Desalination 299 (2012) 115

Contents lists available at SciVerse ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Trends in electro-Fenton process for water and wastewater treatment: An overview

P.V. Nidheesh, R. Gandhimathi
Department of Civil Engineering, National Institute of Technology, Tiruchirappalli, Tamilnadu, India

a r t i c l e

i n f o

a b s t r a c t
Organic compound, especially aromatic compound is the main pollutant in industrial efuent. Conventional wastewater treatment processes are inefcient for the removal of these types of toxic and hazardous pollutants from wastewater. Electro Fenton is one of the powerful and environmentally friendly emerging technologies for the remediation of wastewaters containing organic, especially aromatic compounds. This paper reviews the fundamentals and recent developments in electro Fenton process. Electro Fenton process utilizes different electrolytic reactors such as bubble reactor, lter press reactor, divided double-electrode electrochemical cell, divided three-electrode electrochemical cell and double compartment cell. Different cathodes as working electrode and anodes as counter electrode used in this process are analyzed. The effects of various operating parameters and their optimum ranges for maximum pollutant removal and mineralization are reviewed. Also various pollutants removed by this process are evaluated. Quick removal and mineralization of pollutants and their intermediate reaction products were reported. 2012 Elsevier B.V. All rights reserved.

Article history: Received 29 February 2012 Received in revised form 3 May 2012 Accepted 5 May 2012 Available online 14 June 2012 Keywords: Electro Fenton Wastewater treatment Degradation Organic pollutant

Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . E-Fenton reactors . . . . . . . . . . . . . . . . . . . . . . 2.1. Bubble reactor (BR) (A) . . . . . . . . . . . . . . . . 2.2. Filter press reactor (FPR) (B) . . . . . . . . . . . . . . 2.3. Divided double-electrode electrochemical cell (DDEC) (C) 2.4. Divided three-electrode electrochemical cell (DTEC) (D) . 2.5. Double compartment cell (DCC) (E) . . . . . . . . . . Electrode materials . . . . . . . . . . . . . . . . . . . . . . Kinetics of E-Fenton process . . . . . . . . . . . . . . . . . Affecting factors . . . . . . . . . . . . . . . . . . . . . . . 5.1. pH . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2. Oxygen sparging rate . . . . . . . . . . . . . . . . . 5.3. Temperature . . . . . . . . . . . . . . . . . . . . . 5.4. Applied current density . . . . . . . . . . . . . . . . 5.5. Fe 2+ concentration . . . . . . . . . . . . . . . . . . 5.6. Hydrogen peroxide concentration and feeding mode . . . 5.7. Distance between the electrodes . . . . . . . . . . . . 5.8. Nature of the supporting electrolyte . . . . . . . . . . Applications . . . . . . . . . . . . . . . . . . . . . . . . . 6.1. Dyes . . . . . . . . . . . . . . . . . . . . . . . . . 6.2. Pesticides and herbicides. . . . . . . . . . . . . . . . 6.3. Phenolic compounds. . . . . . . . . . . . . . . . . . 6.4. Leachate . . . . . . . . . . . . . . . . . . . . . . . 6.5. Drugs . . . . . . . . . . . . . . . . . . . . . . . . . 6.6. Others . . . . . . . . . . . . . . . . . . . . . . . . Degradation pathway of organic pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2 2 2 3 3 4 4 6 7 7 7 7 8 8 9 9 9 10 10 10 11 11 11 12 12

3. 4. 5.

6.

7.

Corresponding author. Tel.: + 91 431 2503171; fax: + 91 431 2500133. E-mail address: rgmathii@nitt.edu (R. Gandhimathi). 0011-9164/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2012.05.011

