Fig. S6
in SM). Hence the points after 1 min of Peak C represent the variation of component HS-Em430-Ex2 (Fig. S6 in SM). Due to the competitive effect from HS-Em460-Ex3, the uorescence of Peak A and
Peak B decreased slightly in the rst 1 min. In the following 3 min
(14 min), both of them suddenly dropped, and especially, Peak B
was almost totally removed. After 4 min, the intensity of Peak A was

Q. Wu et al. / Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 359364

and 51408298), Jiangsu Scientic Innovation Project for Graduate


Students (KYLX_0054), the Scientic Research Foundation of Graduate School of Nanjing University and Shanghai Tongji Gao Tingyao
Environmental Science & Technology Development Foundation
(STGEF).

700

peak A
peak B
peak C

600

Intensity (a.u)

500

363

400
300

Supplementary materials

200

Supplementary material associated with this article can be found,


in the online version, at doi:10.1016/j.jtice.2015.08.015.

100
0
0

10

12

14

16

18

20

22

Time (min)
Fig. 5. Intensity of uorescence peaks as a function of reaction time.

gradually reduced. During the ozonation process, the uorescent


DOM species were decomposed in the order of HS-Em460-Ex3, Peak
B, HS-Em430-Ex2 and Peak A. In the form of EEM, ozonation rstly
reduced humic-like uorescence and then aniline-like uorescence
(Fig. S4 in SM).
To build an automatic control system, the online feedback signal is very critical. With the development of eld-portable uorometer, the uorescence technique is very promising for online monitoring [29]. When its application in the O3 -BAF system for advanced
treatment of textile wastewater, it is recommended to monitor the
aniline-like uorescence for automatic optimization of ozone dosage
and the parameters can be set similar to protein-like or tryptophan
uorescence.
4. Conclusions
A pilot-scale O3 -BAF process was applied for advanced treatment biologically treated textile wastewater. EEM and HPLC
multi-excitation/emission uorescence scan were applied to study
the behavior of uorescent DOM during the O3 -BAF treatment. The
following conclusions could be drawn:
(1) Ozone is highly ecient in the decolorization of textile
wastewater, but less ecient in terms of COD removal.
(2) The combination of ozonation and BAF process is effective
on the advanced treatment of the biological treatment textile
wastewater. With the ozone dosage of 35 mg/L and hydraulic
retention time of BAF at 2.5 h, the COD of the euent from
O3 -BAF process was below 50 mg/L, meeting the Chinese Discharge Standard.
(3) High removal eciency of color and UV254 during ozonation
process was mainly due to the removal of components with
the triple-excitation peaks at Em460 in EEM.
(4) HPLC excitation-time-maps indicated that during the ozonation process, the uorescent DOM species were decomposed
in the order of humic substances with Em at 460 nm (HSEm460-Ex3), the hydrophobic aniline-like species (Peak B), humic substances with Em at 430 nm (HS-Em430-Ex2) and the
hydrophilic aniline-like species (Peak A).
(5) For the advanced treatment of textile wastewater by O3 -BAF
system, it is recommended to monitor the aniline-like, especially the hydrophilic aniline-like uorescence for automatic
optimization of ozone dosage.
Acknowledgments
We gratefully acknowledge generous support provided by
National Natural Science Foundation of China (51438008, 51378251

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