Chemosphere 78 (2010) 4651

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Chemosphere
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Technical Note

Removal of Acid Orange 7 in simulated wastewater using a three-dimensional electrode reactor: Removal mechanisms and dye degradation pathway
Hua-Zhang Zhao *, Yan Sun, Li-Na Xu, Jin-Ren Ni
Department of Environmental Engineering, College of Environmental Sciences and Engineering, Peking University, The Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing 100871, PR China

a r t i c l e

i n f o

a b s t r a c t
The removal of Acid Orange 7 (AO7) in simulated wastewater was experimentally investigated using a three-dimensional electrode reactor with granular activated carbon as the particle electrode, ACF (activated carbon ber)/Fe as the anode, and ACF/Ti as the cathode. Particular attention was paid to the reaction mechanisms and the dye degradation pathway in the system. The removal of AO7 in the system was mainly dependent on the oxidation by the produced active substances (OH, etc.) and the coagulation by Fe(II) or Fe(III) dissolved from the anode. The former mechanism was predominant. A possible pathway for AO7 degradation was proposed by monitoring the temporal evolution of intermediates in the solution, with the use of some techniques including GC/MS, FTIR and HPLC. The AO7 molecule was observed to be rstly decomposed to aromatic intermediates, further degraded to ring opening products and nally mineralized to CO2, H2O and inorganic salts. The intermediates increased the biodegradability of the wastewater, which was proved by the increase of the BOD/COD value after electrolysis treatment. The threedimensional electrode method can be considered an effective alternative to dye wastewater pretreatment prior to the biological process. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 27 June 2009 Received in revised form 12 October 2009 Accepted 13 October 2009 Available online 7 November 2009 Keywords: Electrolytic treatment Three-dimensional electrode reactor Acid Orange 7 Removal mechanisms Degradation pathway

1. Introduction In recent years, the negative effect of dye wastewater on the ecological environment has brought about wide concern. Various wastewater treatment methods, such as physico-chemical (Shu et al., 1994; Wu et al., 1999) and biological methods (Coughlin et al., 2002), usually in a combination (Ghoreishi and Haghighi, 2003; Carvalho et al., 2007), are applied to treat dye wastewater to meet the discharge limits. Among these methods, electrochemical treatment is an emerging technology, and its application to dye decontamination has received increasing attention recently due to such advantages as high efciency, ease of operation and environmental compatibility (Martinez-Huitle and Brillas, 2009). As an electrochemical method, a three-dimensional electrode was characteristic of many small particles used in the reactor (Blackhur et al., 1969). Under the inuence of an electric eld with an appropriate voltage, these particles can be polarized to form charged microelectrodes, by virtue of which, the transfer distance between the reactant and the electrode can be shortened and thereby the specic surface area of the working electrode can be increased signicantly. Furthermore, the rate of the electrochemical reaction is dependent on the specic surface area of the elec* Corresponding author. Tel.: +86 10 62754292x815; fax: +86 10 62756526. E-mail address: zhaohuazhang@pku.edu.cn (H.-Z. Zhao). 0045-6535/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2009.10.034

trode (Fockedey and Van Lierde, 2002); accordingly, the threedimensional electrode method can achieve higher electrolytic efciency in comparison to the two-dimensional method. Hitherto, the technology of the three-dimensional electrode has been successfully applied to the electrosynthesis of organic compounds (Dieckmann and Langer, 1997) and the removal of metal ions (Xiong and Karlsson, 2002) or cyanide (Elghaoui et al., 1982) from solution. In recent years, several papers have proposed the application of this technology to eliminate organic pollutants including dyes from wastewater (Kong et al., 2006; Xu et al., 2008). As these papers reported, the organic compounds can be ultimately mineralized by the three-dimensional electrode method (Tennakoon et al., 1996; Polcaro et al., 2000; Xiong et al., 2003). Acid Orange 7 (AO7) or Orange II is a typical dye in which degradation has been studied by different electrochemical methods including electrocoagulation (Xiong et al., 2001; Daneshvar et al., 2003; Mollah et al., 2004), electrochemical oxidation (Chen et al., 2003; Hastie et al., 2006; Szpyrkowicz et al., 2007), electro-Fenton (Daneshvar et al., 2008; Peralta-Hernandez et al., 2008), and photoelectro-Fenton (Peralta-Hernandez et al., 2008). Electrocoagulation uses a current to dissolve Fe (or steel) or Al sacricial anodes, giving rise to coagulants that bring about charge neutralization or adsorption for dyes separation from the wastewater. High decolorization efciency (>98%) is usually achieved when the AO7 solution is treated with electrocoagulation (Daneshvar et al., 2003; Mollah