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

1. Introduction The focus on waste minimization and water conservation in the recent years resulted in the discovery of various treatment processes, one of them being Advanced Oxidation Processes (AOPs). These refer to the chemical treatment processes which follow oxidation route and are particularly employed to degrade biologically toxic and non degradable chemicals [1]. AOPs have been broadly dened as near ambient temperature treatment processes based on highly reactive radicals, especially the hydroxyl radical (OH) as the primary oxidant [2]. Many processes such as chemical oxidation, Fenton and photoFenton processes, ultraviolet (UV)-based processes, photo-catalytic redox processes, supercritical water oxidation, sonolysis, and electron beams and -ray irradiation come under advanced oxidation techniques [1]. The main function of AOPs is the generation of highly reactive free radicals. Hydroxyl radicals (HO) are effective in destroying organic chemicals because they are reactive electrophiles (electron preferring) that react rapidly and non-selectively with nearly all electron-rich organic compounds [3]. Among AOPs, oxidation using Fenton's reagent is an attractive and effective technology for the degradation of a large number of hazardous and organic pollutants because of the lack of toxicity of the reagents, eventually leaving no residues and the simplicity of the technology [4]. Maleic acid oxidation was the rst Fenton process reported by Fenton [5]. The main steps involved in the Fenton process are (i) Oxidation, (ii) Neutralization, (iii) Flocculation and (iv) Sedimentation. The Fenton process is most effective at pH near to 3 [6]. Normally the organic substances are removed at two stages of oxidation and coagulation [7]. Oxidation of organic substances is due to OH radicals and coagulation is ascribed to the formation of ferric hydroxo complexes [8]. The degradation mechanism of organic pollutants by Fenton reaction is given in Eqs. (1) to (4) [9,10]. The main advantages and disadvantages of Fenton process are given in Table 1. Fe
2

[2224]. Moreover, electricity as a clean energy source is used in the process, so the overall process does not create secondary pollutants [21]. Since E-Fenton process is not using any harmful reagents, it is an environment friendly method for water and wastewater treatment [25]. The typical mechanism of E-Fenton process is illustrated in Fig. 1. O2 2H 2e H2 O2

This review reports on the most recent experimental studies and developments in the eld of E-Fenton process. Fundamentals, experimental setups, main reactions, the parameters that affect these processes and various applications are discussed in detail. Different cathodes and anodes used for E-Fenton process are also analyzed in this work. 2. E-Fenton reactors Electrolytic reactor is one of the essential parts of E-Fenton process. There are several types of electrolytic cells used by researchers. Some of the important types of such cells are explained below. 2.1. Bubble reactor (BR) (Fig. 2A) The E-Fenton bubble reactor (a glass cylindrical reactor) having working volume of 0.675 L was operated in batch mode with total reux or continuous mode by Rosales et al. [27]. The cathode and anode bars were placed at a distance of 30 mm and 270 mm above the bottom of the cell, respectively. Steel bars having a total contact surface area of 3.14 cm 2 or graphite bars having a total contact surface area of 1.27 cm 2 were used. A constant potential difference (15 V) was applied with a power supply and the process was monitored with a multimeter. 2.2. Filter press reactor (FPR) (Fig. 2B) Prabhakaran et al. [28] used lter press reactor of capacity 2 L for the removal of resin efuents. The uid ow circuit consists of a reservoir, a magnetically driven self priming centrifugal pump, a ow meter and the electrolytic cell. The electrical circuit consists of a

H2 O2 Fe

OH HO

1 2

RH HO R H2 O where, RH denoting organic pollutants R Fe Fe

2 3

R Fe
3

HO Fe

OH

Table 1 Advantages and disadvantages of the Fenton process. Advantages Disadvantages Ferrous ions are consumed more rapidly than they are regenerated [12] Treatment of the sludge-containing Fe ions at the end of the wastewater treatment is expensive and needs large amount of chemicals and manpower [14] It is limited by a narrow pH range (pH 23) [16] Iron ions may be deactivated due to complexion with some iron complexing reagents such as phosphate anions and intermediate oxidation products [16] Additional water pollution caused by the homogeneous catalyst that added as an iron salt, cannot be retained in the process [11]

Electrochemical advanced oxidation processes (EAOPs) based on Fenton's reaction chemistry are eco-friendly methods that have recently received much attention for water remediation [18]. The most popular EAOP is the electro Fenton (E-Fenton) process [19]. EFenton process has two different congurations. In the rst one, Fenton reagents are added to the reactor from outside and inert electrodes with high catalytic activity are used as anode material while in the second conguration, only hydrogen peroxide is added from outside and Fe 2+ is provided from sacricial cast iron anodes [20]. Compared to the conventional Fenton process, the electro-Fenton process has the advantage of allowing better control of the process and avoiding the storing and transport of the H2O2 [21]. In this approach, H2O2 is continuously supplied to the contaminated solution by a twoelectron oxygen reduction in an acidic medium according to Eq. (5)

