Professional Documents
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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].
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
Table 1
Characterization of textile wastewater after coagulation and sedimentation.
pH
Color (times)
COD (mg/L)
BOD (mg/L)
8.59
130200
1.01.5
70100
510
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
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:
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
361
Table 2
The HPLC elution procedure.
Time (min)
Solvent B (%)a
Solvent D (%)b
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
80
60
40
20
0
0
10
20
30
40
Fig. 2. The performance of the pilot-scale O3 -BAF system: (a) color, (b) UV254 and
(c) COD.
362
Fig. 3. EEM spectra of samples from O3 -BAF process: (a) feeding wastewater, (b) ozonation euent and (c) BAF euent.
700
peak A
peak B
peak C
600
Intensity (a.u)
500
363
400
300
Supplementary materials
200
100
0
0
10
12
14
16
18
20
22
Time (min)
Fig. 5. Intensity of uorescence peaks as a function of reaction time.
References
[1] Verma AK, Dash RR, Bhunia P. A review on chemical coagulation/occulation
technologies for removal of colour from textile wastewaters. J Environ Manage
2012;93:15468.
[2] Bafana A, Devi SS, Chakrabarti T. Azo dyes: past, present and the future. Environ
Rev 2011;19:35070.
[3] Sarayu K, Sandhya S. Current technologies for biological treatment of textile
wastewatera review. Appl Biochem Biotech 2012;167:64561.
[4] Selcuk H, Eremektar G, Meric S. The effect of pre-ozone oxidation on acute toxicity
and inert soluble COD fractions of a textile nishing industry wastewater. J Hazard
Mater 2006;137:25460.
[5] Dafale N, Wate S, Meshram S, Neti NR. Bioremediation of wastewater containing
azo dyes through sequential anaerobicaerobic bioreactor system and its biodiversity. Environ Rev 2010;18:2136.
[6] Forgacs E, Cserhati T, Oros G. Removal of synthetic dyes from wastewaters: a review. Environ Int 2004;30:95371.
[7] Saratale RG, Saratale GD, Chang JS, Govindwar SP. Bacterial decolorization and
degradation of azo dyes: a review. J Taiwan Inst Chem E 2011;42:13857.
[8] Laing IG. The impact of euent regulations on the dyeing industry. Rev Prog Color
Rel Top 1991;21:5671.
[9] Tehrani-Bagha AR, Mahmoodi NM, Menger FM. Degradation of a persistent organic dye from colored textile wastewater by ozonation. Desalination
2010;260:348.
[10] Fan J, Li HB, Shuang CD, Li WT, Li AM. Dissolved organic matter removal using
magnetic anion exchange resin treatment on biological euent of textile dyeing
wastewater. J Environ Sci-China 2014;26:156774.
[11] Zheng YP, Yu SC, Shuai S, Zhou Q, Cheng QB, Liu MH, et al. Color removal and COD
reduction of biologically treated textile euent through submerged ltration using hollow ber nanoltration membrane. Desalination 2013;314:8995.
[12] Solis M, Solis A, Perez HI, Manjarrez N, Flores M. Microbial decolouration of azo
dyes: a review. Process Biochem 2012;47:172348.
[13] Blanco J, Torrades F, Moron M, Brouta-Agnesa M, Garcia-Montano J. Photo-Fenton
and sequencing batch reactor coupled to photo-Fenton processes for textile
wastewater reclamation: feasibility of reuse in dyeing processes. Chem Eng J
2014;240:46975.
[14] Chu W, Ma CW. Quantitative prediction of direct and indirect dye ozonation kinetics. Water Res 2000;34:315360.
[15] Soares OSGP, Orfao JJM, Portela D, Vieira A, Pereira MFR. Ozonation of textile efuents and dye solutions under continuous operation: inuence of operating parameters. J Hazard Mater 2006;137:166473.
[16] Colindres P, Yee-Madeira H, Reguera E. Removal of Reactive Black 5 from aqueous solution by ozone for water reuse in textile dyeing processes. Desalination
2010;258:1548.
[17] Perkowski J, Kos L, Ledakowicz S. Application of ozone in textile wastewater treatment. Ozone Sci Eng 1996;18:7385.
[18] Fu ZM, Zhang YG, Wang XJ. Textiles wastewater treatment using anoxic lter
bed and biological wriggle bed-ozone biological aerated lter. Biores Technol
2011;102:374853.
[19] He YZ, Wang XJ, Xu JL, Yan JL, Ge QL, Gu XY, et al. Application of integrated ozone
biological aerated lters and membrane ltration in water reuse of textile euents. Biores Technol 2013;133:1507.
[20] Qi LQ, Wang XJ, Xu QK. Coupling of biological methods with membrane ltration
using ozone as pre-treatment for water reuse. Desalination 2011;270:2648.
[21] Wang XJ, Chen SL, Gu XY, Wang KY, Qian YZ. Biological aerated lter treated textile washing wastewater for reuse after ozonation pre-treatment. Water Sci Technol 2008;58:91923.
[22] Lotito AM, Fratino U, Bergna G, Di Iaconi C. Integrated biological and ozone treatment of printing textile wastewater. Chem Eng J 2012;195:2619.
[23] Sevimli MF, Sarikaya HZ. Ozone treatment of textile euents and dyes: effect
of applied ozone dose, pH and dye concentration. J Chem Technol Biotechnol
2002;77:84250.
[24] Coble PG, Green SA, Blough NV, Gagosian RB. Characterization of dissolved organic-matter in the Black-Sea by uorescence spectroscopy. Nature
1990;348:4325.
[25] Ishii SKL, Boyer TH. Behavior of reoccurring PARAFAC components in uorescent
dissolved organic matter in natural and engineered systems: a critical review. Environ Sci Technol 2012;46:200617.
[26] Li WT, Xu ZX, Li AM, Wu W, Zhou Q, Wang JN. HPLC/HPSEC-FLD with multiexcitation/emission scan for EEM interpretation and dissolved organic matter
analysis. Water Res 2013;47:124656.
364
[27] Li WT, Chen SY, Xu ZX, Li Y, Shuang CD, Li AM. Characterization of dissolved organic matter in municipal wastewater using uorescence PARAFAC analysis and
chromatography multi-excitation/emission scan: a comparative study. Environ
Sci Technol 2014;48:26039.
[28] Li WT, Xu ZX, Wu Q, Li Y, Shuang CD, Li AM. Characterization of uorescentdissolved organic matter and identication of specic uorophores in textile efuents. Environ Sci Pollut Res 2015;22:41839.