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et al., 2004). Electrochemical oxidation includes direct anodic oxidation (direct electron transfer to the anode) and indirect oxidation (chemical reaction with electrogenerated species such as OH from water discharge at the anode). AO7 could be mineralized effectively (90100% of COD decay) at some anodes with high O2 evolution overpotential (i.e. boron-doped diamond thin lm electrodes) (Hastie et al., 2006; Szpyrkowicz et al., 2007; Daneshvar et al., 2008). In an electro-Fenton process, AO7 can be oxidized with homogeneous OH formed from Fentons reaction between added catalytic Fe2+ and H2O2 electrogenerated from O2 reduction at a cathode. The photoelectro-Fenton process is an electro-Fenton process augmented by UV radiation. AO7 solution is decolorized completely in a short time in an electro-Fenton or photoelectro-Fenton process (Daneshvar et al., 2008; Peralta-Hernandez et al., 2008). The 80% of TOC removal efciency is achieved in the photoelectro-Fenton process due to more OH generated there, higher than that in the electro-Fenton process (63%) (Peralta-Hernandez et al., 2008). Some researchers have studied the degradation pathways of AO7 in the OH oxidation process. The study from Liu et al. (2005) showed that OH would mainly be added to the naphthalene nucleus in AO7 to form the corresponding hydroxyl adducts, while a hydrated electron e attacked AO7 molecules to form aq hydrazyl free radicals with the help of the H+ catalysis, and aniline compounds were formed after the azo-bond in AO7 was cleaved. Li et al. (2006) showed that a certain amount of toxic quinone substances would be accumulated after the electro-catalytic oxidation of AO7, while the photocatalytic oxidation or the electrochemically assisted photocatalytic oxidation could avoid it. The degradation mechanism and reaction pathway may also be different to some degree when the same dye molecule is treated with different methods or under different reaction conditions (Zhang et al., 2005). In a three-dimensional electrode system, stainless steel or Fecontaining material was usually used as the anode. It has not received enough attention that the application of the Fe-containing anode would inuence the efciency and the mechanism of the three-dimensional electrode system. In this system, besides direct anodic oxidation, the electrochemical degradation mechanism of organics also includes the electro-Fenton reaction caused by cathode reduction (Fockedey and Van Lierde, 2002). In previous work, we studied the feasibility of the three-dimensional electrode system with activated carbon ber (ACF) as the cathode and stainless steel as the anode in removing AO7 in solution (Xu et al., 2008). We found that more H2O2 was generated and the removal efciency of AO7 was improved in the three-dimensional electrode system with the cathode of ACF in comparison with other cathode materials, including graphite and stainless steel. We also found that the AO7 removal efciency was related, but not directly proportional, to the OH concentration in the system. The efciency of AO7 removal was also related to the dissolution of Fe2+ from the Fe-containing anode material. Therefore, the role of coagulation of the Fe species was also important for reasons other than the advanced oxidation of OH in the three-dimensional electrode system. So far, the amount of research on the removal mechanism of AO7 in the Fe-containing three-dimensional electrode system is still relatively small. In the present paper, we investigate the reaction mechanisms and degradation pathway of AO7 removal by a three-dimensional electrode reactor with ACF/Fe (ACF attached to a piece of stainless steel) as the anode and ACF/Ti (ACF attached to a titanium grid) as the cathode. The contribution of the electro-Fenton and coagulation mechanisms to the AO7 removal efciency was determined. Reaction intermediates of AO7 in the investigated system were identied in detail by HPLC, FTIR, and GCMS, and a possible degradation pathway was proposed.