No energy input is necessary to activate hydrogen peroxide [11] Fenton's reagent is relatively inexpensive and the process is easy to operate and maintain [13] Short reaction time among all advanced oxidation processes [15] There is no mass transfer limitation due to its homogeneous catalytic nature [17] There is no form of energy involved as catalyst [17]

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

Fig. 1. Reaction mechanism of E-Fenton process [26].

regulated D.C. power supply; ammeter and the cell with the voltmeter are connected in parallel to the reactor.

volume. A digital DC power supply was connected to the electrodes. 1 N H2SO4 solution was used to adjust the pH between 3 and 5.

2.3. Divided double-electrode electrochemical cell (DDEC) (Fig. 2C) Reactor consisting of a 0.5 L glass beaker equipped with iron cathode and anode, installed in parallel was used by Kurt et al. [29]. Electrodes having a total effective electrode area of 45.0 cm2 were plunged into the beaker, containing tannery wastewater with a 0.4 L working

2.4. Divided three-electrode electrochemical cell (DTEC) (Fig. 2D) Zhou et al. [30] used DTEC reactor for the removal of methyl red from aqueous solution. This type of reactor contains a saturated calomel electrode (SCE) as reference electrode in addition to DDEC. Potential controlled electrolysis is the main purpose of SCE in DTEC.

(1)

(6)
(4)

(8) (7) (5) (1)

(9) (2) (3) (6) (6) (10)

(A)
A V

(B)
(1) (1)

(1)

(4) (13) (3) (4) (12)

(3)

(3)

(11)

(11)

Compartment 1

Compartment 2

(C)

(D)

(E)

Fig. 2. Schematic diagram of electrolytic reactors (A) BR [27] (B) FPR [28] (C) DDEC [29] (D) DTEC [30] (E) DCC [31] (1) power supply, (2) air compressor, (3) cathode, (4) anode, (5) control unit, (6) pumps, and (7) reux (8) rotameter (9) reservoir (10) electro chemical reactor (11) magnetic stirrer (12) oxygen tank (13) SEC.

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

Fig. 3. Recent citations of E-Fenton reactors.

Fig. 5. Comparison of recently used cathodes in E-Fenton process.

2.5. Double compartment cell (DCC) (Fig. 2E) DCC contains two compartments for electrolytic action. Yuan et al. [31] conducted experiments with DCC type of reactor for the degradation of Rhodamine B. Anode (Pt akes) and cathode (Pt akes) were placed in compartment 1, whereas in compartment 2 only cathode was placed. Direct current was provided by a power supply. Salt bridge lled with saturated K2SO4 and agar was used to connect the compartments. Micro bubbles of H2 and O2 were generated in compartment 1 by water electrolysis. Excess production of H + compared with OH results in lowering of pH in between 2 and 3. Cathode 2 in compartment 2 was used as a bypass to accumulate OH and to neutralize the low pH efuent from compartment 1 [31]. The recent citation of above reactors is shown in Fig. 3. From Fig. 3, it is observed that DDEC and DTEC reactors were used in the E-Fenton process by many researchers. 3. Electrode materials Selection of anode and cathode material is one of the signicant steps in E-Fenton process. For example, selection of unstable anode will cause deterioration of electrode in electrolytic cells. High-oxygen

overvoltage anode can produce hydroxyl radicals in E-Fenton process as in Eq. (6) [32], H2 OHO H e

Fig. 4. Comparison of recently used anodes in E-Fenton process.

