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Accepted Manuscript

Advanced Oxidation Processes for In-situ production of Hydrogen peroxide/Hydroxyl


radical for Textile Wastewater Treatment: A Review

Anam Asghar, Abdul Aziz Abdul Raman, Wan Mohd Ashri Wan Daud

PII: S0959-6526(14)00940-8
DOI: 10.1016/j.jclepro.2014.09.010
Reference: JCLP 4695

To appear in: Journal of Cleaner Production

Received Date: 31 May 2014


Revised Date: 23 August 2014
Accepted Date: 5 September 2014

Please cite this article as: Asghar A, Abdul Raman AA, Daud WMAW, Advanced Oxidation Processes
for In-situ production of Hydrogen peroxide/Hydroxyl radical for Textile Wastewater Treatment: A
Review, Journal of Cleaner Production (2014), doi: 10.1016/j.jclepro.2014.09.010.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT

1 Advanced Oxidation Processes for In-situ production of Hydrogen

2 peroxide/Hydroxyl radical for Textile Wastewater Treatment: A Review

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3 Anam Asghar, Abdul Aziz Abdul Raman, Wan Mohd Ashri Wan Daud

Chemical Engineering Department, Faculty of Engineering, University Malaya, 50603

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5 Kuala Lumpur, Malaysia
6 Corresponding author: Tel.: +60 3 79674615; fax; +60 3 79675319

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7 Email address: [email protected]

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1 Abstract

2 Fenton Process, a type of Advanced Oxidation Processes is an efficient method for treating

3 textile wastewaters. However, excessive use of hydrogen peroxide and catalyst has made this

4 process economically non-feasible. Besides, industrial grade hydrogen peroxide costs $390–500

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5 per ton. One of the means to overcome this problem is the in-situ production of hydrogen

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6 peroxide. In this paper, a detailed review was conducted on the generation methods, degradation

7 potential and optimum operating parameters for in-situ production of hydrogen

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8 peroxide/hydroxyl radicals. Additionally the scavenging aspect for hydroxyl radicals was also

9 investigated. From this review, it can be concluded that hydroxyl radical is highly oxidative and

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non selective in nature and its in-situ production can be performed through application of
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11 catalyst, ozonation, photocatalysis, electro and microbial fuel cells. Furthermore, optimization of
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12 operating parameters can result in an increase in the yield of hydroxyl radicals/hydrogen

13 peroxide. Sonolysis as an auxiliary tool have potential to induce synergetic effects in


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14 combination with Advanced Oxidation Processes to increase in-situ hydrogen peroxide


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15 production. However, the problem of the scavenging effect is an aspect that needs to be dealt

16 with, as hydroxyl radicals are prone to deactivation by scavengers. Therefore based on the
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17 review, it is concluded that in-situ production of hydrogen peroxide/hydroxyl radical for treating

18 textile wastewater is economically viable and practically feasible if careful selection of process is
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19 conducted through selective research.


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20 Keywords

21 Hydrogen peroxide, Hydroxyl radicals, Fenton process, Textile wastewater, Advanced Oxidation

22 Process, Sonolysis

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1 Graphical Abstract

3 • AOPs/US

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• Synergetic effect
4 • Increase H2O2/HO•
H2 production

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substituted
5 Organic
Iron

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6 O2/pH=7 catalyzed
Process
Ozonation O3/pH=11

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7 MNs/Fe0/FeS2/
H2O2/HO• O2
production
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8 UV
O2/pH=3

Electro-
9 O2/pH=3
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chemical (cathode);
Photo-
oxidation pH=7(anode) catalysis
10 Cl‾
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Microbial HCO3‾/
Fuel cells CO32‾/ SO4-2/
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OH/ Cl‾/Br‾ SO4-2
Consumption
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HO•
13 Power Scavengers Holes
Scavengers
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AOPs for in-situ H2O2/HO• production


15 for textile wastewater treatment

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1 1. Introduction

2 Textile industry consumes immense amounts of process water and chemicals. Approximately

3 21-377m3 of water is consumed for one ton of textile product (Sahunin et al., 2006) and chemical

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4 consumption normally varies from 10% to over 100% of the weight of the cloth (Ozturk et al.,

5 2009). Estimates indicate that approximately, 7×105 tons of dyestuffs are produced annually and

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6 280,000 tons of the textile dyes are discharged into water sinks through textile effluents (Eren,

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7 2012; Jin et al., 2007). That, explains why textile effluent is characterized by high COD (150-

8 10,000mgL), BOD (100-4,000 mg/L), pH (6-10) and color content (50-2500) (Kalra et al., 2011).

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9 Moreover, discharge of even a small quantity (ca.1 mg/L) of dye is not acceptable and may
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10 produce toxic compounds at the end of treatment process (Ghodbane and Hamdaoui, 2009).

11 Since dyes are designed to resist degradation, these are chemically stable, non-biodegradable
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12 and exist as substances that possess toxic and carcinogenic characteristics (Turhan et al., 2012).
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13 Therefore, a proper treatment strategy is required to meet the pollution control requirements.
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14 Majority of the conventional treatment methods comprise of adsorption (Yeh et al., 2002),

15 coagulation (Alinsafi et al., 2005), filtration (Métivier‐Pignon et al., 2003) and biological
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16 treatment (Paprowicz and Słodczyk, 1988). These methods are less efficient because dyes are

17 stable against biological degradation (Wu et al., 2008), which results in sludge formation,
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18 membrane fouling and incomplete mineralization (Yeh et al., 2002; Alinsafi et al., 2005; Liu et
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19 al., 2007).

20 Advanced Oxidation Processes (AOPs) comprise a series of methods including ozonation,

21 photocatalysis, electrochemical oxidation, Fenton and Fenton-like processes. Although these

22 processes use different reacting systems, all are characterized by similar chemical feature of

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1 utilizing highly reactive oxidizing agent such as hydroxyl radical (HO•) with redox potential of

2 2.80eV (Krishnakumar and Swaminathan, 2011). However, the process that has gained attention

3 is Fenton process because of rapid formation of HO• radicals in acidic medium according to the

4 following chemical reaction:

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5 Fe+2 + H2O2 → Fe+3 + HO• + HO‾ (1)

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6 Technical feasibility study of Fenton oxidation together with other AOPs has been discussed

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7 in detail (Chong et al., 2012). Nevertheless, there are various factors that hinders the efficacy of

8 the process such as reaction parameters (Tosik, 2005), types of salt used (Ledakowicz et al.,

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2000), high cost of hydrogen peroxide (H2O2) and excess consumption of chemicals exclusively
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10 H2O2 (Hassan et al., 2012). Additionally, hazards associated with the transport, handling and
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11 storage of bulk quantities of H2O2 have made the process unsafe and economically challenging

12 (Sheriff et al., 2007). It was also evident from the study conducted by Meric et al (2004) in
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13 which the authors reported that 400mg/L H2O2 and 100mg/L iron salt were consumed for
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14 degrading 100mg/L of synthetic dye. Similarly, Argun and Karastas (2011) used 2000mg/L of

15 H2O2 for degrading 200mg/L of synthetic dye. High consumption of H2O2 is not economically
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16 viable and it intensifies the need to find some cost effective and technically feasible alternatives

17 for textile wastewater treatment.


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18 One such option is in-situ production of H2O2/HO• or some other oxidants with redox

19 potential comparable to HO•. In this context, several research groups have reported in-situ

20 production of H2O2/HO• (Tosik, 2005; Yang et al., 2010) and some other oxidants such as sulfate

21 radicals (SO4•‾), permanganate (MnO4‾), hypochlorite (ClO‾), chlorine dioxide (ClO2) and ozone

22 (O3) for textile wastewater treatment (Anipsitakis and Dionysiou, 2003; Xu et al., 2005; Méndez-

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1 Díaz et al., 2009; Turhan et al., 2012). Out of all these oxidants, in-situ production of H2O2/HO•

2 has received much attention because of its high redox potential and non-selective nature for most

3 of the organic contaminants (Neyens and Baeyens, 2003). The redox potential of few oxidizing

4 agents is provided in Table 1. Possible methods that are available in literature for in-situ

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5 production of H2O2/HO• include AOPs such as ozonation, photocatalysis, electrochemical

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6 oxidation and microbial fuel cells. Therefore, this review aims at discussing literature relevant to

7 in-situ H2O2/HO• production by AOPs. However, there are some economical, technological and

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8 operational issues with commercial production of H2O2 that must be considered before going

9 into the detail of in-situ production of H2O2/HO•.

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10 1.1.Challenges with Commercially Available H2O2

Hydroxyl radical (HO•) is unstable in nature that is why for wastewater treatment
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12 applications commercially available H2O2 is used as a source of HO• production. It is one of the
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13 cleanest and ideal oxidants for the degradation of dyes and organic contaminants present in
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14 wastewater (Sheriff et al., 2007). Globally, demand for H2O2 has increased. According to the

15 statistical report published by ICON Group, H2O2 with the total worth of US$ 383,067 (Parker,
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16 2004) was exported in 2005 which was increased by 37% in 2011(Parker, 2010). This group

17 also discussed the breakdown of market in context of its supply and consumption in different
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18 regions of the world as shown in Fig.1.


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19 Besides increase in demand, the cost of commercially available H2O2 is also high. Industrial

20 grade H2O2 costs $390-500 per ton (Zhu and Logan, 2013a). Commercially, H2O2 is produced by

21 the oxidation of anthrahydroquinone as shown in Fig. 2. Successive developments in this

22 technology have reduced the cost of chemicals by replacing conventional Raney-Ni by highly

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1 selective and highly active Pd/Al2O3 (Chen, 2006). However, energy requirement of the process

2 is still higher. This is because, for trade purposes, the product formed must be concentrated up to

3 70% (Campos-Martin et al., 2006) which makes the process energy intensive and increase the

4 cost of the product

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5 Fig. 1. World supplies of Exported Hydrogen Peroxide (2005)

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6 Fig. 2. Conventional method for H2O2 production (Campos-Martin et al., 2006)

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7 Direct method is another option where direct contact of hydrogen and oxygen over the

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8 surface of catalyst leads to the formation of H2O2. It is a simple process as oxygen and hydrogen
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9 are naturally available. But there are several problems that must be dealt with such as side

10 reactions, decomposition of H2O2 over the surface of catalyst (Campos-Martin et al., 2006) and
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11 formation of explosive mixture from hydrogen and oxygen (Voloshin et al., 2007). Possible ways

12 to overcome these limiting issues have also been proposed but their practical applications have
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13 not been realized (Voloshin et al., 2007; Lunsford, 2003).


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14 Several authors have also studied the potential of other oxidizing agents such as SO4• ‾, O3,
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15 MnO4‾ etc based on their redox potential as given in Table 1. It is observed that most of the

16 oxidizing agents have redox potential comparable to the H2O2 and HO•. Thus it is possible to use
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17 these oxidants for textile wastewater treatment. In order to confirm it, Co+2/PMS system as a
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18 source of SO4• ‾ free radical was investigated for the degradation of Acid Red 88 (AR88) dye. In

19 this study, it was found that SO4• ‾ widens the pH range of the system but its selective nature for

20 most of the oxidizing agents limit its application. Moreover, oxone which is used as a source of

21 SO4• ‾ is two times as costly as H2O2 (Anipsitakis and Dionysiou, 2003; Madhavan et al., 2009).

22 Xu et al (2005) examined decolorization efficiency of ten different dyes by utilizing KMnO4 and

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1 found that MnO4‾ was efficient for decolorization and could be used as pre-treatment step for

2 biological processes. However, concentration of MnO4‾ and pH is important to control for

3 achieving high decolorization efficiencies. In another study, Mendez-Diaz et al (2009) collated

4 the performance of conventional oxidizing agents (ClO‾, ClO2, KMnO4), O3, O3/H2O2,

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5 O3/activated carbon for the removal of sodium dodecylbenzenesulphonate (SDBS) and achieved

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6 80% SDBS removal within 30 minutes with O3/PAC while others showed insignificant results.

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Table 1. Redox potential of oxidizing agents

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8 It is suggested that conventional oxidizing agents are more suitable to perform decolorization
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9 than mineralization (Xu et al., 2005). Limited works have been conducted on conventional

10 oxidizing agents in this decade. Although, SO4• ‾ has redox potential comparable to HO• (Table
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11 1), its selective nature for organic contaminants hinders its practical application. Therefore, it is

concluded that HO• is the most suitable option for textile or any other wastewater treatment.
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13 Therefore, this study was attempted to review and conclude all aspects of literature that
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14 determine the feasibility of in-situ production of H2O2/HO• for textile wastewater treatment by
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15 using common AOPs.

16 2. In-situ Production of Hydrogen Peroxide/Hydroxyl radical from AOPs


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17 In-situ production of H2O2/HO• means its production at the time of treatment. From

18 literature, possible methods that can be employed are AOPs comprising of iron catalyzed

19 reaction, ozonation, photocatalysis, electrochemical or microbial fuel cells. Thus, this review is

20 attempted to summarize AOPs studies that only focus on in-situ H2O2/HO• production.

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1 2.1. Hydrogen substituted organic compounds as a source of H2O2

2 The concept of hydrogen substituted organic compound for in-situ H2O2 production has been

3 suggested to overcome the shortcomings of direct method such as formation of explosive

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4 mixture of hydrogen and oxygen (Voloshin et al., 2007). Choudhary and Jana (2007) employed

5 hydroxylamine as a source of hydrogen to react with oxygen to form H2O2 over Pd/Al2O3

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6 catalyst [Eq. 2-3].

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7 2NH2OH + O2 →N2 + 2H2O + H2O2 (2)

8 2NH2OH + 2O2 → N2 + 3H2O2 (3)

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9 This process was characterized by high reaction rates at neutral pH. However, net formation

10 of H2O2 was decreased with increase in reaction time because of the decomposition of H2O2 over
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11 the surface of catalyst (Choudhary and Jana, 2007). However, Br‾ or Cl‾ ions can possibly be

12 used as inhibitors to suppress the decomposition of H2O2. But excess concentrations of Cl‾ ions
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13 act as scavengers for HO• formed within the system (Ledakowicz et al., 2000). Park et al (2000)
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14 discussed novel idea of catalyst loaded with organic compound for in-situ H2O2 production. They

15 reported 1.5 times higher activity of zeolite beta supported Pd adsorbed with hydroquinone
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16 compared to zeolite beta supported with Pd alone.