2. Materials and methods 2.1. Materials ACF (Beijing Pacic Activated Carbon Products Co., Ltd., China) had a thickness of 3 mm, a surface area of 764 m2 g1, and an average pore diameter of 1.92 mm. ACF attached to a piece of stainless steel (ACF/Fe) and the one attached to a titanium grid (ACF/Ti) were adopted as the anode and cathode, respectively. Granular activated carbon (GAC, model: KC-40) with a specic surface area of 910 m2 g1 and an average pore diameter of 2.10 nm was purchased from Beijing Kecheng Guanghua Activated Carbon Co., Ltd. (Beijing, China) and used as the particle electrodes in the study. AO7 (dye content 93%) was purchased from Aldrich Chemical Company (USA) and used as received. Other chemicals used in the experiments were of analytical reagent grade if not otherwise noted. Throughout this study, deionized water was used and the initial concentration of simulative wastewater was 300 mg L1. Anhydrous sodium sulfate was added as a supporting electrolyte at a concentration of 3.0 g L1. The initial pH of the solution was adjusted to 3.0 by the addition of 1 M H2SO4 to achieve the optimal conditions for the electro-Fenton reaction (Brillas et al., 2004). 2.2. Apparatus and procedure The electrolytic treatment of AO7 was conducted in a threedimensional electrode reactor, which was an undivided, cylindrical tank with a capacity of about 1.0 dm3. The experimental setup used is the same as that in the previous work (Xu et al., 2008). Compressed air was sparged into the reactor through a microporous plate attached to the lower part of the tank. The effective surface area of both the anode and cathode was 7.0 cm 5.0 cm. The electrodes were positioned vertically and parallel to each other with an inter-electrode gap of 3.0 cm. GAC (50.0 g) was packed between the anode and cathode to form a three-dimensional electrode. Before electrolytic treatment, the GAC and ACF electrodes were exposed to 10 cycles of a batch experiment to preclude dye removal due to its adsorption on the GAC and ACF (Xiong et al., 2001; Xu et al., 2008). The batch experiment was carried out under the same experimental conditions as the electrolytic degradation and each cycle lasted for 60 min. Firstly, a total of 500 mL of simulated wastewater was fed into the reactor. The system was timed to start when the d.c. power with a constant voltage of 20 V and compressed air supply with a ow rate of 3.0 L min1 were both switched on. During the process, liquid samples were withdrawn from the reactor at regular intervals, and then centrifuged at 10 000 rpm on a TGL-16C centrifuge (Shanghai Anting Scientic Instrument Co., Ltd., China) for 10 min before further analysis. To study the effect of the coagulation of Fe dissolved from the ACF/Fe anode on the dye removal efciency, a sample was drawn from the solution after electrolysis for 60 min, and divided into two parts: one was centrifuged, ltered and then its TOC was measured; a certain amount of H2SO4 solution was added to the second part, until the occules were completely dissolved or disappeared. The TOC was then measured and calculated (based on the dilution with H2SO4 solution). The TOC removed by coagulation can be characterized by the difference between the two TOC values mentioned above. 2.3. Analytical methods The total organic carbon (TOC), chemical oxygen demand (COD), biochemical oxygen demand (BOD) and pH of the samples were determined on a Multi N/C 3000 TOC apparatus (Analytik Jena

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AG, Germany), a COD analyzer (Hach, USA), the respirometric method (OxiTop IS6, Germany) and a pH-201 meter (Hanna, Italy), respectively. Quantitative analysis of AO7 and its degradation products was carried out on a high performance liquid chromatography (HPLC) system. An Agilent 1100 LC was equipped with an Agilent Zorbax SB-C18 column (150 4.6 mm, particle size 5 lm) and a VWD detector set at 254 nm. The mobile phase of methanol/water ranged from 0/100 to 100/0 in 30 min with a ow rate of 0.8 mL min1. The identication of AO7 and sulfanilic acid (SA) was achieved using an external standard method, and the retention time of AO7 and SA was 16.2 and 2.47 min, respectively. Gas chromatography/mass spectrometry (GC/MS) and Fourier transform infrared (FTIR) were also performed to identify the fate of AO7 wastewater in the three-dimensional electrode system. Prior to GC/MS determination, a 300 mL sample was extracted using 10 mL of CH2Cl2 (chromatogram pure grade, Fisher, USA) three times at acidic, neutral and alkaline conditions, respectively. The three extract layers were mixed, dehydrated with anhydrous sodium sulfate and dried under nitrogen. The residue was dissolved in 1.0 mL of CH2Cl2 and 1 lL was injected into a 6890 N/ 5973 GC/MS system (Agilent, USA) for analysis. A DB-5MS capillary column with an inner diameter of 0.250 mm and a length of 30 m was adopted in the separation system. The GC column was operated in a temperature programmed mode by maintaining the temperature at 40 C for 5 min, then increasing to 290 C with an increment of 3 C min1 and nally holding at 290 C for 10 min. Electron impact (EI) mode at 70 eV was used and the mass range scanned was 0550 m/z. The substance analysis was undertaken with reference to the NIST02 mass spectral library database. FTIR of the solution was recorded on a Vector22 FTIR spectrometer (Bruker, German). Before analysis, the samples were vacuum freeze-dried to a constant weight, then grounded with KBr powder and nally pressed at 40 MPa to form a uniform disk.