Pt has been used for a long time as an electrode material due to its good conductivity and chemical stability even at high potentials and in very corrosive media [33]. Pt anode was used in more numbers for the degradation of pollutants in E-Fenton system (Fig. 4). The different forms of Pt anodes such as Pt sheet [19,3439], Pt gauze [25,4042], Pt foil [43], Pt akes [31], Pt grid [44,45], platinum plate [46], Pt mesh [39] etc. were used for the degradation of pollutants. But it is rarely used for a practical purpose because of its high cost. The various anodes other than Pt being recently used are shown in Fig. 4. Boron-doped diamond (BDD) electrode synthesized by the hot lament chemical vapor deposition technique on singlecrystal p-type Si (100) wafers was used by Isarain-Chavez et al. [47] for the mineralization of atenolol. Borra's et al. [48], zcan et al. [44], Pozzo et al. [49] and Sire's et al. [39] used BDD as an anode for wastewater treatment. Feasibility of Titanium (Ti) rod coated with IrO2/RuO2 in the E-Fenton process has been studied by Huang et al. [50] and Prabhakaran et al. [28]. RuO2/Ti mesh [51] and Iron [52] are some other types of anodes being used recently in E-Fenton process. Efciency of E-Fenton system depends more on efciency of cathode. Hence it is also known as working electrode. The various cathode materials used for laboratory-scale and pilot-scale are shown in Fig. 5. Commercial graphite felt [34], carbon felt [35,38,40,42,46,53], BDD plate [54],carbon-polytetrauoroethylene (PTFE) [37,39,43], graphitePTFE [30], graphite [55], reticulated vitreous carbon (RVC) [25,41], activated carbon ber (ACF) [51], Pt akes [31], carbon sponge [44], stainless steel [28,48,49], and titanium [52] are some of the recently used working electrodes in wastewater treatment. The details of anode and cathode including cell conguration are summarized in Table 2. Different congurations of cathode were also used by various researchers. The usage of composite electrodes is the emerging trend in E-Fenton system. Fan et al. [64] prepared Fe-CHI/Ni|ACF|Fe-CHI/ Ni sandwich lm cathode for the removal of Rhodamine B (Note: Fe-CHI Fe 2+-chitosan, Ni Nickel). Fe@Fe2O3/ACF [19], Cu2O/ CNTs/PTFE (Note: CNT Carbon Nanotubes) [36] and Fe@Fe2O3/ CNT [65] were also used as composite cathodes in E-Fenton process. Wang et al. [66] used platinum wire anode placed inside a hollow cylindrical cathode (2.9 cm diameter and 7 cm height), composed of one layer of polyacrylonitrile (PAN) based activated carbon ber cloth held by two plastic screens. This design makes the primary

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

Fig. 6. Pathway of Acid Red 97 degradation products using carbon felt cathode and Pt anode [40].

current or potential distribution more uniform. The oxygen gas from an oxygen cylinder was dispensed directly at the bottom of the hollow cylindrical cathode [66]. Different congurations were used for the application of electrochemical remediation techniques and the electrodes could be made of different materials. A signicant interest in the effectiveness of different electrode materials has recently arisen, with the use of stainless steel, graphite, platinum, PbO2, titanium compounds, boron doped diamond, and ceramics [27]. Oxidation capacity and removal efciency of different electrodes were also compared by different researchers. Sire's et al. [39] evaluated and compared the oxidizing power of the four E-Fenton systems to mineralize chlorophene solutions from the Total Organic Carbon (TOC) decay. Four different EFenton systems are: (i) a Pt/O2 diffusion cell (ii) a BDD/O2 diffusion cell (iii) a Pt/carbon felt cell and (iv) a BDD/carbon felt cell. A

continuous, but slow, TOC abatement with 52% of mineralization has been observed in the Pt/O2 diffusion cell after 660 min of electrolysis at 300 mA. But BDD/O2 diffusion cell has a removal efciency of 100% with rapid and total mineralization by applying high currents. This indicates that BDD has greater oxidation ability than that of Pt [39]. Isarain-Chavez et al. [56] also reported a same trend for degradation of atenolol from aqueous solution. The study demonstrated that BDD/carbon felt cell has higher oxidizing power than Pt/carbon felt cell to decontaminate the solution completely in a shorter time [56]. Siminiceanu et al. [37] reported better performances by the replacement of Pt with BDD anode. The mineralization current efciency becomes 1.53 to 3.25 times higher; whereas specic energy consumption is 1.43 to 2.81 times lower for BDD than that of Pt [37]. zcan et al. [44] reported that the formation rate of hydroxyl radicals and the decay rate of organics are faster on BDD anode than that of Pt. Hammami et al. [67] also