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17 Yalfani et al (2011) compared the performance of hydrazine, formic acid and hydroxylamine
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18 as hydrogen substitutes for H2O2 production. Among all, formic acid was observed to be the least

19 efficient for H2O2 production. However, efficacy of the process was improved when H2O2

20 produced was utilized at the same time. Moreover, hydrazine was found to be dependent on

21 acidic conditions which cause the corrosion of catalyst. Furthermore, its decomposition over

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1 catalyst surface resulted in rapid formation of H2O2 which in turn decomposed rapidly rather

2 than participating in oxidation process (Yalfani, Contreras et al., 2011).

3 Since this method has been successfully applied for the treatment of organic contaminants; it

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4 can possibly be used for textile wastewater. Although, it can overcome the limitations

5 encountered in direct method, incomplete conversion of organic compound may increase the

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6 toxicity of the treated textile wastewater. Also, there may be the reaction between organic

compound and in-situ HO• (conversion of in-situ H2O2 to HO• in the presence of Fe+2) which

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8 lowers the process efficiency (Choudhary and Jana, 2007). Thus, it is suggested to use this

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9 process if organic compound (source of H2O2) is already present in the textile wastewater.
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10 2.2. Iron Catalyzed H2O2 Production

11 Among transition metals, iron is known as a suitable catalyst for generation of HO• radicals
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12 through Fenton process (Anipsitakis and Dionysiou, 2004). Its role in in-situ production of
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13 H2O2/HO• was explored in the last decade.


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14 Borda et al (2003) explored the catalytic ability of iron pyrite to produce HO• radical.

According to the study, water adsorbed on the catalyst surface dissociates on sulfur deficient
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16 sites and forms HO• radical in oxygen free medium. Later, in 2012, Wang et al (2012) extended
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17 the idea of Borda and his co-workers for in-situ production of HO• radicals. The report suggested
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18 that in the presence of oxygen, pyrite was thermodynamically unstable and either dissolved

19 oxygen or Fe+2 ions was available in suspension for the production of oxidizing agents as shown

20 in Fig. 3. Moreover, Fe+2 ions formed Fenton reagent system with H2O2 for degradation of

21 organic contaminants (Wang et al., 2012). In both studies, it was found that production of sulfate

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1 ions SO4‾2 is an inevitable phenomenon and it may affect the yield of HO• radicals by

2 scavenging process (Liu et al., 2012).

3 Fig. 3. In-situ production of H2O2/ HO• by iron pyrite (Wang et al., 2012)

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4 Fang et al (2013) exploited the reductive property of magnetic nano-particles for

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5 transformation of oxygen into H2O2. Here, transformation of oxygen into H2O2 takes place in

6 two consecutive single electron transfers steps from MNPs sorbed Fe+2 with subsequent

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7 protonation with H+. Then H2O2 reacts with dissolved Fe+2 in bulk medium to produce HO•

8 radical through Fenton reaction. From reaction mechanism, it was observed that pH has a

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profound effect on the type of oxidizing species available in reaction medium. As shown in Fig.
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10 4, superoxide radical (O2• ‾) is dominant at alkaline pH while HO• is dominant at acidic
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11 condition.

12 Although the application of above mentioned processes have not yet been investigated for
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13 textile wastewater treatment, comparison of these techniques with conventional Fenton oxidation
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14 processes portrays the feasibility of these methods for textile wastewater treatment.
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15 Fig. 4. Reaction pathways for in-situ production of HO•/H2O2 utilizing MNPs

16 (Fang et al., 2013)


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17 Besides, zero valent iron (Fe0) has potential for in-situ generation of H2O2. Degradation

18 phenomenon by Fe0 is attributed to the direct transfer of electron from metal surface to the dye or

19 organic contaminant prior to in-situ production of H2O2, (Cao et al., 1999). This degradation step

20 takes place via oxidizing agents such as H2O2 and other oxidative species depending on pH in

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1 oxic condition which in turn produce HO• radical for decolorization of dyes through Fenton

2 process [Eq. 4, 1 & 5] (Yang et al.,2010).

3 Fe0 + O2 + 2H+ →H2O2 + Fe+2 (4)

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4 Fe+3+ Fe0→ Fe+2 (5)

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5 Wang et al (2010) reported that under oxic conditions, high COD removal was obtained

6 because of the combined effect of oxidation and adsorption of dyes on iron hydroxides,

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7 generated from Fe0 oxidation. From above mentioned reaction equations, it can be inferred that

8 the efficacy of Fe0 depends on the transfer of electron from the iron surface to the targeted

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contaminants. Lee et al (2007) investigated the oxidation of Fe0 accelerated by peroxometalate
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10 (POM) as electron shuttle to improve the catalytic performance of the Fe0. POM is not suitable

11 for the degradation of dyes waste; however quinone intermediates can possibly be used to
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12 accelerate the transfer of electrons.


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13 Among aforementioned alternatives, iron catalyzed production of in-situ H2O2/HO• is a


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14 viable option for textile wastewater treatment. Moreover, it has some advantages over hydrogen

15 substituted organic compound as there may be incomplete conversion of organic compound in


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16 later option, no matter produced H2O2 is utilized in-situ or ex-situ. Furthermore, iron catalyzed
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17 in-situ production of H2O2/HO• is also cost effective because single catalyst can be used for
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18 oxidant production as well as for degradation of dyes in textile wastewater. As evident from one

19 study, the operating cost for Remazol Brilliant blue R (RBBR) degradation by Fe0/air reduced

20 from 0.015US$/g of dye (Fenton process) to 0.00113 US$/g of dye(Chang et al. 2009).

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1 2.3. Ozonation for in-situ H2O2/HO• production

2 Ozonation is an environmentally sound technique because of no sludge formation; potential to

3 perform decolorization and degradation in a single step; decomposition of residual ozone into

4 water and oxygen; less space requirement for equipment installation; less hazardous as no stock

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5 of H2O2 is required for the oxidation step and ease of operation (Chu and Ma, 2000; Oguz et al.,

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6 2005). Therefore, it is recommended to consider it an efficient option for in-situ production of

7 H2O2/ HO• for dye degradation.

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8 Ozonation is suitable for complete decolorization rather than mineralization (Tosik, 2005).

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9 Ozonation process follows two different routes for degradation of textile dyes based on pH
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10 value. Under acidic conditions, ozone selectively attacks the aromatic and conjugated double

11 bonds of chromophores in dye structures (Turhan et al., 2012) and leads to the formation of
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12 aldehydes, carboxylic acids and other by-products (Nawrocki and Kasprzyk-Hordern, 2010).
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13 However, at high pH values, ozonation mechanism changes from direct ozonation to


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14 complex chain mechanism. As a result, HO•, HO2• and HO4• radicals are formed (Glaze, Kang

15 and Chapin, 1987). Among these, HO• is dominant and it has a potential to open aromatic rings
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16 of dye present in textile wastewater (Chu and Ma, 2000). It was also explained by the findings of

17 Turhan et al (2012) that the reported COD removal of direct dyestuff in wastewater at pH 6.5
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18 was 23.33% after 2 hrs of ozone bubbling which increased to 64.96% when pH value increased
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19 to 12.

20 Moreover, pH also effects the time required for complete decolorization. For example, time

21 required for decolorizing direct dye stuff reduced to 59.62% when pH increased from 2 to 12

22 (Turhan et al., 2012). In another experimental study by Muthukumar et al (2004), it was reported

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1 that the time required for complete decolorization of Acid Red 88 (AR88) by ozonation

2 increased till pH 7 and then decreased which clearly indicates the decomposition of O3 into HO•.

3 The COD value obtained as a result of regression analysis at alkaline pH was 64% according to

4 the study done by Muthukumar et al (2004).

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5 From this review, it can therefore be concluded that pH is the key parameter for accelerating

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6 in-situ production of HO•. Few investigations have discussed analogous results. For example, De

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7 Souza et al (2010) and Tehrani-Bagha et al (2010) reported slight change in dye degradation

8 efficiencies at high pH values as compared to acidic conditions. They supported this result by

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9 argumenting that it was buffered or non-buffered solution that played a role in promoting in-situ
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10 HO• production at high pH values. They explained that in non-buffered solution, pH value

11 decreased because of the formation of acidic products and left no effects at the end. To
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12 overcome this problem, catalytic ozonation is an efficient alternative because ozone can

13 decompose itself to produce HO• in the presence of catalyst. Furthermore, use of catalyst also
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14 promotes controlled decomposition of ozone into HO• resulting in effective mineralization of dye
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15 and organic contaminants (Nawrocki and Kasprzyk-Hordern, 2010; Kasprzyk-Hordern et al.,


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16 2003).

17 Wu et al (2008) compared catalytic ozonation for homogeneous (Mn(II)) and heterogeneous


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18 (UV/TiO2 & MnO2) catalytic system for degradation of Reactive Red 2 (RR2) with subsequent
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19 mechanisms. And they observed high degradation of RR2 as a result of radial chain reaction and

20 surface mechanism.

21 Performance of catalytic ozonation can further be improved in the presence of activated

22 carbon as it enhances the chances of in-situ HO• radical formation. For this, Faria et al (2009)

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1 demonstrated the activity of composite AC0-Ce-O for ozonation of one acid and two reactive

2 dyes. They observed that improvement in the performance of ozonation was due to the

3 adsorption and accelerated decomposition of O3 into HO•. Moreover, this decomposition step

4 depends on textural properties of activated carbon i.e. type of functional groups present, ash

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5 content, pore volume, surface area and pre-treatment of activated surface (Rivera-Utrilla and

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6 Sánchez-Polo, 2002; Sánchez-Polo et al., 2005). To realize it, Sanchez et al (2005) treated the

7 activated carbon with urea and detected the presence of pyrodine and pyrrol groups on carbon

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8 surface with increased surface area. It was elucidated that pyrrolic groups present on activated

9 carbon surface yield N-oxide type groups and hydroperoxide radical in presence of O3 (Sánchez-

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Polo et al., 2005) and thus enhances decomposition rate to form HO• for mineralization of
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11 recalcitrant intermediates (Staehelin and Hoigne, 1982).
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12 Thus, ozonation can be an efficient alternative for in-situ production of H2O2 as evident from

13 the examples discussed in Table 2 that with ozonation maximum COD removal achieved was
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14 60.2%. However, there are several problems that must be dealt in for its industrial applications.
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15 These include intense energy requirement for in-situ ozone generation, selectivity for organic
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16 substrates, pH sensitivity (Song et al., 2007), mass transfer limitations, high consumption rate of

17 ozone and increase in turbidity level of effluents (Ince and Tezcanlı́, 2001). It has been reported
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18 that energy consumption for ozonation of Congo red dye increases linearly and to achieve 80%
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19 TOC removal, 528kWh/m3 power was consumed which was 254kWh/m3 for electrochemical

20 oxidation process (Faouzi Elahmadi etal., 2009).

Table 2. Application of AOPs for in-situ production of H2O2/HO• for textile wastewater

treatment

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1 2.4.Photocatalysis

2 Photocatalysis makes the use of semiconducting materials to generate holes and free radicals

3 for degradation of recalcitrant organic contaminants. These radicals include HO•, O2• ‾, HOO•,

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4 produced based on the interaction with the oxidizing species (Lachheb et al., 2002; Tanaka et al.,

5 2000). Semiconducting oxides like TiO2, ZnO, Fe2O3, ZnS and CdS can be used as photocatalyst

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6 (Umar and Aziz, 2013). Among all, TiO2 has been probed frequently for observing reductive as

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7 well as oxidative reactions on its surface (Chong et al., 2010).

8 In wastewater treatment applications, semiconductors (ZnO, TiO2 etc) have the potential to

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perform degradation of organic contaminants directly as well as through production of
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10 chemically active species i.e. HO• (Boroski et al., 2009). It is well established that holes in

11 valence band and electrons in conduction band are formed when semiconducting material is
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12 exposed to photons with energy higher than band gap energy. The radical generation mechanism
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13 has been presented in Fig. 6. Holes are oxidizing agents that have capability to oxidize organic
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14 compounds and H2O into mineralization products and HO• respectively [Eq. 6] (Boroski et al.,

15 2009).
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16 h+ + H2O → HO• + H+ (6)


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17 Electrons present in conductive band react with O2 as a reducing agent and form superoxide
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18 [Eq. 7], which has wonderful chemistry not only for the production of H2O2 but also for the

19 degradation of intermediates depending on pH (Fang et al., 2013; Boroski et al., 2009). Thus pH

20 plays a key role for in-situ production of HO•.

21 O2 + e‾ → O2•‾ (7)

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2 The role of ZnO is the same as that of TiO2 for in-situ HO• production for textile wastewater

3 treatment. Peternel et al (2007) collated the performance of TiO2 and ZnO for degradation of C.I.

4 Reactive red 45(RR45) and observed same mechanism for both. The observed decolorization

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5 efficiency with TiO2 was 71% at pH 3 while it was only 60.1% at neutral pH with 5 times more

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6 dosage of ZnO. Although ZnO has been found to be more efficient than TiO2, it has disadvantage

7 of photo-corrosion when exposed to UV light (Kaur and Singh, 2007).