the macromolecular hydrophobic substances from water (Yang et al., 2004). Although the coagulation has a considerable contribution to the AO7 removal, the oxidation is the main mechanism for AO7 removal in the three-dimensional electrode system. 3.2. Analysis of degradation products 3.2.1. HPLC analysis When AO7 degradation occurs, aromatic amines such as sulfanilic acid (SA) and 1-amino-2-naphthol (1-amn-2-naph) may be released initially (Davies et al., 2006; Liu et al., 2007). However, 1-amn-2-naph is very unstable and may induce auto-oxidation when exposed to air. Therefore, among these aforementioned three compounds, only AO7 and SA can be detected by employing the HPLC method. The temporal change of AO7 and SA concentration is given in Fig. 1. Comparing the two curves in this gure, it is evident that there was a distinct difference in the temporal change of AO7 and SA. During the treatment process, AO7 suffered continuous degradation and its concentration decayed with electrolysis time. It was reduced rapidly from 300 mg L1 to 23.6 mg L1 within 20 min and then slowly declined to 0.4 mg L1 after 90 min of treatment, with a removal efciency of almost 100%. As for SA, its concentration reached a maximum of 23.0 mg L1 after 20 min of electrolysis and then was reduced gradually, from which it may be concluded that at this stage of experiment, the velocity of SA generation was much lower than its degradation in the electrolytic system and adsorption on the electrode surface (Davies et al., 2006). 3.2.2. FTIR spectra analysis Fig. 2 illustrates the FTIR spectra of AO7 solution before and after 60 min of electrolysis in the three-dimensional electrode system. Several bands can be distinguished in the spectra of initial AO7 wastewater. The vibrations located at 1617 cm1 (a combination of phenyl ring vibrations with stretching of the C@N group), 1512 cm1 (N@N bond vibrations or aromatic ring vibrations sensitive to the interaction with the azo-bond, or the bending vibration mode d(NH) of the azo dye), 1403 cm1 (OH bending vibrations), and 1172 cm1 (symmetric vibrations of the sulfonate groups) represented the characteristic adsorption of AO7 in the infrared band (Stylidi et al., 2003). After 60 min of electrolysis, the FTIR spectrum was obviously modied with respect to the aforementioned spectrum of the initial wastewater. It can be observed that the bands at 1512 and 1617 cm1, which were associated with the azo-chromophore, almost disappeared after 60 min

3. Results and discussion 3.1. AO7 removal mechanism In the present three-dimensional electrode system, the AO7 removal efciency is attributed to the combination of oxidation and coagulation. The contributions of oxidation and coagulation to the treatment efciency of AO7 were identied, respectively. After electrolysis for 60 min in the three-dimensional electrode system, the remaining TOC was 36.9 mg L1, accounting for 39.6% of the initial TOC; 19.3 mg L1 of TOC can be removed through coagulation, accounting for 20.7% of the initial TOC; the other 39.7% of TOC might be degraded by the oxidation. The oxidation is mainly due to the direct electro-oxidation at the ACF/Fe anode and the polarized GAC anodes and the indirect oxidation caused by H2O2, OH and other active substances produced in the electro-Fenton process (Fockedey and Van Lierde, 2002; Brillas et al., 2004). The indirect oxidation is more important than the direct oxidation in the electrochemical oxidation process. Structures with a high density of electronic cloud in the molecular pollutants (such as aromatic compounds) are attacked easily by OH, and then the intermediates prone to further oxidation are formed, or the ring structure is directly opened and degraded, and nally they are mineralized to CO2 and H2O (Zhang et al., 2005). It can be found from the above-mentioned results that the coagulation caused by Fe(II) and Fe(III) in the system also makes a large contribution to the treatment efciency. These Fe(II) and Fe(III) species in solution can be transformed into hydroxy complexes with a high adsorption ability, such as Fe(OH)2, Fe(OH)3, nFe(OH)2mFe (OH)3, and so on, which can coagulate and remove

350

25

AO7 concentration (mg L )

210 140 70 0 0 40 80 120 160

15 10 5 0 200

Time (min)
Fig. 1. Concentration of AO7 and SA detected by HPLC vs. electrolysis time.