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

Table 2 Specications of anodes and cathodes used in E-Fenton process. No Reactor conguration 1 2 3 4 5 6 7 8 9 10 Open and undivided tank reactor containing 100 mL of solution A small, open and undivided cylindrical glass cell of 6 cm diameter and 250 mL capacity A glass reactor of capacity 600 mL 0.5 L glass beaker with a 0.4 L working volume. Borosil glass of capacity 0.5 L 0.40 L open and undivided cylindrical glass cell of internal diameter 60 mm Open undivided cylindrical glass cell of 6 cm diameter and 500 mL capacity Reservoir of capacity 5 L Glass reactor of capacity 300 mL Glass cell of 6 cm diameter and 250 mL capacity Anode specication Pt sheet of 99.99% purity Cylindrical Pt mesh or a 25 cm2 thin-lm boron-doped diamond Ti/RuO2 Iron plate of size 6.0 cm 7.5 cm Iron plate of size 55 mm 40 mm Cylindrical Pt grid 4.5 cm2 Pt cylindrical mesh Cathode specication Carbon-PTFE, carbon felt of area 3 cm2 Carbon-felt of size 14 cm 5 cm each side and 0.5 cm in width Stainless steel Iron of size 2.0 mm 6.0 cm 7.5 cm Graphite of size 75 mm 30 mm 6 mm and having an effective electrode area of 22 cm2. Carbon felt of dimensions 6 cm 8 cm 0.6 cm and 6 cm 17 cm 0.6 cm. Carbon felt having an area of 60 cm2 (15 cm 4 cm) Stainless steel cylinder with an inside diameter of 8 cm and a height of 17.5 cm Carbon felt of size 3 cm 5 cm. A 3 cm2 carbon-PTFE and 70 cm2 (17 cm 4.1 cm) carbon felt Reference [56] [57] [58] [29] [59] [60] [61] [32] [62] [39]

11 12 13 14 15 16 17 18 19 20

An undivided cylindrical glass cell of capacity 0.175 L Open undivided cylindrical glass cell of 6 cm diameter and 250 mL capacity Open undivided cylindrical glass cell of 500 mL capacity Cylindrical cell of 250 mL capacity An open undivided cylindrical glass cell of 100 mL capacity A divided thermostatic cell of 150 mL in volume Undivided glass electrochemical cell of 600 mL capacity An open and undivided cell with a capacity of 0.55 L An undivided glass electrochemical cell of capacity 500 mL Glass beakers of capacity 250 mL

Titanium rod coated with RuO2/IrO2 with an outside diameter of 1.5 cm and a height of 16 cm. Platinum gauze 3 cm2 Pt sheet, 3 cm2 BDD thin-lm deposited on conductive single crystal p-type Si wafers and a 4.5 cm2 Pt cylindrical mesh BDD thin-lm electrode which is deposited on Carbon sponge of size 1.0 cm 1.0 cm 4.0 cm both sides of a niobium substrate (3.0 cm 4.0 cm) 2 A 60 cm2 carbon felt 4.5 cm Pt cylindrical mesh Pt sheet of 1 cm2 area Pt gauze of area 6 cm2 Platinum (geometric area, 4 cm2) Pt sheet (purity: 99.99%) of area 2.0 cm2 Platinum gauze of an area 3.8 cm2 RuO2/Ti mesh of area 20 cm2 Platinum gauze of an area 3.8 cm Pt akes of size 1 1 cm
2

[44] [63] [34] [40] [54] [36] [25] [51] [41] [31]

Graphite felt of thickness = 0.4 cm, having an area of 9.5 cm2 Carbon felt of size 12.5 cm 4 cm BDD plate having geometric area of 2 cm2 Cu2O/CNTs/PTFE having an area of 3.0 cm2 Reticulated vitreous carbon (RVC) sheet of an area of 35 cm2 and thickness of 0.9 cm. 20 cm2 area of ACF felt RVC sheet of dimensions 5 cm 7 cm 0.9 cm Pt akes of size 1 1 cm