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8 Fig. 5. Schematic presentation of mechanism of oxidative species production

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9 (Stylidi et al., 2003)
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10 Photocatalysis can potentially be used for in-situ H2O2/HO• productions but there are several
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11 factors that must be considered. One of the issues with TiO2 is the difficult separation of the

12 particles. For this, Sathishkumar et al (2013) investigated CoFe2O4 loaded TiO2 nano-particles
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13 for degradation of Reactive red 184 (RR184) and successfully achieved both Photocatalytic as
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14 well as magnetic properties. The purpose of enhanced magnetic properties is to achieve easy

15 separation just by applying the magnetic field. Another common problem that has been
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16 frequently highlighted in several investigations is the recombination of electrons and holes. In

17 order to resolve it, Ozer and Ferry (2001) successfully investigated the performance of
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18 Polyoxomethalate (POM) anions as electron shuttle and explained the mechanism as shown in
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19 Fig. 6. As discussed earlier, quinone groups are known to serve as electron shuttles for aromatic

20 compounds such as azo dyes. Hence, improved production of photocatalytically induced in-situ

21 HO• can possibly be observed for textile wastewater treatment (Lee et al., 2007).

22 Fig. 6. Electron transfer in presence of POM

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1 Apart from the above mentioned constraints, catalyst loading and dye concentration have to

2 be optimized for enhanced production of HO•. Initial increase in the catalyst loading is directly

3 proportional to the dye degradation. Above optimum value, catalyst loading results in decrease in

4 the dye degradation. The reason for such behavior is an increase in the number of active sites at

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5 lower concentrations which in turn increase the production of primary and active HO•. Increase

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6 in the catalyst loading results in either agglomeration of the particles in the suspension or

7 reflectance of light which reduces the HO• production. This is in exact agreement with the results

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8 achieved by Krishnakumar and Swaminathan (2011) and Sun et al (2008) while degrading Acid

9 Violet 7 (AV7) and Orange G (OG) respectively.

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10 It has also been reported by Krishnakumar and Swaminathan (2011) that increasing dye

11 degradation, reduces the probability of dye molecules to react with the HO• as concentration of
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12 catalyst and intensity of UV light are the same. Same reason has been addressed in another way

13 by Muruganandham and Swaminathan (2006). It has been reported that degradation of Orange G
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14 (OG) dye decreased from 98.79% to 23.91% above optimum concentration of dye. It was
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15 reported that above some optimum value, dye molecules affected the catalytic activity of the
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16 catalyst. Additionally, high concentrations also decrease the path length of the photon entering

17 which reduces the photocatalytically produced in-situ HO•.


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18 Furthermore, TiO2 can only absorb ultraviolet light which is only 4% of the solar light (Ni et
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19 al., 2007). To avoid it, TiO2 is usually doped with other semiconducting material such as Cu2O, a

20 p-type semiconductor which has narrow band gap but high conduction band (Yu et al., 2004).

21 When exposed to visible light, electrons in conduction band of Cu2O transfer to that of TiO2 and

22 thus increase the photocatalytic degradation of TiO2 (Zhang et al., 2007).

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1 Photocatalysis has been demonstrated successfully by several authors for production of HO•

2 along with the degradation of textile waste. This process has the potential to achieve maximum

3 of 80% COD and 90% color removal efficiencies (Table 2) with modifications. However, it

4 cannot be considered as an alternative for in-situ H2O2 production because: 1) it is energy

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5 intensive. For instance, it consumed 8×104 kW power reactive azo dye treatment (Mahamuni and

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6 Adewuyi, 2010) which is several times of ozonation (Mehrjouei et al., 2014) 2) Textile

7 wastewater is highly variable in concentration and photocatalysis is limited for small streams and

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8 low concentration of dyes.

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9 2.5.Electrochemical and Microbial fuel cells
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10 Electrochemical oxidation is an effective alternative as it employs either direct or indirect
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11 oxidation approach for wastewater treatment (Fu et al., 2010). In direct electrochemical

12 oxidation, degradation is carried out through adsorption of the contaminants on the anode surface
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13 without any involvement of oxidizing agent. However, indirect oxidation in electrochemical fuel
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14 cells employs the sparging of oxygen in cathode chamber to produce H2O2 through direct

15 application of electric current (Panizza and Cerisola, 2009). This mechanism has been
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16 successfully applied in textile wastewater treatment in several investigations as clear from Table

17 3.
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18 High degradation rates and complete mineralization at optimum conditions are the main

19 features of the process but intense energy requirement hinders its practical application for in-situ

20 H2O2/HO• production(Fu et al., 2010; Martínez and Uribe, 2012). In one investigation, it has also

21 been found that electrochemical oxidation is more economic in comparison with ozonation in

22 terms of energy consumption for in-situ H2O2 production (Faouzi Elahmadi et al., 2009). The

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1 possible reason may be the use of modified boron doped diamond electrode. Thus there is an

2 intense need of alternative that requires less energy and must be environmental friendly.

3 Wastewater can be a renewable energy source for the production of electricity, fuels and

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4 chemicals (Rozendal et al., 2008). Recently, several findings have explored the potential of

5 wastewater for the in- situ production of H2O2 (hence in-situ Fenton oxidation) in microbial fuel

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6 cells (Fu et al., 2010; Kalathil et al., 2011; Li et al., 2010; Modin and Fukushi, 2013). However,

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7 it has been frequently investigated for the generation of electricity from wastewater and many

8 authors have also reported the production of water in cathode chamber (Du et al., 2007; Rabaey

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9 et al., 2003; Han et al., 2010). For in-situ production of H2O2/HO•, bacterial species present in
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10 the wastewater (in anode chamber) plays an important role. It is confirmed by R. Bond and

11 Lovely (2002) and his co-worker that among all bacterial species, presence of Geobacter
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12 Sulfurreducens in anode compartment favors the production of H2O2 in cathode compartment.

13 However, G. Sulfurreducens species are highly sensitive to oxygen therefore, Fernantez de Dios
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14 et al (2013) suggested the use of Shewanella species which is facultative exoelectrogen and
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15 obtained 82% mineralization of dye mixture through H2O2 production (in-situ Fenton oxidation)

16 in cathode chamber of WBMFCs. Thus, microbial fuel cells use electrochemically active
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17 microorganisms (Rozendal et al., 2008) present in the wastewater to convert the chemical energy
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18 stored in organic compounds into electrical energy (Gil et al., 2003; Moon et al., 2006). This
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19 oxidation step is coupled by in-situ production of H2O2 for the degradation of refractory waste in

20 cathode compartment (Zhu and Ni, 2009).

21 Rozendal et al (2009) investigated the production of H2O2 in cathode chamber by using

22 oxygen as an electron acceptor. At applied voltage of 0.5V, about 1.9 to 2 kg H2O2/m3/day was

23 successfully produced. In this study, voltage was applied to accelerate the production of

20
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1 electrons and start-up time. It is in agreement with the findings of Wang et al (2009) according to

2 which applied voltage enhanced the production of electricity in microbial fuel cells.

3 The study conducted by Rozendal et al (2009) was not based on the in-situ production of

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4 H2O2 but it is still beneficial to estimate the potential of microbial fuel cell for degradation of dye

5 in future investigations. It can be proved by the findings of Fu et al (2010), who examined the

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6 in-situ generation of H2O2 for degradation of azo dye (amaranth) under neutral cathodic

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7 conditions and reported that by utilizing 0.5 mmole/L Fe+3 as catalyst 76.5% degradation

8 efficiency could be achieved within one hour.

9
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The literature concerning in-situ H2O2 production in microbial fuel cells has frequently
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10 discussed the dual chamber configuration. It has been reported that performance of dual chamber
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11 MFCs is affected by high internal resistance caused by proton exchange membrane (Zhu and

12 Logan, 2013a). Thus, with an attention of reducing the cost and eliminating the effect of
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13 membrane, membrane-less single chamber microbial fuel cell was suggested to use as a low
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14 power source for performing in-situ H2O2 production in electro-Fenton reactor (Zhu and Logan,

15 2013b). However, distances between anode and cathode may contribute to an increase in the
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16 resistance of the microbial fuel cell. Therefore, in-situ H2O2 production in microbial fuel cells

17 should be further explored to increase the efficiency of the process.


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18 Performance of microbial fuel cells also depends on several other factors that must be taken

19 into account while discussing the in-situ production of H2O2. These include hydraulic retention

20 time, pH, characteristic of effluent, external resistance, type of co-substrates (Solanki et al.,

21 2013), start up times (Liu et al., 2011) and irreversible nature of the reactions (Rismani-Yazdi et

22 al., 2008). However, the cost and properties of electrode material have significant importance.

21
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1 Electrode material must have good electrical conductivity, high surface area, chemical stability

2 and appropriate strength and toughness (Zhou et al., 2011). Many authors have collated different

3 electrodes such as graphite, platinum, IrO2, RuO2, PbO2 and boron-doped diamond electrodes in

4 their investigations. It has been found that IrO2 and RuO2 electrodes have low reactivity for

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5 organic oxidation and graphite electrodes are inexpensive but all of them have low current

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6 efficiencies (Tan et al., 2011). Platinum exhibits excellent electro catalytic properties (Jaccoud et

7 al., 2006) but its high cost always limits its application (Du et al., 2007). To improve the

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8 performance of microbial fuel cell, simple graphite anode was heated and used in single

9 chamber microbial fuel cell and 75% of the recalcitrant contaminant was mineralized through in-

10 situ H2O2 (hence in-situ Fenton oxidation).


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11 Microbial fuel cell is a versatile technology because electricity production is accompanied by
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12 the production of H2O2 in cathode chamber (Li et al., 2010, Rozendal et al., 2009). Much work

13 has been done on improving the production of electricity to-date (Feng et al., 2010a; Feng et al.,
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14 2010b). To-date, power produced has been used as a low power source for operating
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15 electrochemical fuel cells (Zhu and Logan, 2013b). Alternatively, power produced can also be
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16 used for the aeration of cathode chamber, which would provide an environmental friendly and

17 cost effective solution for textile wastewater treatment through in-situ H2O2 (in-situ Fenton
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18 oxidation). Being at initial stages of the process, maximum TOC removal of 76% has been
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19 obtained through microbial fuel cell application at low concentrations of pollutant (Table 3). It is

20 lesser than that obtained in electrochemical oxidation thus highlighting the need of optimizing

21 the operating parameters for achieving results comparable to electrochemical oxidation process.

Table 3. Electrochemical and microbial fuel cells for in-situ production of H2O2/HO•
22

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1 3. Improvements for in-situ H2O2/HO• production through sonolysis

2 Sono-chemical degradation of dyes is considered as AOPs (Vončina and Majcen-Le-

3 Marechal, 2003) because of its potential to produce HO• radical by homogeneous reactions or

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4 enhancing the activity of catalyst in heterogeneous reactions. In aqueous medium, ultrasound

5 waves (‘))’) provoke the formation and collapse of cavitation bubbles. Cavitation produces hot

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6 spots of high temperature and pressure for shorter time which during collapsing phase cause

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7 splitting of water molecules into HO• and H• radical (Chitra, 2004). Local concentration of HO•

8 and H• radical is high but an estimated 80% of H• and HO• radicals recombine and reduces the

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9 bulk concentration of these radicals (Stock, Peller et al., 2000; Gültekin et al., 2009).Thus, major
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10 portion of the mechanical energy is lost due to recombination reaction.

H2O + )) → •OH + •H
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11 (8)


12 OH + •H → H2O (9)
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13 Dyes are highly hydrophilic so they can be degraded in bulk in comparison with the volatile

14 organic compounds which can only be degraded thermally inside the gas bubble (Adewuyi,
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15 2001). However, reactive azo dyes are non-volatile, water soluble and their reaction at interface

16 is not observed (Vajnhandl and Le Marechal, 2007). It indicates that dye interaction with HO•
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17 radicals can only be possible in the bulk solution. However, if hydrophilic organic compounds
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18 are concentrated in the solution additional degradation mechanism then quickly takes place at

19 gas-liquid interface (Okitsu et al., 2005).

20 Concentration of HO• radicals is reported to be improved in bulk dye solution in the presence

21 of dissolved oxygen, ozone or catalyst. Thermal decomposition of dissolved oxygen and water

23
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1 produce more HO• and other chemical reactive species [Eq. 8, 10-13]. However, recombination

2 phenomenon still cannot be overcome (Destaillats et al., 2000).

3 O2 +)) → 2•O (10)

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4 HO• + •O → •OOH (11)

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5 O + H2O → 2 HO• (12)

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6 H + O2 → •OOH (13)

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7 In several investigations, it has been suggested that sonolysis should combine with ozonation
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8 for in-situ H2O2/ HO• production without alkaline conditions as discussed in Table 4. When

9 sonicated liquid is bubbled with ozone, mass transfer rates of the ozone is improved which is the
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10 main issue with ozonation alone. In the presence of O3 alone 30% mineralization can be achieved

with methyle orange. In combination with Ultrasound, synergetic effect is produced and
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11

12 mineralization achieved exceeds 80% within pH range of 5.5-6.5 (Destaillats et al., 2000).
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13 Reason for this synergetic effect is that every O3 molecule decomposes to yield two molecules of

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14 OH radicals in the presence of Sonolysis (Vecitis et al., 2010).

15 Aside from homogeneous reaction, activity of the catalytic process has been observed to
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16 improve because of the synergized effect induced by the ultrasound waves. As mentioned before
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17 Fe0 deactivates due to the precipitation of hydroxyl/iron oxides which results in the decrease in

18 the porosity of the catalyst with time (Gillham and O'Hannesin, 1994). However, US/Fe0 not

19 only increases the active surface area of catalyst by rupture or pitting, but also increase the

20 concentration of HO• at increased loading of the iron catalyst. That is the reason that

24
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1 decolorization of the C.I. Acid Orange 7 (AO7) improved from 63% to 91% due in a study done

2 by Zhang et al (2005). However, with zero-valent copper (Cu0), the efficiency is lower in

3 comparison with Fe0 regardless of dye concentration and sound frequency. It may be because of

4 the acidic conditions which cause protonated dyes to repel the catalyst surface (positively

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5 charged) and Cu has less potential than iron species (Eren and Ince, 2010).

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6 Photocatalyst mainly TiO2 and ZnO intensify in-situ production of HO• by dissociating water

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7 molecule because of combined effect of UV and US. Table 4 summarizes the ultrasound

8 conditions, dye concentration and subsequent outcomes for AOPs demonstrated by several

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9 authors specifically for HO• radical production. An increase in HO• radical production in
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10 combinative process may be attributed to the accelerated mass transfer of reactants and products

11 to and from the catalyst surface. It may also be caused by an increase in the activity of the
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12 catalyst by particle disaggregation which increases the surface area of the catalyst (Stock et al.,

13 2000). However, effect of US, UV and photocatalyst are more significant than either
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14 combination with the photocatalyst. For example Acid Orange 8 dye has completely been
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15 degraded within 4 hrs under sonophotocatalysis while in the absence of US, 79% degradation has
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16 been achieved (Selli, 2002). It has also been reported that synergetic effect of ultrasound waves

17 convert H2O2 into more HO• radicals which makes this process efficient. Therefore, dye and
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18 catalyst concentrations are equally sensitive for combined process (González and Martínez,
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19 2008; Bejarano-Pérez and Suárez-Herrera, 2007).