SA concentration (mg L )

-1

280

20

-1

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0 min 60 min
1110 1500 2000 2500
-1

3000

Wavelength (cm )
Fig. 2. FTIR spectra of AO7 solution before (0 min) and after treatment (60 min) in the three-dimensional electrode system.

of treatment. This phenomenon showed the disappearance of the chromophore of AO7, which is in accordance with the results shown in Fig. 1. The strong absorption at 1617 and 1403 cm1 becomes very weak or even disappeared, also indicating the degradation of AO7 molecules in the electrolytic process. Furthermore, a new absorption peak of 1640 cm1 was observed, which can be assigned as the stretching of C@O in carboxylic groups, aldehydes or ketones (Bauer et al., 2001; Zhang et al., 2005; Li et al., 2006) generated in the process. The presence of this band indicated the formation of new species, which originated from the fragmentation of the parent AO7 molecule (Stylidi et al., 2004).

3.2.3. GC/MS analysis A GC/MS analysis was performed to further identify the intermediate products formed in the liquid phase during the electrochemical treatment process in the three-dimensional electrode reactor. The reaction intermediates of AO7 identied by GC/MS are presented in Table 1. It can be seen that after 30 min of electrolysis, ve naphthalene-type compounds, including 1,2-naphthalenediol (1), 2-naphthalenol (2), 1,2-naphthalenedione (3), 2H-1benzopyran-2-one (4) and 2-hydroxy-1,4-naphthalenedione (5), and three heterocyclic compounds such as ninhydrin (6), 1(3H)isobenzofuranone (7) and 1H-isoindole-1,3(2H)-dione (8) were detected by GC/MS. In addition, one aromatic compound such as 2hydroxybenzaldehyde (9) was also detected, which might be a degradation product of the partial oxidation of the aforementioned naphthalene-type and heterocyclic compounds. During the treatment process, some new organic compounds, including phthalic anhydride (10), p-benzoquinone (11), 2-formylbenzoic acid (12) and salicylic acid (13), 2-(1-oxopropyl)-benzoic acid (14), were produced after 60 min and 120 min of electrolysis, respectively. Finally, after 180 min of treatment, only three organic acids were newly generated in the system, which included hexanoic acid (15), enanthic acid (16) and hexylacetic acid (17). Comparison of these reaction intermediates given in the table suggested that an increase of the treatment time was accompanied by the simplication of the molecular structures in the system. 3.3. AO7 degradation pathway Based on the degradation products identied by the HPLC and GC/MS methods, a possible pathway for AO7 degradation in the three-dimensional electrode system is proposed in Fig. 3. Decomposition of AO7 was rstly initiated by the cleavage of N@N, with the hydrazo derivative, namely SA, and 1-amn-2-naph as possible intermediates. The sulfonic group in the SA molecule renders it thermally stable and highly soluble in water, whereas 1-amn-2naph is oxygen sensitive and may be decomposed under aerobic conditions (Kudlich et al., 1999). Therefore, neither of these two intermediates was detectable in the GC/MS analysis. Afterwards, SA underwent further desulfonation, resulting in the formation of p-benzoquinone (11) that was further oxidized to organic acids and then completely mineralized as many literatures pointed out (Canizares et al., 2004; Li et al., 2005; Liu et al., 2009). The 1amn-2-naph was oxidized to some naphthalene-type compounds, such as 1,2-naphthalenediol (1) and 2-naphthalenol (2), as shown in Table 1. The formation of these naphthalene-type products has also been corroborated in several previous studies concerning AO7 degradation (Stylidi et al., 2003; Velegraki et al., 2006). The phenolic hydroxy group contained in (1) and (2) was subsequently oxidized to a quinine radical, resulting in the formation of the oxidized products denoted as 1,2-naphthalenedione (3), 2H-1-benzopyran-2-one (4) and 2-hydroxy-1,4-naphthalenedione (5). The above organic compounds were further degraded to generate heterocyclic compounds containing a six- and a ve-atom ring, via a series of complicated degradation reactions that cannot be identied in detail (Li et al., 2006). These compounds later underwent deep degradation to form benzene-type intermediates, the further oxidation of which resulted in aromatic ring cleavage and generation of aliphatic acids, such as hexanoic acid (15), enanthic acid (16) and hexylacetic acid (17). Finally, these organic acids were decomposed to CO2 to accomplish the entire mineralization process. Overall, the electrolysis decomposition of AO7 in the threedimensional electrode system can be described by a series of consecutive degradation steps. AO7 was rstly decomposed to aromatic intermediates, further oxidized to ring opening products and nally mineralized to CO2, H2O and inorganic salts.