reported similar results for BDD and Pt anodes in the E-Fenton process. Wang et al. [51] compared the efciency of activated carbon ber and graphite cathodes for removing azo dye and Acid Red 14 from aqueous solution. For ACF cathode, after 360 min of electrolysis under the operating conditions of 0.36 A current, 1 mmol/L Fe2+ at pH 3, 70% TOC removal and 100% color removal were achieved. For the same operating conditions, graphite cathode shows less removal efciency than that of ACF [51]. Sudoh et al. [68] reported that the graphite was the best cathode material for electrogeneration of H2O2 while metal cathodes such as copper, stainless steel, lead and nickel were likely to decompose H2O2. This agrees with the results reported by Rosales et al. [27] for lissamine green B dye (LGB) removal from aqueous solution using graphite and stainless steel electrodes. The graphite electrodes have the highest LGB discoloration rate, with total discoloration after 10 h. Moreover, gradual corrosion was detected in stainless steel electrodes [27]. zcan et al. [44] compared the propham degradation rate for BDD//Pt, Pt//CS (Note: CS Carbon Sponge) and BDD//CS systems in acidic media. The decay rate of propham was higher in BDD//CS system than in BDD//Pt system. This result indicates that H2O2 production ability of CS was higher than that of Pt. A slight increase in removal rate was observed in the case of BDD//CS compared to Pt//CS system [44]. 4. Kinetics of E-Fenton process The decay of organic pollutants via E-Fenton process can be represented as: RH OH Oxidation products

treatment [69]. The rate of decay of organic pollutants can be written as: d RH k RHOH abs dt 8

Since [OH] is constant at steady state, kabs [OH] is equal to kapp. Where kabs and kapp are absolute and apparent rate constants, respectively. The value of kabs can be determined by kinetic competition method using the benzoic acid as standard substrate having a kabs value of 4.3 10 9 L mol 1 s 1 [70,71]. Eq. (8) can be rewritten as: d RH k RH app dt 9

Integration of Eq. (9) gives the rst order kinetic equation of EFenton process as: In RHo kapp t RHt 10

Where [RH]0 and [RH]t are the concentration of organic pollutant at beginning and time t, respectively. The kapp can be determined analytically from the slope of concentration vs. time plot in accordance with the above equation. The second order kinetic equation of EFenton is given as [4]:

7 RHt 1 RHo 1 ktRHo 11

As OH is a very reactive species it does not accumulate in the solution, and its concentration takes a steady-state value during

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115 Table 3 Optimum pH values of E-Fenton process in various studies. No 1 2 3 4 5 6 7 Pollutant Dyeing wastewater LGB Methyl red Sunset yellow FCF Dyeing wastewater Rhodamine B Biologically treated coking wastewater Electrodes Activated carbon ber-Pt wire Steel-graphite Graphite PTFE-Pt RVC-Pt Graphite-Pt/Ti Fe@Fe2O3/CNT-Pt ACF-Ti/RuO2 Optimum pH 3 2 3 3 3 3 4 Efciency (%) 75.2 40 80 100 70 99.6 55 Time (min) 240 120 20 120 150 120 480 Reference [66] [27] [30] [25] [55] [65] [79]

5. Affecting factors 5.1. pH

process is reported in Table 3. From Table 3, it was found that the optimum pH for E-Fenton process varies from 2 to 4. 5.2. Oxygen sparging rate

The pH is one of the most important factors for the E-Fenton process. Generally Fenton process was conducted in acidic medium. Most of the studies reported that the optimum pH of Fenton process is around 3 [25,30,55,65]. In traditional Fenton process, iron species begin to precipitate as ferric hydroxides at higher pH values. On the other hand, iron species form stable complexes with H2O2 at lower pH values, leading to deactivation of catalysts. Consequently, the oxidation efciency dramatically decreases [66]. Acidic medium is the favorable condition for the production of H2O2 (Eq. (5)) [66]. However, a low pH also promotes hydrogen evolution, as given in Eq. (12), reducing the number of active sites for generating hydrogen peroxide [66]. In addition, at pH below 3, hydrogen peroxide would remain steady according to + the formation of oxonium ion (e.g., H3O2 as in Eq. (13)) [30]. 2+ Due to the regeneration of Fe , through reaction between Fe 3+ and H2O2, Fenton process becomes less effective at pH b 3 [72,73]. At higher pH, the efciency of E-Fenton process decreases rapidly, especially pH > 5. This is due to the fact that H2O2 is unstable in basic solution. H2O2 rapidly decomposes to oxygen and water at neutral to high pH with rate constant of 2.3 10 2 and 7.4 10 2 min 1 at pH 7.0 and 10.5, respectively [74,75]. H2 O2 2H 2e 2H2 O