20 Sonolysis is an auxiliary tool for in-situ HO• radicals production for textile wastewater

21 treatment through AOPs. Economic analysis conducted by Adewuyi (2001) states that overall

22 cost for sonolysis alone is not economically acceptable on large scale. However, addition of

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1 additive or combination of the US with AOPs is more economical. The cost for US combined

2 with ozonation is 1.67 ×105 USD and for ultrasound it is 2.11×108 USD. For reactive azo dye

3 degradation, the power consumed by sonolysis is 6.58×105kW which is more than that of

4 ozonation (Mahamuni and Adewuyi, 2010). There are several additional factors that must be

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5 dealt with before considering scale-up including properties of fluid and dissolved gases, amount

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6 and frequency of the sonication required for HO• production. In addition, nature of dye structure

7 present in the textile wastewater will also affect the reaction rate (Thompson and Doraiswamy,

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8 1999). These factors make large scale application of sonolysis doubtful because incoming textile

9 wastewater contains variety of dyes with different concentrations and properties. So,

10
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optimization of operating parameters may be an issue for scale up.
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Table 4. Ultrasound as an auxiliary tool for AOPs: In-situ production of H2O2/HO•
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11
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12 4. Considerations during the in-situ H2O2/HO• production process


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13 Real textile effluents contain carbonates, bicarbonates and chlorides in addition to dyes.
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14 These inorganic anions reduce the degradation efficiency of the dyes by scavenging the

15 oxidizing agents. One of the most challenging scavenging phenomenon is the formation of H2O2
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16 in the presence of excessive HO• [Eq. 14] (Borda et al., 2003).


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17 OH + •OH → H2O2 (14)

18 Bicarbonates and carbonates are the most commonly available anions in wastewater and can

19 easily scavenge radicals available for textile wastewater treatment [Eq. 15-16]. Faria et al (2009)

26
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1 reported the influence of carbonates and bicarbonates as HO• scavenger on the efficacy of the

2 process. It was found that scavenging effect of carbonate ions was more as compared to

3 bicarbonate ions at both moderate and high pH value.

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4 HCO3‾ + HO•→ CO3• ‾ + H2O (15)

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5 CO32‾ + HO• → CO3• ‾ + HO‾ (16)

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6 Moreover, presence of di-hydrogen phosphate ion H2PO4‾ and mono hydrogen phosphate ion

7 HPO4‾ also lowers the efficiency by scavenging HO• (Karthikeyan et al., 2011) [Eq. 17-18].

8
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HO• + H2PO4‾ → OH‾ + H2PO4˙ (17)
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9 HO• + HPO4‾→ OH‾ + H2PO4‾ (18)
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10 Halides ions have potential to scavenge the hydroxyl radicals as follows [Eq. 19]:
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11 Cl‾ + •OH→ ClOH•‾ (19)


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12 That is why FeSO4.7H2O is always preferred over FeCl2.4H2O in Fenton process. Moreover,
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13 Cl‾ ions can also scavenge the holes in photocatalysis system and reduce the yield of the in-situ

14 hydrogen peroxide formation [Eq. 20]:


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15 Cl‾ + h+ → Cl• (20)

16 In ozonation, the effect of inorganic ions is more pronounced as they inhibit the decomposition

17 of ozone but it put positive impact on the decolorization of the dye because of the presence of

18 molecular ozone (Tehrani-Bagha et al., 2010).

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1 Same phenomenon can be observed in the presence of NO3‾ and SO4-2 radicals. In the presence

2 of sulfate ions, it seems difficult to decide either sulfate ions are scavengers or playing a

3 productive role for formation of other radicals. According to reaction Eq. 21 & 22, sulfate ions

4 are scavenging holes and HO• but at the same time transformation to SO4• ‾ are also taking place.

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5 And SO4• ‾ have redox potential comparable to the HO• (see Table 1) and can degrade the dyes

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6 present in the wastewater (Huang et al., 2005). But as they are less reactive as compared to HO•

7 and holes so their role is more as scavengers as compared to promoter.

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8 SO4-2 + h+ → SO4• ‾ (21)

9
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SO4-2 + HO•→ SO4• ‾ + HO‾ (22)
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10 Scavenging of HO• is unavoidable because these anions are naturally present in wastewater.
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11 Separation of these anions is also not possible because this requires more sophisticated

12 experimental setup and is not economically viable. This suggests the need to find some
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13 alternative to suppress the effect of anions as scavenger.


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14 5. Conclusion
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15 Fenton process is an efficient method for degradation of dyes and recalcitrant organic
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16 contaminants present in textile wastewater. However, excessive use of reagents, acidic


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17 conditions, and high cost of hydrogen peroxide hinder its industrial applications. It is also unsafe

18 to transport and store bulk quantities of H2O2. To overcome this problem, in-situ H2O2/HO•

19 production by Advanced Oxidation Processes including iron-catalyzed processes, ozonation,

20 photocatalysis, electrochemical oxidation and microbial fuel cells is an option worth

21 consideration. Based on this review, the following main conclusions are drawn:

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1 In-situ H2O2 production by iron catalyzed process has advantage of forming Fenton oxidation

2 system in itself. Economically, it is a suitable alternative as the operating cost has been found to

3 reduce from 0.015 to 0.00113 US$/g of dye for RRB treatment with Fe0/air. However, zero

4 valent iron has been found to be deactivated with time. Similarly, ozonation follows radical chain

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5 reaction mechanism to produce HO• radical either in alkaline conditions or in the presence of

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6 catalyst, However, there are few constraints such as alkaline conditions, high power consumption

7 of 34.98kW/gallons of dye and mass transfer limitations that reduce the efficiency and economic

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8 viability of the process.

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9 Besides, Photocatalysis which is with an intense energy requirement of 80kW/gallon of dye can
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10 efficiently induce dye degradation through in-situ HO• radical production. Replacing UV with

11 solar energy is economically beneficial but photocatalysis is limited for small and less
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12 concentrated streams of the textile wastewater. Alternatively, smooth and efficient production of

13 HO• and high mineralization rates are achievable in electrochemical oxidation process. However,
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14 its energy requirement is more intense than Photocatalysis which indicates the process is not
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15 economically viable. The most viable solution to this problem is the use of microbes present in

16 the wastewater in microbial fuel cells to produce H2O2/HO• with simultaneous power production.
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17 In this way, microbial fuel cell will be used as a low power source for electrochemical oxidation
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18 or aeration of the cathode chamber of microbial fuel cell. Use of ultrasound in combination with
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19 AOPs provokes the formation of HO• by following the splitting mechanism of water molecules.

20 According to the reported data, sonolysis requires 658kW energy/gallon of reactive dye treated.

21 It is a more economical option when combined with other AOPs such as ozonation and

22 Photocatalysis. However, types of the fluid, frequency and power of sonolysis need to be

23 determined for its application in in-situ HO• radical production. Apart from that, scavenging of

29
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1 HO• by anions is unavoidable. This is because these anions are naturally present in real

2 wastewater and their removal requires a few pre-treatment steps that increase the total cost of the

3 treatment process.

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4 Therefore, it is concluded that in-situ H2O2 is technically and economically viable for textile

5 wastewater treatment. It may overcome issues currently linked with commercially available

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6 H2O2. Being under its developing stages, this concept requires further research in optimizing the

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7 operating parameters and methodology so that its commercial applications could be ensured in

8 near future in the view of its economical and ecological importance.

9 Acknowledgement
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10 The authors are grateful to the Faculty of Engineering University of Malaya, High Impact

11 Research Grant (HIR-MOHE- D000037-16001) from the Ministry of Higher Education Malaysia
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12 and University of Malaya Bright Sparks Unit which financially supported this work.
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13 Abbreviations
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14 AOPs: Advance Oxidation Processes; HO•: Hydroxyl radical; H2O2: Hydrogen Peroxide; SO4• ‾:

15 Sulfate free radicals; MnO4‾: Permanganate; ClO‾: Hypochlorite; ClO2: Chlorine dioxide; Co+2:
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16 Cobalt ion; PMS: Peroxymonosulfate; AR88: Acid red 88; SDBS: Sodium

Dodecylbenzenesulphonate; PAC: Powdered Activated Carbon; O2•‾: Superoxide Radical; Fe0:


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17
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18 Zero-valent iron; POM: Peroxometalate; RBBR: Remazol Brilliant Blue R; RR2: Reactive red 2;

19 ACo: Activated Carbon; Ce-O: Cerium Oxide; ACo-Ce-O: Ceria-activated carbon composite; h+:

20 Holes; e‾: electrons; RR45: C.I. Reactive Red 45; RR184: C.I. Reactive Red 184; AV7:Acid

21 Violet 7; OG: Orange G; AO7: C.I. Acid Orange 7.

22

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1 Reference

2 Adewuyi, Y.G., 2001. Sonochemistry: Environmental Science and Engineering Applications.


3 Ind. Eng. Chem. Res. 40, 4681-4715.

4 Aguedach, A., Brosillon, S., Morvan, J., Lhadi, E.K., 2008. Influence of ionic strength in the

PT
5 adsorption and during photocatalysis of reactive black 5 azo dye on TiO2 coated on non woven
6 paper with SiO2 as a binder. J. Hazard. Meter. 150, 250-256.

RI
7 Akyol, A., Bayramoglu, M., 2008. The degradation of an azo dye in a batch slurry photocatalytic
8 reactor. Chem. Eng. Process. 47, 2150-2156.

SC
9 Alinsafi, A., Khemis, M., Pons, M.N., Leclerc, J.P., Yaacoubi, A., Benhammou, A., Nejmeddine,
10 A., 2005. Electro-coagulation of reactive textile dyes and textile wastewater. Chem. Eng.
11 Process. 44, 461-470.

U
12 Anipsitakis, G.P., Dionysiou, D.D., 2003. Degradation of Organic Contaminants in Water with
13 Sulfate Radicals Generated by the Conjunction of Peroxymonosulfate with Cobalt. Environ. Sci.
AN
14 Technol. 37, 4790-4797.

15 Anipsitakis, G.P., Dionysiou, D.D., 2004. Radical Generation by the Interaction of Transition
16 Metals with Common Oxidants. Environ. Sci. Technol. 38, 3705-3712.
M

17 Arami-Niya, A., Wan Daud, W.M.A., S. Mjalli, F., Abnisa, F., Shafeeyan, M.S., 2012.
18 Production of microporous palm shell based activated carbon for methane adsorption: Modeling
D

19 and optimization using response surface methodology. Chem. Eng. Res. Des. 90, 776-784.
TE

20 Baban, A., Yediler, A., Lienert, D., Kemerdere, N., Kettrup, A., 2003. Ozonation of high
21 strength segregated effluents from a woollen textile dyeing and finishing plant. Dyes Pigm. 58,
22 93-98.
EP

23 Barakat, M.A., 2011. Adsorption and photodegradation of Procion yellow H-EXL dye in textile
24 wastewater over TiO2 suspension. J. Hydro-Environ. Res. 5, 137-142.
C

25 Bejarano-Pérez, N.J., Suárez-Herrera, M.F., 2007. Sonophotocatalytic degradation of congo red


26 and methyl orange in the presence of TiO2 as a catalyst. Ultrason. Sonochem. 14, 589-595.
AC

27 Bensalah, N., Alfaro, M.A.Q., Martínez-Huitle, C.A., 2009. Electrochemical treatment of


28 synthetic wastewaters containing Alphazurine A dye. Chem. Eng. J. 149, 348-352.

29 Borda, M.J., Elsetinow, A.R., Strongin, D.R., Schoonen, M.A., 2003. A mechanism for the
30 production of hydroxyl radical at surface defect sites on pyrite. Geochim. Cosmochim. Acta 67,
31 935-939.

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1 Boroski, M., Rodrigues, A.C., Garcia, J.C., Sampaio, L.C., Nozaki, J., Hioka, N., 2009.
2 Combined electrocoagulation and TiO2 photoassisted treatment applied to wastewater effluents
3 from pharmaceutical and cosmetic industries. J. Hazard. Meter. 162, 448-454.

4 Campos-Martin, J.M., Blanco-Brieva, G., Fierro, J.L.G., 2006. Hydrogen Peroxide Synthesis: An
5 Outlook beyond the Anthraquinone Process. Angew. Chem. Int. Ed. 45, 6962-6984.

PT
6 Cao, J., Wei, L., Huang, Q., Wang, L., Han, S., 1999. Reducing degradation of azo dye by zero-
7 valent iron in aqueous solution. Chemosphere 38, 565-571.

RI
8 Cao, Y., Hu, Y., Sun, J., Hou, B., 2010. Explore various co-substrates for simultaneous
9 electricity generation and Congo red degradation in air-cathode single-chamber microbial fuel
10 cell. Bioelectrochemistry 79, 71-76.

SC
11 Chakrabarti, S., Dutta, B.K., 2004. Photocatalytic degradation of model textile dyes in
12 wastewater using ZnO as semiconductor catalyst. J. Hazard. Meter. 112, 269-278.

U
13 Chang, S.-H., Chuang, S.-H., Li, H.-C., Liang, H.-H., Huang, L.-C., 2009. Comparative study on
14 the degradation of I.C. Remazol Brilliant Blue R and I.C. Acid Black 1 by Fenton oxidation and
AN
15 Fe0/air process and toxicity evaluation. J. Hazard. Meter. 166, 1279-1288.

16 Chen Q., 2006. Towards cleaner production of hydrogen peroxide in China. J. Clean. Prod. 14,
M

17 708-712.