Table 1 Identied reaction intermediates of AO7 by GCMS.

Electrolysis Time (min) Identified reaction intermediates

Absorbance

(1)
1,2-naphthalenediol

(2)
2-naphthalenol

(3)
1,2-naphthalenedione

(4)
2H-1-benzopyran-2-one

(5)
2-hydroxy-1,4-naphthalenedione

(6)
ninhydrin

30 (7)
1(3H)-isobenzofuranone

(8)
1H-isoindole-1,3(2H)-dione

(9)
2-hydroxybenzaldehyde

(10)
phthalic anhydride

(11)
p-benzoquinone

(12)
2-formylbenzoic acid

60

(13)
salicylic acid

(14)
2-(1-oxopropyl)-benzoic acid

120 (15)
hexanoic acid

(16)
enanthic acid

180

(17)
hexylacetic acid

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AO7

N=N cleavage

sulfanilic acid (SA)

1-amino-2-naphtol

(11)

(1) (2)

(3)

(4) (5)

(7) (10)

(6) (8)

(13) (9)

(14) (12)

(15), (16), (17)

Fig. 3. A possible pathway for the degradation of AO7 in the three-dimensional electrode system (the identifying numbers of the compounds are the same as those in Table 1).

3.4. Biodegradability analysis The results of BOD measurements as a function of electrolysis time are illustrated in Fig. 4. As can be seen, the BOD values of AO7 can be enhanced from 5.0 to 35.0 mg L1 after the initial 30 min electrolytic treatment, and then reduced to 30.0 mg L1 after 90 min. This phenomenon might be due to two different mechanisms for the electrochemical method during the treatment process, namely electrochemical conversion and electrochemical combustion. The former refers to the fact that non-biocompatible organics are transformed to biocompatible organics such as aliphatic acids (Table 1) for further biological treatment, while the latter indicates that organics are ultimately oxidized to CO2 to achieve complete mineralization (Comninellis, 1994). In the initial 30 min, the conversion played a more important role than the combustion and induced the distinct increase of BOD values accordingly. Nevertheless, an opposite effect was observed after 90 min and the predominance of combustion over conversion resulted in the subsequent reduction of the BOD value. Besides the BOD value, the biochemical to chemical oxygen demand ratio (BOD/COD) is also shown in Fig. 4. The BOD/COD for initial AO7 wastewater of only 1.7% indicated that AO7 was not

amenable to biological treatment. The BOD/COD rose with the increase of electrolysis time and reached 49.9% after 180 min of electrolysis. Therefore, considering the direct ratio relationship

50

BOD BOD/COD

50 40

40

30

30 20 10 0

20

10

30

Time (min)

60

90

120

180

Fig. 4. Temporal change of BOD and BOD/COD.

BOD/COD (%)

BOD (mg L )

-1

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between the biodegradability of wastewater and its BOD/COD, the results suggest that the three-dimensional electrode system can be considered an effective alternative to AO7 wastewater pretreatment prior to the biological process.

4. Conclusions A three-dimensional electrode system using ACF material as the anode and cathode was applied to the removal of AO7 in simulated wastewater. The removal of AO7 in the three-dimensional electrode system was mainly dependent on the oxidation by active substances (OH, etc.) and the coagulation by Fe(II) or Fe(III) dissolved from the anode. The former mechanism was predominant. In the oxidation process, decomposition of AO7 was proposed to be rstly initiated by the cleavage of N@N, which resulted in decolorization of the solution. Afterwards, the reaction intermediates underwent a series of successive degradation steps, leading to the formation of naphthalene- and benzene-type compounds and then to aliphatic acids resulting from the aromatic ring cleavage. Finally, these organic acids were decomposed to CO2 to accomplish an entire mineralization process. The aromatic ring cleavage and the aliphatic acid production increased the biodegradability of the wastewater, which was proven by the increase of the BOD/ COD value after electrolysis treatment. The three-dimensional electrode method can be regarded as an effective alternative to AO7 wastewater pretreatment. Acknowledgement The authors are grateful for the nancial support from the National Natural Science Foundation (Grant No. 20607001). References
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