Oxygen is one of the major factors that limit the performance of EFenton system, because increasing the oxygen sparging rate can increase the dissolved oxygen concentration and the mass transfer rate of dissolved oxygen and nally increase the production of hydrogen peroxide [66]. Chen and Lin [80] reported that the electrochemical oxidation of TOC correlates well with the hydrogen peroxide generated at the cathode, wherein the saturated solubility of oxygen in wastewater has been almost achieved at the oxygen ow rate of 100 mL/min. But the color removal efciency remained almost constant at a current density of 68 A/m 2 even when the oxygen sparging rate increased from 0.3 to 0.4 L/min [55]. The results indicate that color removal began to be controlled by the kinetics of the production of hydrogen peroxides when the oxygen sparging rate exceeded 0.3 L/min [55]. Similar results are reported by Wang et al. [66] after the oxygen sparging rate was over 150 L/min for COD removal. 5.3. Temperature Although temperature has a positive effect on the treatment efciency in Fenton and related processes, the increase in organic compound removal due to temperature is relatively small compared to the other factors. Too low and too high temperatures negatively impact the process efciency. An optimal temperature of 30 C has been reported by Guedes et al. [81] for the degradation of cork cooking wastewater. Temperature between 20 and 30 C can be considered as an optimum range because of relatively higher treatment efciency in this temperature range [82]. Zhang et al. [83] reported that COD removal efciency of Fenton process increased slightly as the temperature increased from 15 to 36 C. Wang [4] reported that the rate of dye degradation was lower at low temperature and the extent of degradation was higher at 2030 C before 100 min. On the other hand Wu et al. [84] found an optimal temperature of 45 C for the degradation of humic acid. Also up to 100% degradation of diisopropanolamine at 60 C has been reported by Khamaruddin et al. [85]. Temperature has two effects on the accumulated H2O2 concentration during the electrolysis. First one is the decrease of O2 solubility in water with increase of the temperature and second one is the low stability of H2O2 at high temperatures [86]. Dye degradation rate has been decreased when the temperature was greater than 30 C

12

13 H2 O2 H H3 O2 The increase in pH during E-Fenton process leads to electrocoagulation whereby pollutants are removed by electrostatic attraction and/or complexation of reactions due to the conversion of Fe 2+ and Fe 3+ to Fe(OH)n type structures [76]. Ting et al. [77] reported that 2,6-dimethylaniline concentration decreased from 36% to 25% in 2 h when pH was increased from 1.5 to 2.0. The complete removal of 2,6-dimethylaniline was achieved after 140 min at pH 2. Also a further increase of pH from 2 to 4 increased 2,6-dimethylaniline concentration from 25% to 85%. Daneshvar et al. [78] suggested the perchloric acid instead of hydrochloric or sulfuric acid to adjust the optimal pH value to obtain optimal removal of dyes. But the optimum pH value shows the disadvantage of E-Fenton process because the pH of most wastewater samples is not within the optimal range. The optimum pH necessary for the different pollutant removal by E-Fenton

Table 4 Optimum temperatures of E-Fenton process in various studies. No Pollutant 1 2 3 Dyeing wastewater Dyeing wastewater Nitrotoluenes Electrodes Pt-PAN-based activated carbon ber Graphite-Pt/Ti PtPt Experimental conditions Temperature (C) Removal efciency (%) 75 70.6 ~ 100 Reference [66] [55] [80]

Current density = 3.2 mA/cm2; oxygen sparging rate = 150 cm3/min; 20 pH = 3; [Fe2+] = 2 mM. pH = 3; oxygen sparging rate = 0.3 L/min; applied current density = 68 A/ 45 m2; [Fe2+] = 15 mM. 40 Electrode potential = 6 V, O2 = 100 mL/min, pH = 0.2, [Fe2+] = 15 mg/L.