18 Chen, Y., Yang, S., Wang, K., Lou, L., 2005. Role of primary active species and TiO2 surface
characteristic in UV-illuminated photodegradation of Acid Orange 7. Photochem. Photobiol. A.
D

19
20 Chem. 172, 47-54.
TE

21 Chiang, Y.-J., Lin, C.-C., 2013. Photocatalytic decolorization of methylene blue in aqueous
22 solutions using coupled ZnO/SnO2 photocatalysts. Powder Technol. 246, 137-143.
EP

23 Chitra, S., Paramasivan, K., Sinha, P.K., Lal, K.B., 2004. Ultrasounic treatment of liquid waste
24 containing EDTA. J.Clean. Prod. 12, 429- 436

25 Chong, M.N., Jin, B., Chow, C.W.K., Saint, C., 2010. Recent developments in photocatalytic
C

26 water treatment technology: A review. Water Res. 44, 2997-3027.


AC

27 Chong, M.N., Sharma, A.K., Burn, S., Saint, C.P., 2012. Feasibility study on the application of
28 advanced oxidation tehcnologies for decentralised wastewater treatment. J. Clean. Prod. 35, 230-
29 238.

30 Choudhary, V.R., Jana, P., 2007. In situ generation of hydrogen peroxide from reaction of O2
31 with hydroxylamine from hydroxylammonium salt in neutral aqueous or non-aqueous medium
32 using reusable Pd/Al2O3 catalyst. Catal. Commun. 8, 1578-1582.

32
ACCEPTED MANUSCRIPT

1 Chu, L.-B., Xing, X.-H., Yu, A.-F., Zhou, Y.-N., Sun, X.-L., Jurcik, B., 2007. Enhanced
2 ozonation of simulated dyestuff wastewater by microbubbles. Chemosphere 68, 1854-1860.

3 Chu, W., Ma, C.-W., 2000. Quantitative prediction of direct and indirect dye ozonation kinetics.
4 Water Res. 34, 3153-3160.

5 de Souza, S.M.d.A.G.U., Bonilla, K.A.S., de Souza, A.A.U., 2010. Removal of COD and color

PT
6 from hydrolyzed textile azo dye by combined ozonation and biological treatment. J. Hazard.
7 Meter. 179, 35-42.

RI
8 Destaillats, H., Colussi, A.J., Joseph, J.M., Hoffmann, M.R., 2000. Synergistic Effects of
9 Sonolysis Combined with Ozonolysis for the Oxidation of Azobenzene and Methyl Orange. The
10 The J. Phys. Chem. A 104, 8930-8935.

SC
11 Ding, H., Li, Y., Lu, A., Jin, S., Quan, C., Wang, C., Wang, X., Zeng, C., Yan, Y., 2010.
12 Photocatalytically improved azo dye reduction in a microbial fuel cell with rutile-cathode.
13 Bioresour. Technol. 101, 3500-3505.

14
U
Du, Z., Li, H., Gu, T., 2007. A state of the art review on microbial fuel cells: A promising
AN
15 technology for wastewater treatment and bioenergy. Biotechnol. Adv. 25, 464-482.

16 Eren, Z., 2012. Ultrasound as a basic and auxiliary process for dye remediation: A review.
M

17 Journal of Environmental Management 104, 127-141.

18 Eren, Z., Ince, N.H., 2010. Sonolytic and sonocatalytic degradation of azo dyes by low and high
frequency ultrasound. J. Hazard. Meter. 177, 1019-1024.
D

19

20 Fang, G.-D., Zhou, D.-M., Dionysiou, D.D., 2013. Superoxide mediated production of hydroxyl
TE

21 radicals by magnetite nanoparticles: Demonstration in the degradation of 2-chlorobiphenyl. J.


22 Hazard. Meter. 250-251, 68-75.
EP

23 Faouzi Elahmadi, M., Bensalah, N., Gadri, A., 2009. Treatment of aqueous wastes contaminated
24 with Congo Red dye by electrochemical oxidation and ozonation processes. J. Hazard. Meter.
25 168, 1163-1169.
C

26 Faria, P.C.C., Órfão, J.J.M., Pereira, M.F.R., 2009. Activated carbon and ceria catalysts applied
27 to the catalytic ozonation of dyes and textile effluents. Appl. Catal. B. Environ. 88, 341-350.
AC

28 Feng, C., Ma, L., Li, F., Mai, H., Lang, X., Fan, S., 2010a. A polypyrrole/anthraquinone-2,6-
29 disulphonic disodium salt (PPy/AQDS)-modified anode to improve performance of microbial
30 fuel cells. Biosens. Bioelectron. 25, 1516-1520.

31 Feng, Y., Yang, Q., Wang, X., Logan, B.E., 2010b. Treatment of carbon fiber brush anodes for
32 improving power generation in air–cathode microbial fuel cells. J. Power Sources 195, 1841-
33 1844.

33
ACCEPTED MANUSCRIPT

1 Fernández de Dios, M.Á., del Campo, A.G., Fernández, F.J., Rodrigo, M., Pazos, M., Sanromán,
2 M.Á., 2013. Bacterial–fungal interactions enhance power generation in microbial fuel cells and
3 drive dye decolourisation by an ex situ and in situ electro-Fenton process. Bioresour. Technol.
4 148, 39-46.

5 Fu, L., You, S.-J., Zhang, G.-q., Yang, F.-L., Fang, X.-h., 2010. Degradation of azo dyes using
6 in-situ Fenton reaction incorporated into H2O2-producing microbial fuel cell. Chem. Eng. J. 160,

PT
7 164-169.

8 Fujishima, A., N. Rao, T., A. Tryk, D., 2000. Titanium dioxide photocatalysis. J. Photochem.

RI
9 Photobiol. C. Photochem. Rev. 1, 1-21.

10 Gao, M., Zeng, Z., Sun, B., Zou, H., Chen, J., Shao, L., 2012. Ozonation of azo dye Acid Red 14

SC
11 in a microporous tube-in-tube microchannel reactor: Decolorization and mechanism.
12 Chemosphere 89, 190-197.

13 Ghodbane, H., Hamdaoui, O., 2009. Intensification of sonochemical decolorization of

U
14 anthraquinonic dye Acid Blue 25 using carbon tetrachloride. Ultrason. Sonochem. 16, 455-461.
AN
15 Gil, G.-C., Chang, I.-S., Kim, B.H., Kim, M., Jang, J.-K., Park, H.S., Kim, H.J., 2003.
16 Operational parameters affecting the performannce of a mediator-less microbial fuel cell.
17 Biosens. Bioelectron. 18, 327-334.
M

18 Gillham, R.W., O'Hannesin, S.F., 1994. Enhanced Degradation of Halogenated Aliphatics by


19 Zero-Valent Iron. Ground Water 32, 958-967.
D

20 Glaze, W.H., Kang, J.-W., Chapin, D.H., 1987. The Chemistry of Water Treatment Processes
21 Involving Ozone, Hydrogen Peroxide and Ultraviolet Radiation. Ozone Sci. Eng. 9, 335-352.
TE

22 González, A.S., Martínez, S.S., 2008. Study of the sonophotocatalytic degradation of basic blue
23 9 industrial textile dye over slurry titanium dioxide and influencing factors. Ultrason. Sonochem.
EP

24 15, 1038-1042.

25 Gul, S., Ozcan, O., Erbatur, O., 2007. Ozonation of C.I. Reactive Red 194 and C.I. Reactive
26 Yellow 145 in aqueous solution in the presence of granular activated carbon. Dyes Pigm. 75,
C

27 426-431.
AC

28 Gültekin, I., Tezcanli-Güyer, G., Ince, N.H., 2009. Sonochemical decay of C.I. Acid Orange 8:
29 Effects of CCl4 and t-butyl alcohol. Ultrason. Sonochem. 16, 577-581.

30 Han, J.-L., Wang, C.-T., Hu, Y.-C., Liu, Y., Chen, W.-M., Chang, C.-T., Xu, H.-Z., Chen, B.-Y.,
31 2010. Exploring power generation of single-chamber microbial fuel cell using mixed and pure
32 cultures. J. Taiwan Inst. Chem. Eng. 41, 606-611.

33 Hassan, D.U.B., Aziz, A.R.A., Daud, W.M.A.W., 2012. On the Limitation of Fenton Oxidation
34 Operational Parameters: A Review. Int. J. Chem. React. Eng. 10.

34
ACCEPTED MANUSCRIPT

1 He, Z., Lin, L., Song, S., Xia, M., Xu, L., Ying, H., Chen, J., 2008. Mineralization of C.I.
2 Reactive Blue 19 by ozonation combined with sonolysis: Performance optimization and
3 degradation mechanism. Sep. Purif. Technol. 62, 376-381.

4 He, Z., Song, S., Xia, M., Qiu, J., Ying, H., Lü, B., Jiang, Y., Chen, J., 2007. Mineralization of
5 C.I. Reactive Yellow 84 in aqueous solution by sonolytic ozonation. Chemosphere 69, 191-199.

PT
6 Huang, K.-C., Zhao, Z., Hoag, G.E., Dahmani, A., Block, P.A., 2005. Degradation of volatile
7 organic compounds with thermally activated persulfate oxidation. Chemosphere 61, 551-560.

RI
8 Ince, N.H., Tezcanlı́, G., 2001. Reactive dyestuff degradation by combined sonolysis and
9 ozonation. Dyes Pigm. 49, 145-153.

SC
10 Jaccoud, A., Fóti, G., Comninellis, C., 2006. Electrochemical investigation of platinum electrode
11 in solid electrolyte cell. Electrochim. Acta 51, 1264-1273.

12 Jin, X.C., Liu, G.Q., Xu, Z.H., Tao, W.Y., 2007. Decolorization of a dye industry effluent by

U
13 Aspergillus fumigatus XC6. Appl. Microbiol. Biotechnol.74, 239-243.
AN
14 Kalathil, S., Lee, J., Cho, M.H., 2011. Granular activated carbon based microbial fuel cell for
15 simultaneous decolorization of real dye wastewater and electricity generation. New Biotechnol.
16 29, 32-37.
M

17 Kalra, S.S., Mohan, S., Sinha, A., Singh, G., 2011. Advance Oxidation processes for Treatment
18 of textile and dye Wastewater: A Review 2nd International Conference on Environmental
Science and Development IACSIT Press, Singapore.
D

19

20 Karthikeyan, S., Titus, A., Gnanamani, A., Mandal, A.B., Sekaran, G., 2011. Treatment of textile
TE

21 wastewater by homogeneous and heterogeneous Fenton oxidation processes. Desalination 281,


22 438-445.
EP

23 Kasprzyk-Hordern, B., Ziółek, M., Nawrocki, J., 2003. Catalytic ozonation and methods of
24 enhancing molecular ozone reactions in water treatment. Appl. Catal. B. Environ 46, 639-669.

25 Kaur, S., Singh, V., 2007. Visible light induced sonophotocatalytic degradation of Reactive Red
C

26 dye 198 using dye sensitized TiO2. Ultrason. Sonochem. 14, 531-537.
AC

27 Kelley, K., Marley, M., Sperry, K., 2003. In Situ Chemical Oxidation, in: Moyer, E., Kostecki,
28 P. (Eds.), MTBE Remediation Handbook. Springer US, pp. 223-241.

29 Khatee, A.,Sheydaei, M., Hassani, A.,Taseidifar, M., Karaca,S., 2015. Sonocatalytic removal of
30 an organic dye using TiO2/Montmorillonite nano-compoiste. Ultrason. Sonochem. 22, 404-411.

31 Krishnakumar, B., Swaminathan, M., 2011. Influence of operational parameters on


32 photocatalytic degradation of a genotoxic azo dye Acid Violet 7 in aqueous ZnO suspensions.
33 Spectrochim. Acta A. Mol. Biomol. Spectrosc. 81, 739-744.

35
ACCEPTED MANUSCRIPT

1 Lachheb, H., Puzenat, E., Houas, A., Ksibi, M., Elaloui, E., Guillard, C., Herrmann, J.-M., 2002.
2 Photocatalytic degradation of various types of dyes (Alizarin S, Crocein Orange G, Methyl Red,
3 Congo Red, Methylene Blue) in water by UV-irradiated titania. Appl. Catal. B. Environ. 39, 75-
4 90.

5 Ledakowicz, S., Maciejewska, R., Gebicka, L., Perkowski, J., 2000. Kinetics of the
6 Decolorization by Fenton's Reagent. Ozone Sci. Eng. 22, 195-205.

PT
7 Lee, J., Kim, J., Choi, W., 2007. Oxidation on Zerovalent Iron Promoted by Polyoxometalate as
8 an Electron Shuttle. . Environ. Sci. Technol. 41, 3335-3340.

RI
9 Li, Z., Zhang, X., Lin, J., Han, S., Lei, L., 2010. Azo dye treatment with simultaneous electricity
10 production in an anaerobic–aerobic sequential reactor and microbial fuel cell coupled system.

SC
11 Bioresour. Technol. 101, 4440-4445.

12 Liang, C., Lee, I.L., 2008. In situ iron activated persulfate oxidative fluid sparging treatment of
13 TCE contamination — A proof of concept study. J. Contam. Hydrol. 100, 91-100.

14
U
Liu, C.-H., Wu, J.-S., Chiu, H.-C., Suen, S.-Y., Chu, K.H., 2007a. Removal of anionic reactive
AN
15 dyes from water using anion exchange membranes as adsorbers. Water Res. 41, 1491-1500.

16 Liu, G., Yates, M.D., Cheng, S., Call, D.F., Sun, D., Logan, B.E., 2011. Examination of
M

17 microbial fuel cell start-up times with domestic wastewater and additional amendments.
18 Bioresour. Technol. 102, 7301-7306.

Liu, H., Li, G., Qu, J., Liu, H., 2007b. Degradation of azo dye Acid Orange 7 in water by
D

19
20 Fe0/granular activated carbon system in the presence of ultrasound. J. Hazard. Meter. 144, 180-
21 186.
TE

22 Liu, Y., Yu, H., Lv, Z., Zhan, S., Yang, J., Peng, X., Ren, Y., Wu, X., 2012. Simulated-sunlight-
23 activated photocatalysis of Methylene Blue using cerium-doped SiO2/TiO2 nanostructured
EP

24 fibers. J. Environ. Sci. 24, 1867-1875.

25 Lunsford, J.H., 2003. The direct formation of H2O2 from H2 and O2 over palladium catalysts. J.
26 Catal. 216, 455-460.
C

27 Ma, C.Y., Xu, J.Y., Liu, X.J., 2006. Decomposition of an azo dye in aqueous solution by
AC

28 combination of ultrasound and visible light. Ultrason. 44, 375-378.

29 Madhavan, J., Maruthamuthu, P., Murugesan, S., Ashokkumar, M., 2009. Kinetics of
30 degradation of acid red 88 in the presence of Co2+-ion/peroxomonosulphate reagent. Appl. Catal.
31 A. Gen. 368, 35-39.

32 Maezawa, A., Nakadoi, H., Suzuki, K., Furusawa, T., Suzuki, Y., Uchida, S., 2007. Treatment of
33 dye wastewater by using photo-catalytic oxidation with sonication. Ultrason. Sonochem. 14,
34 615-620.

36
ACCEPTED MANUSCRIPT

1 Mahamuni, N.N., Adewuyi, Y.G., 2010. Advanced oxidation processes (AOPs) involving
2 ultrasound for waste water treatment: A review with emphasis on cost estimation. Ultrason.
3 Sonochem. 17, 990-1003.

4 Mahmoodi, N.M., 2013. Photocatalytic ozonation of dyes using multiwalled caron nanotube. J.
5 Mol. Catal. A. Chem. 366, 254-260.

PT
6 Martínez, S.S., Uribe, E.V., 2012. Enhanced sonochemical degradation of azure B dye by the
7 electroFenton process. Ultrason. Sonochem. 19, 174-178.

RI
8 McMullan, G., Meehan, C., Conneely, A., Kirby, N., Robinson, T., Nigam, P., Banat, I.M.,
9 Marchant, R., Smyth, W.F., 2001. Microbial decolourisation and degradation of textile dyes.
10 Appl. Microbiol. Biotechnol. 56, 81-87.

SC
11 Mehrjouei, M., Muller, S., Moller, D., 2014. Energy consumption of three different advanced
12 oxidation methods for water treatment: a cost effectiveness study. J. Clean. Prod. 65, 178-183.

U
13 Méndez-Díaz, J.D., Sánchez-Polo, M., Rivera-Utrilla, J., Bautista-Toledo, M.I., 2009.
14 Effectiveness of different oxidizing agents for removing sodium dodecylbenzenesulphonate in
AN
15 aqueous systems. Water Res. 43, 1621-1629.

16 Meric, S., Kaptan, D. Olmez, T., 2004. Color and COD removal from wastewater containing
M

17 Reactive Black 5 using Fenton’s oxidation process. Chemosphere 54, 435- 441.

18 Métivier‐Pignon, H., Faur‐Brasquet, C., Jaouen, P., Le Cloirec, P., 2003. Coupling ultrafiltration
D

19 with an activated carbon cloth for the treatment of highly coloured wastewaters : A
20 techno‐economic study. Environ. Technol. 24, 735-743.
TE

21 Modin, O., Fukushi, K., 2013. Production of high concentrations of H2O2 in a bioelectrochemical
22 reactor fed with real municipal wastewater. Environ. Technol. 34, 2737-2742.
EP

23 Moon, H., Chang, I.S., Kim, B.H., 2006. Continuous electricity production from artificial
24 wastewater using a mediator-less microbial fuel cell. Bioresour. Technol. 97, 621-627.

25 Muruganandham, M., Swaminathan, M., 2006. Photocatalytic decolourisation and degradation of


C

26 Reactive Orange 4 by TiO2-UV process. Dyes Pigm. 68, 133-142.


AC

27 Muthukumar, M., Sargunamani, D., Selvakumar, N., Venkata Rao, J., 2004. Optimisation of
28 ozone treatment for colour and COD removal of acid dye effluent using central composite design
29 experiment. Dyes Pigm. 63, 127-134.

30 Nawrocki, J., Kasprzyk-Hordern, B., 2010. The efficiency and mechanisms of catalytic
31 ozonation. Appl. Catal. B. Environ. 99, 27-42.

32 Neelavannan, M.G., Ahmed Basha, C., 2008. Electrochemical-assisted photocatalytic


33 degradation of textile washwater. Sep. Purif. Technol. 61, 168-174.

37
ACCEPTED MANUSCRIPT

1 Neyens, E., Baeyens, J., 2003. A review of classic Fenton’s peroxidation as an advanced
2 oxidation technique. J. Hazard. Mater. 98, 33-50.

3 Ni, M., Leung, M.K.H., Leung, D.Y.C., Sumathy, K., 2007. A review and recent developments
4 in photocatalytic water-splitting using for hydrogen production. Sust. Energ. Rev. 11, 401-425.

5 Oguz, E., Keskinler, B., Çelik, Z., 2005. Ozonation of aqueous Bomaplex Red CR-L dye in a

PT
6 semi-batch reactor. Dyes Pigm. 64, 101-108.

7 Okitsu, K., Iwasaki, K., Yobiko, Y., Bandow, H., Nishimura, R., Maeda, Y., 2005. Sonochemical

RI
8 degradation of azo dyes in aqueous solution: A new heterogeneous kinetics model taking into
9 account the local concentration of OH radicals and azo dyes. Ultrason. Sonochem. 12, 255-262.

SC
10 Özcan, A., Oturan, M.A., Oturan, N., Şahin, Y., 2009. Removal of Acid Orange 7 from water by
11 electrochemically generated Fenton's reagent. J. Hazard. Meter. 163, 1213-1220.

12 Ozer, R.R., Ferry, J.L., 2001. Investigation of the Photocatalytic Activity of

U
13 TiO2−Polyoxometalate Systems. Environ. Sci. Technol. 35, 3242-3246.
AN
14 Ozturk, E., Yetis, U., Dilek, F.B., Demirer, G.N. 2009. A chemical substitution study for a wet
15 processing textle mill in Turkey. J. Clean. Prod. 17, 239- 247.
M

16 Panizza, M., Cerisola, G., 2009. Electro-Fenton degradation of synthetic dyes. Water Res. 43,
17 339-344.

Paprowicz, J., Słodczyk, S., 1988. Application of biologically activated sorptive columns for
D

18
19 textile waste water treatment. Environ. Technol. Lett. 9, 271-280.
TE

20 Park, S.-E., Huang, L., Lee, C.W., Chang, J.-S., 2000. < Generation of H2O2 from H2 and O2
21 over zeolite beta containing Pd and heterogenized organic compounds. Catal. Today 61, 117-
22 122.
EP

23 Parker, P.M., 2004. Global Trade Perspective 2005 - Hydrogen Peroxide. ICON Group
24 International, Inc., p. 1.
C

25 Parker, P.M., 2010. The 2011 Import and Export Market for Hydrogen Peroxide in Europe.
26 Regional Trade Reports, N.PAG.
AC

27 Patil, B.N., Naik, D.B., Shrivastava, V.S., 2011. Photocatalytic degradation of hazardous
28 Ponceau-S dye from industrial wastewater using nanosized niobium pentoxide with carbon.
29 Desalination 269, 276-283.

30 Peng, X., Yu, H., Wang, X., Gao, N., Geng, L., Ai, L., 2013. Enhanced anode performance of
31 microbial fuel cells by adding nanosemiconductor goethite. J. Power Sources 223, 94-99.

38
ACCEPTED MANUSCRIPT

1 Peralta-Hernández, J.M., Meas-Vong, Y., Rodríguez, F.J., Chapman, T.W., Maldonado, M.I.,
2 Godínez, L.A., 2008. Comparison of hydrogen peroxide-based processes for treating dye-
3 containing wastewater: Decolorization and destruction of Orange II azo dye in dilute solution.
4 Dyes Pigm.76, 656-662.

5 Peternel, I.T., Koprivanac, N., Božić, A.M.L., Kušić, H.M., 2007. Comparative study of
6 UV/TiO2, UV/ZnO and photo-Fenton processes for the organic reactive dye degradation in

PT
7 aqueous solution. J. Hazard. Meter. 148, 477-484.

8 R. Bond, D., R. Lovley, D., 2002. Electricity Production by Geobacter sulfurreducens Attached

RI
9 to Electrodes. Appl. Environ. Microbiol. 69, 1548-1555.

10 Rabaey, K., Lissens, G., Siciliano, S., Verstraete, W., 2003. A microbial fuel cell capable of

SC
11 converting glucose to electricity at high rate and efficiency. Biotechnol. Lett. 25, 1531-1535.

12 Rismani-Yazdi, H., Carver, S.M., Christy, A.D., Tuovinen, O.H., 2008. Cathodic limitations in
13 microbial fuel cells: An overview. J. Power Sources 180, 683-694.

14
U
Rittmann, B.E., 2008. Opportunities for renewable bioenergy using microorganisms. Biotechnol.
AN
15 Bioeng. 100, 203-212.

16 Rivera-Utrilla, J., Sánchez-Polo, M., 2002. Ozonation of 1,3,6-naphthalenetrisulphonic acid


M

17 catalysed by activated carbon in aqueous phase. Appl. Catal. B. Environ. 39, 319-329.

18 Robinson, T., McMullan, G., Marchant, R., Nigam, P., 2001. Remediation of dyes in textile
effluent: a critical review on current treatment technologies with a proposed alternative.
D

19
20 Bioresour. Technol. 77, 247-255.
TE

21 Rozendal, R.A., Hamelers, H.V.M., Rabaey, K., Keller, J., Buisman, C.J.N., 2008. Towards
22 practical implementation of bioelectrochemical wastewater treatment. Trends biotechnol. 26,
23 450-459.
EP

24 Rozendal, R.A., Leone, E., Keller, J., Rabaey, K., 2009. Efficient hydrogen peroxide generation
25 from organic matter in a bioelectrochemical system. Electrochem. Commun. 11, 1752-1755.
C

26 Ruiz, E.J., Arias, C., Brillas, E., Hernández-Ramírez, A., Peralta-Hernández, J.M., 2011.
27 Mineralization of Acid Yellow 36&#xa0;azo dye by electro-Fenton and solar photoelectro-
AC

28 Fenton processes with a boron-doped diamond anode. Chemosphere 82, 495-501.

29 Sahunin, C., Kaewboran, J., Hunsom, M., 2006. Treatment of textile dyeing wastewater by photo
30 oxidation using UV/H2O2/Fe+2 Reagents. Sci. Asia 32, 181-186.

31 Sala, M., Gutierrez-Bouzan, M.C., 2014. Electrochemical treatment of industrial wastewater and
32 effluent reuse at laboratory and semi-industrial scale. J. Clean. Prod. 65, 458-464.

39
ACCEPTED MANUSCRIPT

1 Sánchez-Polo, M., von Gunten, U., Rivera-Utrilla, J., 2005. Efficiency of activated carbon to
2 transform ozone into OH radicals: Influence of operational parameters. Water Res. 39, 3189-
3 3198.

4 Sathishkumar, P., Mangalaraja, R.V., Anandan, S., Ashokkumar, M., 2013. CoFe2O4/TiO2
5 nanocatalysts for the photocatalytic degradation of Reactive Red 120 in aqueous solutions in the
6 presence and absence of electron acceptors. Chem. Eng. J. 220, 302-310.

PT
7 Selli, E., 2002. Synergistic effects of sonolysis combined with photocatalysis in the degradation
8 of an azo dye. Phys. Chem. Chem. Phys. 4, 6123-6128.

RI
9 Sevimli, M.F., Sarikaya, H.Z., 2005. Effect of Some Operational Parameters on the
10 Decolorization of Textile Effluents and Dye Solutions by Ozonation. Environ. Technol. 26, 135-

SC
11 144.

12 Sheriff, T.S., Cope, S., Ekwegh, M., 2007. Calmagite dye oxidation using in situ generated
13 hydrogen peroxide catalysed by manganese(ii) ions. Dalton Trans. 5119.

14
U
Solanki, K., Subramanian, S., Basu, S., 2013. Microbial fuel cells for azo dye treatment with
AN
15 electricity generation: A review. Bioresour. Technol. 131, 564-571.

16 Song, S., Xu, L., He, Z., Chen, J., Xiao, X., Yan, B., 2007a. Mechanism of the Photocatalytic
M

17 Degradation of C.I. Reactive Black 5 at pH 12.0 Using SrTiO3/CeO2 as the Catalyst.


18 Environmental Science & Technology 41, 5846-5853.

Song, S., Xu, L., He, Z., Ying, H., Chen, J., Xiao, X., Yan, B., 2008. Photocatalytic degradation
D

19
20 of C.I. Direct Red 23 in aqueous solutions under UV irradiation using SrTiO3/CeO2 composite as
21 the catalyst. J. Hazard. Meter. 152, 1301-1308.
TE

22 Song, S., Ying, H., He, Z., Chen, J., 2007b. Mechanism of decolorization and degradation of CI
23 Direct Red 23 by ozonation combined with sonolysis. Chemosphere 66, 1782-1788.
EP

24 Staehelin, J., Hoigne, J., 1982. Decomposition of ozone in water: rate of initiation by hydroxide
25 ions and hydrogen peroxide. Environ. Sci. Technol .16, 676-681.
C

26 Stock, N.L., Peller, J., Vinodgopal, K., Kamat, P.V., 2000. Combinative Sonolysis and
27 Photocatalysis for Textile Dye Degradation. Environ. Sci. Technol. 34, 1747-1750.
AC

28 Stylidi, M., Kondarides, D.I., Verykios, X.E., 2003. Pathways of solar light-induced
29 photocatalytic degradation of azo dyes in aqueous TiO2 suspensions. Appl. Catal. B. Environ.
30 40, 271-286.

31 Sun, J., Bi, Z., Hou, B., Cao, Y.-q., Hu, Y.-y., 2011. Further treatment of decolorization liquid of
32 azo dye coupled with increased power production using microbial fuel cell equipped with an
33 aerobic biocathode. Water Res. 45, 283-291.

40
ACCEPTED MANUSCRIPT

1 Sun, J., Qiao, L., Sun, S., Wang, G., 2008. Photocatalytic degradation of Orange G on nitrogen-
2 doped TiO2 catalysts under visible light and sunlight irradiation. J. Hazard. Meter. 155, 312-319.

3 Tan, C., Xiang, B., Li, Y., Fang, J., Huang, M., 2011. Preparation and characteristics of a nano-
4 PbO2 anode for organic wastewater treatment. Chem. Eng. J. 166, 15-21.

5 Tanaka, K., Padermpole, K., Hisanaga, T., 2000. Photocatalytic degradation of commercial azo

PT
6 dyes. Water Res. 34, 327-333.

7 Tavares, M.G., da Silva, L.V.A., Sales Solano, A.M., Tonholo, J., Martínez-Huitle, C.A., Zanta,

RI
8 C.L.P.S., 2012. Electrochemical oxidation of Methyl Red using Ti/Ru0.3Ti0.7O2 and Ti/Pt
9 anodes. Chem. Eng. J. 204–206, 141-150.

SC
10 Tehrani-Bagha, A.R., Mahmoodi, N.M., Menger, F.M., 2010. Degradation of a persistent organic
11 dye from colored textile wastewater by ozonation. Desalination 260, 34-38.

12 Tezcanli-Güyer, G., Ince, N.H., 2004. Individual and combined effects of ultrasound, ozone and

U
13 UV irradiation: A case study with textile dyes. Ultrasonics 42, 603-609.
AN
14 Thompson, L.H., Doraiswamy, L.K., 1999. Sonochemistry: Science and Engineering. Ind. Eng.
15 Chem. Res. 38, 1215-1249.
M

16 Tosik, R., 2005. Dyes Color Removal by Ozone and Hydrogen Peroxide: Some Aspects and
17 Problems. Ozone Sci. Eng. 27, 265-271.

Turhan, K., Durukan, I., Ozturkcan, S.A., Turgut, Z., 2012. Decolorization of textile basic dye in
D

18
19 aqueous solution by ozone. Dyes Pigm. 92, 897-901.
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20 Umar, M., Aziz, H.A., 2013. Photocatalytic Degradation of Organic Pollutants in Water.

21 Vajnhandl, S., Le Marechal, A.M., 2007. Case study of the sonochemical decolouration of textile
EP

22 azo dye Reactive Black 5. J. Hazard. Mater. 141, 329-335.

23 Vecitis, C.D., Lesko, T., Colussi, A.J., Hoffmann, M.R., 2010. Sonolytic Decomposition of
24 Aqueous Bioxalate in the Presence of Ozone. J. Phys. Chem. A. 114, 4968-4980.
C

25 Vlyssides, A.G., Papaioannou, D., Loizidoy, M., Karlis, P.K., Zorpas, A.A., 2000. Testing an
AC

26 electrochemical method for treatment of textile dye wastewater. Waste Manage. 20, 569-574.

27 Voloshin, Y., Halder, R., Lawal, A., 2007. Kinetics of hydrogen peroxide synthesis by direct
28 combination of H2 and O2 in a microreactor. Catal. Today 125, 40-47.

29 Vončina, D.B., Majcen-Le-Marechal, A., 2003. Reactive dye decolorization using combined
30 ultrasound/H2O2. Dyes Pigm. 59, 173-179.

41
ACCEPTED MANUSCRIPT

1 Wang, A., Guo, W., Hao, F., Yue, X., Leng, Y., 2014. Degradation of Acid Orange 7 in aqueous
2 solution by zero-valent aluminium under ultrasonic irradiation. Ultrason. Sonochem. 21, 572-
3 575.

4 Wang, W., Qu, Y., Yang, B., Liu, X., Su, W., 2012. Lactate oxidation in pyrite suspension: A
5 Fenton-like process in situ generating H2O2. Chemosphere 86, 376-382.

PT
6 Wang, X., Feng, Y., Ren, N., Wang, H., Lee, H., Li, N., Zhao, Q., 2009. Accelerated start-up of
7 two-chambered microbial fuel cells: Effect of anodic positive poised potential. Electrochim. Acta
8 54, 1109-1114.

RI
9 Wu, C., Kuo, C., Chang, C., 2008. Decolorization of C.I. Reactive Red 2 by catalytic ozonation
10 processes. J. Hazard. Mater. 153, 1052-1058.

SC
11 Wu, C.H., 2008. Effects of sonication on decolorization of C.I. Reactive Red 198 in UV/ZnO
12 system. J. Hazard. Mater. 153, 1254-1261.

U
13 Xu, X.-R., Li, H.-B., Wang, W.-H., Gu, J.-D., 2005. Decolorization of dyes and textile
14 wastewater by potassium permanganate. Chemosphere 59, 893-898.
AN
15 Yadav, A.K., Dash, P., Mohanty, A., Abbassi, R., Mishra, B.K., 2012. Performance assessment
16 of innovative constructed wetland-microbial fuel cell for electricity production and dye removal.
M

17 Ecol. Eng. 47, 126-131.

18 Yalfani, M.S., Contreras, S., Medina, F., Sueiras, J.E., 2011. Hydrogen substitutes for the in situ
generation of H2O2: An application in the Fenton reaction. J. Hazard. Mater. 192, 340-346.
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19

20 Yang, S., Wang, P., Yang, X., Shan, L., Zhang, W., Shao, X., Niu, R., 2010. Degradation
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21 efficiencies of azo dye Acid Orange 7 by the interaction of heat, UV and anions with common
22 oxidants: Persulfate, peroxymonosulfate and hydrogen peroxide. J. Hazard. Mater. 179, 552-
23 558.
EP

24 Yeh, R.Y.-L., Hung, Y.-T., Liu, R.L.-H., Chiu, H.-M., Thomas, A., 2002. Textile Wastewater
25 Treatment With Activated Sludge And Powdered Activated Carbon. Int. J. Environ. Stud. 59,
26 607-622.
C

27 Yu, Y., Du, F.-P., Yu, J.C., Zhuang, Y.-Y., Wong, P.-K., 2004. One-dimensional shape-
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28 controlled preparation of porous Cu2O nano-whiskers by using CTAB as a template. J. Solid


29 State Chem. 177, 4640-4647.

30 Zhang, H., Duan, L., Zhang, Y., Wu, F., 2005. The use of ultrasound to enhance the
31 decolorization of the C.I. Acid Orange 7 by zero-valent iron. Dyes Pigm. 65, 39-43.

32 Zhang, L., Li, J., Chen, Z., Tang, Y., Yu, Y., 2006. Preparation of Fenton reagent with H2O2
33 generated by solar light-illuminated nano-Cu2O/MWNTs composites. Appl. Catal. A. Gen. 299,
34 292-297.

42
ACCEPTED MANUSCRIPT

1 Zhang, S., Wang, D., Zhang, S., Zhang, X., Fan, P., 2013a. Ozonation and carbon-assisted
2 Ozonation of Methylene Blue as Model Compound: Effect of solution pH. Procedia Environ.
3 Sci. 18, 493-502.

4 Zhang, X.b., Dong, W.-y., Yang, W., 2013b. Decolorization efficiency and kinetics of typical
5 reactive azo dye RR2 in the homogeneous Fe(II) catalyzed ozonation process. Chem. Eng. J.
6 233, 14-23.

PT
7 Zhang, Y.-G., MA, L.-L., Li, J.-L., YU, Y., 2007. In Situ Fenton Reagent Generated From
8 TiO2/Cu2O Composite Film: a New Way to Utilize TiO2 Under Visible Light Irradiation

RI
9 Environ. Sci. Technol.

10 Zhao, J., Zhang, Y., Quan, X., Chen, S., 2010. Enhanced oxidation of 4-chlorophenol using

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11 sulfate radicals generated from zero-valent iron and peroxydisulfate at ambient temperature. Sep.
12 Purif. Technol. 71, 302-307.

13 Zhou, M., Chi, M., Luo, J., He, H., Jin, T., 2011. An overview of electrode materials in microbial

U
14 fuel cells. J. Power Sources 196, 4427-4435.
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15 Zhu, X., Logan, B.E., 2013a. Using single-chamber microbial fuel cells as renewable power
16 sources of electro-Fenton reactors for organic pollutant treatment. J. Hazard. Mater. 252-253,
17 198-203.
M

18 Zhu, X., Logan, B.E., 2013b. Using single-chamber microbial fuel cells as renewable power
19 sources of electro-Fenton reactors for organic pollutant treatment. J. Hazard. Mater. 252–253,
198-203.
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20

21 Zhu, X., Ni, J., 2009. Simultaneous processes of electricity generation and p-nitrophenol
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22 degradation in a microbial fuel cell. Electrochem. Commun. 11, 274-277.

23 Zhuang, L., Zhou, S., Yuan, Y., Liu, M., Wang, Y., 2010. A novel bioelectro-Fenton system for
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24 coupling anodic COD removal with cathodic dye degradation. Chem. Eng. J. 163, 160-163.

25
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List of Table Captions

Table 1. Redox potential of oxidizing agents

Table 2. Application of AOPs for in-situ production of H2O2/HO• for textile wastewater
treatment

PT
Table 3. Electrochemical and microbial fuel cells for in-situ production of H2O2/HO•

Table 4. Ultrasound as an auxiliary tool for AOPs: In-situ production of H2O2/HO•

RI
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AC
ACCEPTED MANUSCRIPT

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Table 1. Redox potential of oxidizing agents

RI
Oxidizing agent Redox potential Reference

SC
Hydrogen peroxide(H2O2) 1.8 (Neyens and Baeyens,
2003; Kelley et al.,
2003)
Hydroxyl radicals(HO•) 2.8 (Kelley et al., 2003)
Holes(h+)
U 2.53 (Fujishima et al., 2000)
AN
Sulfate free radicals(SO4• ‾) 2.5-3.1 (Kelley et al., 2003;
Zhao et al., 2010)
M

Ozone(O3) 2.1 (Kelley et al., 2003)


Persulfate anions(S2O8‾2) 2.01 (Kelley et al., 2003;
Liang and Lee, 2008)
D

Permanganate (MnO4‾) 1.70 (Kelley et al., 2003)


TE
C EP
AC
ACCEPTED MANUSCRIPT

Table 2. Application of AOPs for in-situ production of H2O2/HO• for textile wastewater treatment

Dye Catalyst/Oxidants [Dye] [Catalyst]/ pH/T(ºC) Color COD/TOC AOPs Reference


mg/L [Oxidants] removal employed

PT
AO7 Feº/air 100 0.0.3 g/L 3/- >99% COD: 97% Catalytic (Yang et al.,
RR120 COD: 87% (Zero valent 2010)

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AB9 COD: 93% iron)
RBBR Feº/air 100 50 3/- >99% COD: 96% Catalytic (Chang et al.,

SC
AB1 >99% COD: 50% (Zero valent 2009)
iron catalyst)
Calmagite Mn(II)/Tiron/ 0.1 mM 50µM/1.50mM/ 8/20 - - H2 substituted (Sheriff et al.,

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NH2OH 100mM organic 2007)

AN
compound
- Pd/Al2O3 with 0.001g 7/27 - - H2 substituted (Choudhary and
NH2OH & O2 organic Jana, 2007)

M
compound
RB19 O3 200 55g/m3 7/25 100% COD: 55% Ozonation (Tehrani-Bagha

D
TOC: 17% et al., 2010)
(800 mg/L

TE
of dye)
AR88 O3 0.5 mM 2g/hr 3/- 98.2% - Ozonation (Muthukumar et
11/- - COD: al., 2004)
EP
60.2%
Dye bath O3 2480a 11 to 111 4.7/20 60~91% 13~22% Ozonation (Sevimli and
C

effluent mg/L min Sarikaya, 2005)


Plant Effluent O3 665a 11 to 111 6.7/20 74% 11~33% Ozonation (Sevimli and
AC

mg/L min Sarikaya, 2005)


Raw O3 1700a 18.5 mg/L 8.3/- 98-99% 7.64~15.88 Ozonation (Baban et al.,
wastewater % 2003)
ACCEPTED MANUSCRIPT

Table 2. Continued

Dye Catalyst/Oxidants [Dye] [Catalyst]/ pH/T(ºC) Color COD/TOC AOPs Reference


mg/L [Oxidants] removal employed

PT
Biologically O3 450a 18.5 mg/L 8.3/- 70-75% 18.88% Ozonation (Baban et al.,
treated 2003)

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wastewater
Congo red O3/O2 500 0.5L/min 12/25 ----- COD: 85% Ozonation (Faouzi et al.,

SC
TOC: 81% 2009)
Reactive O3 230 132mg/L -/20 100% TOC:80% Ozonation (Chu et al.,

U
Black 5 (micro-bubbles) 2007)
Acid Red 14 O3 200 19.26g/hr -/25 98% COD: 45% Ozonation (Gao et al.,

AN
2012)
C.I Reactive O3/UV/TiO2 100 1 mg/L 6.9/- Catalytic (Wu et al.,

M
Red 2 Mn(II)/O3 0.1 mg/L 2/- >95% 17-21% ozonation 2008)
MnO2/O3 0.8 mg/L 2/-

D
O3:

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200ml/min
RR194 O3 /GAC 100 O3: 28 mg/L 6.3/- COD:80% Catalytic (Gul et al.,
GAC: 10 TOC: 50% ozonation 2007)
EP
g/L
RY145 5.9/- COD:90%
C

TOC: 50%
AC

Brilliant Red Cu2O/MWNT/ 200 1g/L 6/- - - solar light (Zhang et al.,
Dye FeSO4 10mmol/L catalytic 2006)
process
ACCEPTED MANUSCRIPT

Table 2. Continued

Dye Catalyst/Oxidants [Dye] [Catalyst]/ pH/T(ºC) Color COD/TOC AOPs Reference


mg/L [Oxidants] removal employed

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AO7 TiO2/UV 40 1g/L / 6 W 6/20 - - Photocatalysis (Chen et al.,
lamp 2005)

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RB5 TiO2/SiO2 in the - TiO2/SiO2 : 1 5.8/21 - - Photocatalysis (Aguedach et
presence of ions (mass ratio) al., 2008)

SC
RR45 UV/TiO2 80 0.5 g/L/ 125 5/ 25 59% TOC: 23% Photocatalysis (Peternel et
W al., 2007)

U
UV/ZnO 80 2.5 g/L/ 58.3% TOC: 22.4% Photocatalysis (Peternel et

AN
125W al., 2007)
MB UV/SiO2/TiO2- 2.5 250W/ 11/25 - - Photocatalysis (Liu et al.,
Ce 100 mg/L 2012)

M
Ce:0.2%
Procion UV/TiO2(P-25) 50 100W 5/- ~100% COD: 89% Photocatalysis (Barakat,

D
yellow H- mercury 2011)

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EXL lamp/1g/L
Ponceau-S Nb2O5/CAC 40 400W/5g/L/1 8/- TOC:78.95% Photocatalysis (Patil et al.,
EP
dye g/L COD: 86.2% 2011)
MB ZnO/SnO2 10 8W/ 0.50 g/L 12/25 96% - Photocatalysis (Chiang and
Air: Lin, 2013)
C

400ml/min
AC

RR180 TiO2 150 24W/2g/L 7/25 97.17% TOC: photocatalysis (Akyol and
83.05% Bayramoglu,
2008)
ACCEPTED MANUSCRIPT

Table 2. Continued

Dye Catalyst/Oxidants [Dye] [Catalyst]/ pH/T(ºC) Color COD/TOC AOPs Reference


mg/L [Oxidants] removal employed

PT
C.I. Direct SrTiO3/CeO2 100 250W/1.5g/L 12/25 97% COD: 69% Photocatalysis (Song et al.,
Red 23 2008)

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Methylene TiO2/Cu2O with 100 2 4/- Catalytic/ (Zhang et al.,
Blue FeSO4 & EDTA Photocatalytic 2007)

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Reactive SrTiO3/CeO2 100 200W/ 12/- 100% TOC:57% Catalytic/ (Song et al.,
Black 5 0.02gL-1/ Photocatalytic 2007)

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0.2m3hr-1
Procion blue Titanium anode 100 6W/2A/dm3/65 3.5/- 100% COD: 90% Electro- (Neelavannan

AN
dye coated with mg/L photocatalytic et al., 2008)
70TiO2/30RuO2/

M
TiO2 catalysts
Acid Violet ZnO/UV/air 5×10‾4 M 2g/L/ 8W/ 9/- ------ COD: Photocatalytic (Krishnakumar

D
7 8.1mL/s 94.4% and

TE
Swaminathan,
2011)
Eosin Y ZnO/UV 50 0.4g/16W 6.9/30 39% COD: 8.1% Photocatalytic (Chakrabarti
EP
and Dutta,
2004)
C

Methylene ZnO/UV 50 0.4g/16W 6.9/30 58% COD: 24% Photocatalytic (Chakrabarti


AC

Blue and Dutta,


2004)
RR2 O3 /Fe(II) 0.45mM 10mg/hr/ 7/25 k2: - Catalytic (Zhang et al.,
0.9mM 2248M/s** ozonation 2013b)
MB O3 /CNTs 30mg/L 5g/hr/0.1g 11/20 100% TOC: 80% Catalytic (Zhang et al.,
ozonation 2013b)
ACCEPTED MANUSCRIPT

Table 2. Continued

Dye Catalyst/Oxidants [Dye] [Catalyst]/ pH/T(ºC) Color COD/TOC


AOPs Reference

PT
mg/L [Oxidants] removal employed
RR198/ UV/O3/MWNTs 150 9W/0.03g/L3/25 100%
- Photocatalytic (Mahmoodi,

RI
DG6 ozonation 2013)
*AO7: Acid Orange 7; RR120: Reactive Red 120; AB9: Acid blue 9; RBBR: I.C Remazol Brilliant Blue; AB1: C.I Acid Black 1;

SC
RB19: C.I Reactive 19; AR88: Acid Red 88; RR2: C.I. Reactive Red 2 ; CR: Congo Red; RR194: C.I. Reactive Red 194; RR145: C.I.

U
Reactive Red 145; AO7: Acid Orange 7; RB5: Reactive Black 5; RR45: C.I Reactive Red 45; MB: Methylene Blue; RR180: Remazol

AN
red F-3B; R23: C.I. Direct Red 23; 4BS: C.I. Direct Red 23; AV7: Acid Violet 7; RR2: Reactive Red 2; MB: Methylene Blue; RR198:

Reactive red 198; DG: Direct Green

M
a

D
Concentration of real wastewater is always reported in terms of COD value.

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**Rate constant EP
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Table 3. Electrochemical and microbial fuel cells for in-situ production of H2O2/HO•

Dye Anode Cathode [Dye] [Catalyst]/ pH/T Color COD/TOC Methods Reference

PT
(mg/L) [Oxidant] (ºC) removal
AZ Boron doped zirconium 500* I: 30 mA/cm2 -/25 100% COD: 95% Electrochemical (Bensalah,

RI
diamond oxidation et al., 2009)
MR Ti/Pt Titanium 100 40mA/cm2 -/25 100% TOC: 50% Electrochemical (Tavares et

SC
plates oxidation al., 2012)
MR Ti/Ru0.3/Ti0.7O2 Titanium 100 40mA/cm2 -/25 100% TOC: 10- Electrochemical (Tavares et
plates 35% oxidation al., 2012)

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Alizarin Pt Grid GDE 120 Fe+2: 1mM 3/35 TOC: 93% Electrochemical (Panizza and

AN
Red Air: 20mL/s oxidation Cerisola,
2009)

M
TDFW Titanium alloy Stainless 1250* - 5/42 100% 90% Electrochemical (Vlyssides et
Steel oxidation al., 2000)

D
DW Titanium alloy Stainless 3325* - 5/42 100% 77% Electrochemical (Vlyssides et
Steel oxidation al., 2000)

TE
CR Boron doped Stainless 500 I: 30mA/cm2 7/25 ---- TOC:100% Electrochemical (Faouzi
diamond steel COD:100% oxidation Elahmadi et
EP
al., 2009)
AO7 carbon felt carbon felt 0.10 mM Fe+3: 0.1mM/ 3-2.8/- TOC: 92% Electro fenton (Özcan et al.,
0.3A 2009)
C

+2
OG-II Graphite cloth Graphite 50 Fe : 0.2mM; 3/- 100% TOC: 80% Photo-electro (Peralta-
AC

cloth UV:75mW/m2 fenton Hernández et


I: 300mA/cm2 al., 2008)
OG-II Graphite cloth Graphite 50 Fe+2: 0.2mM; 3/- 100% TOC: 63% Electro Fenton (Peralta-
cloth I: 300mA/cm2 Hernández et
al., 2008)
ACCEPTED MANUSCRIPT

Table 3. Continued

Dye Anode Cathode [Dye] [Catalyst]/ pH/T Color COD/TOC Methods Reference

PT
(mg/L) [Oxidant] (ºC) removal
AY36 Boron doped carbon-PTFE 108 Fe+2: 3/35 100% TOC: 71% Electro-Fenton (Ruiz et al.,

RI
diamond air diffusion 0.5mM/3A 2011)
cathode
Fe+2:

SC
AY36 Boron doped carbon-PTFE 108 3/35 100% TOC: 95% Solar Photo- (Ruiz et al.,
diamond air diffusion 0.5mM/3A Electro Fenton 2011)
cathode

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MO Graphite Rutile coated 10 Vis Light 2.4/25 73.4% ---- Microbial fuel (Ding et al.,

AN
graphite Cells 2010)
Azo dye Granular SPG rod 75 Fe+2:1 7/20 90% TOC: 31 % Microbial fuel (Fu et al.,

M
graphite mmole/L cells 2010)
Fe+3:0.5
mmole/L

D
TE
Real dye Granular Granular carbon 2080* Air: 12.4/30 Anode: COD:76% Microbial fuel (Kalathil et
waste carbon 200L/min 73% cells al., 2011)
EP
Cathode:
77%
ABRX3B Porous carbon Porous carbon 300 ------ -/30 ---- COD:24.8% Microbial fuel (Sun et al.,
C

cells 2011)
AC

RhB Carbon Felt Fe@Fe2O3/NFC 15 ------ 3/- ----- TOC: 90% Microbial fuel (Zhuang et
cells al., 2010)
Lissamine Graphite rod Graphite rod 10 Air: 2L/min 6-8 ----- TOC: 82% In-situ (Fernandez
Green B Fe+2: 0.05 Microbial fuel de Dios et
mole/L cells al., 2013)
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Table 3 Continued

Dye Anode Cathode [Dye] [Catalyst]/ pH/T Color COD/TOC Methods Reference

PT
(mg/L) [Oxidant] (ºC) removal
Crystal Graphite rod Graphite rod 10 Air: 2L/min 6-8 ----- TOC: 72% In-situ (Fernandez
Fe+2: 0.05

RI
Violet Microbial fuel de Dios et
mole/L cells al., 2013)
* Red; TDFW: Wastewater from total dyeing and finishing stages; DW: Wastewater from dyeing stages Alphazurine A: AZA; MR:

SC
Methylene; OG-II: Orange II; AY36: Acid Yellow 36; MO: Methyle Orange; ABRX3: Active Brilliant Red X-3B; RhB: Rhodamine

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Table 4. Ultrasound as an auxiliary tool for AOPs: In-situ production of H2O2/HO•

Dye Catalyst/O [Dye] [Catalyst]/ Frequency pH/T(ºC) Color COD/TOC Method Reference

PT
xidant (mg/L) [Oxidant] (kHz) removal
AO7 Fe0/GAC 1000 12g/2.3g 40 4/22 80% TOC: 57% Iron catalyzed (Liu et al., 2007)

RI
R5 O3 363 3.36 g/L 520 7/20 ----- TOC: 76% Ozonation (Ince and
Tezcanlı́, 2001)

SC
RY84 O3 500 4.5 g/h 20 4.5/25 ---- TOC: 56% Ozonation (He et al., 2007)
AB & O3 10µM ------ 500 6.5/15 TOC; 80% Ozonation (Destaillats et al.,
MO 2000)

U
4BS O3 100 3.2g/h 20 8/- 100% ------- Ozonation (Song et al.,

AN
2007)
RB19 US/O3 500 3.8g/h 20 8/- 100% TOC: 65% Ozonation (He et al., 2008)

M
Azure B Fe+2; 5×10‾4 0.8×10‾3 23 2.8/25 COD: ~85% Electro- (Martínez and
dye carbon mol/L mol/L Fenton Uribe, 2012)

D
electrode
RR198 ZnO/UV 20 1g/L/ 15W 40 7/30 ----- TOC: 75% photocatalytic (Wu, 2008)
AO7 UV/O3 50 µM 18W/40g/m
3
TE 520 5.5/25 TOC: 45% photo-
ozonation
(Tezcanli-Güyer
and Ince, 2004)
EP
AO7 UV 50 100mW/mm 20 -/22 65% ----- photolysis (Ma et al., 2006)
2
C

AO52 UV/TiO2 25 20/0.6g/L 200 -/25 100% TOC: 35% photocatalysis (Maezawa et al.,
AC

2007)
BB3 TiO2/MM 10 1g/L/300W - 7/25 80% - Photocatalysis (Khataee et al.,
2015)
AO7 ZVAI 20 2g/L/300W 20 2.5/25 96% - Ultrasound (Wang et al.,
2014)
ACCEPTED MANUSCRIPT

*AO7: Acid Orange 7; R5: C.I. Reactive 5; RY84: Reactive Yellow 84: AB: Azo Benzene dye; MO: Methyle Orange; 4BS: C.I.

Direct Red 23; RR198: C.I. Reactive Red 198; AO52: C.I. Acid Orange 52; GAC: Granular Activated Carbon; BB3: Basic Blue;

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TiO2/MM: TiO2/ montmorillonite; AO7: Acid Orange 7; Zero-valent iron: ZVAI

RI
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ACCEPTED MANUSCRIPT

List of Figure Captions

Fig. 1. World supplies of Exported Hydrogen Peroxide (2005)

Fig. 2. Conventional method for H2O2 production

Fig. 3. In-situ production of H2O2/ HO• by iron pyrite

PT
Fig. 4. Reaction pathways for in-situ production of HO•/H2O2 utilizing MNPs

Fig. 5. Schematic presentation of mechanism of oxidative species production

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Fig. 6. Electron transfer in presence of POM

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AN
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AC
ACCEPTED MANUSCRIPT

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Asia
N.America & 15%

U
Caribbean
20% Latin
America
AN
8%
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Middle East
& Others
2%
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Europe
55%
EP

Fig. 1. World supplies of Exported Hydrogen Peroxide (2005)


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H2O2

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O2
OH O
AN
M

OH O
D

H2
TE

Fig. 2. Conventional method for H2O2 production (Campos-Martin et al., 2006)


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AC
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Pyrite
Surface
Fe+3 defect site transformation

Fe+3
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H2O
Fe+3
Fe+2
AN
+e
˙OH H2O2
Fe+2
M

-e
H2O2
Fe+3 O2˙‾
D
TE

Fig. 3. In-situ production of H2O2/ HO• by iron pyrite (Wang et al., 2012)
C EP
AC
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PT
RI
U SC
Fe+2
O2 Fe+2 Fe +3 Fe +2 Fe +3
AN

e O2˙‾ H2O2 OH
MNPs
+
2H O2˙‾ O2
M

O2
D

Fig. 4. Reaction pathways for in-situ production of HO•/H2O2 utilizing MNPs (Fang et al.,
TE

2013)
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PT
RI
SC
O2

U
O2˙‾
AN
e‾
hv
TiO2 TiO2
h+
M
D

H+ + ˙OH
TE

H2O
EP

Fig. 5. Schematic presentation of mechanism of oxidative species production

(Stylidi et al., 2003)


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AC
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PT
RI
SC
O2

O2 • ‾

U
POMoxi
hv e‾
TiO2
AN
TiO2
h+

Orgoxi POMred
M

Org
D

Fig. 6. Electron transfer in presence of POM


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EP
C
AC

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