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

due to decomposition of H2O2 at a higher temperature [4]. The negative effect of temperature on the pollutant removal percentage can also be explained by the lower concentration of dissolved oxygen and the self-decomposition of hydrogen peroxide at higher temperatures [66]. Namely, the concentration of hydrogen peroxide decreased as the temperature increased because increasing temperatures can decrease oxygen solubility in the wastewater [66]. In addition, the rate of self decomposition of hydrogen peroxide to water and oxygen increased with the temperature [55,66]. But Hameed and Lee [87] reported that degradation of malachite green increased from 85.59 to 98.14% as a consequence of increasing the temperature from 30 to 50 C within the rst 10 min of Fenton process. Also Homem et al. [88] reported that the reaction rate of amoxicillin degradation was increased by increasing the temperature (in between 22 and 57 C). Zazo et al. [89] reported that increasing the temperature clearly improves both the oxidation rate and the degree of mineralization of phenol by Fenton oxidation allowing working with reduced amounts of H2O2 and Fe2+. This may be due to the fact that the increase in reaction rate between hydrogen peroxide and any form of ferrous/ferric iron (chelated or not) at higher temperature increases the rate of generation of oxidizing species such as OH radical or high-valence iron species [90]. The optimum temperatures and corresponding removal efciencies reported by various researchers are given in Table 4. 5.4. Applied current density The applied current is the driving force for the reduction of oxygen leading to the generation of hydrogen peroxide at the cathode. Higher applied current increases the quantum of hydrogen peroxide produced, thus increasing the number of hydroxyl radicals in the electrolyte medium, which are highly reactive and responsible for the degradation [91]. Higher applied current density means higher applied voltage on the electrochemical system [66]. Also higher electro-regeneration of ferrous ion from ferric ion (Eq. (14)) with increasing current increased the efciency of Fenton chain reactions [32]. Fe
3

2H 2e H2

16

The degradation rate of organic pollutants is constant after 300 mA. This is due to the formation of H2O as in Eq. (17) [42].

4H O2 4e 2H2 O

17

Some studies indicated that the current density in the E-Fenton process should be no larger than 10 A/m 2, while others indicated that the upper limit value should be 6.4 A/m 2 [92]. The optimum current or current densities and corresponding removal efciencies of EFenton process are given in Table 5. 5.5. Fe 2+ concentration Suitable ferrous ion concentration is an important prerequisite in the E-Fenton process [30]. Generally the efciency of E-Fenton process increases with Fe 2+ concentration because the concentration of hydroxyl radical, which is the main oxidizing agent in the E-Fenton process increases with the increase in Fe 2+ concentration (Eq. (1)). Also the oxidizing power of hydrogen peroxide was not enough to destroy large molecules, such as dyestuffs in real dyeing wastewater in the absence of ferrous ions [66]. The color removal efciency was markedly increased from 9% to 46% by externally adding a small amount of ferrous ions (5 mM) [55]. Wang et al. [66] reported that the presence of Fe 2+ signicantly improved the COD removal percentage. The COD removal percentage markedly increased from 19.8% to 43.1% by externally adding a Fe 2+ concentration of 0.33 mM [66]. Zhou et al. [30] reported that the removal of methyl red increased from 45% to 75% in 10 min in the presence of Fe 2+. Wang et al. [51] observed an increase in the rate of TOC decay by EFenton process, when initial Fe 2+ concentrations were increased from 0 to 1 mM. However, ferrous ions in the electrolyte solution, when present in excess, could consume the hydroxyl radicals and affect the extent of degradation [91]. The plausible interpretation is given by a competitive reaction between hydroxyl radicals and ferrous ions, which could diminish the concentration of hydroxyl radicals as in Eq. (4) [93,94]. The effect of Fe 2+ concentration on the kinetic rate constants, for 2,6-dimethylaniline degradation was studied by Ting et al. [77]. The kinetic rate constant increased with increasing Fe 2+ concentration from 1.0 to 1.5 mM and does not increase signicantly as the dosage of ferrous ions increased from 1.5 to 2.0 mM [77]. The optimum Fe 2+ concentrations and corresponding E-Fenton process removal efciencies are given in Table 6.

e Fe

14

The efciency of E-Fenton will be less at higher current density efciency. This is due to the competitive electrode reactions in the electrolytic cell. The discharge of oxygen at anode (Eq. (15)) and the evolution of hydrogen at cathode (Eq. (16)) occur at a higher current. These reactions inhibit main reactions such as reactions (6) and (14) [32], which lead to decrease in efciency of E-Fenton. 2H2 O4H O2 4e

15

Table 5 Optimum current/current densities of E-Fenton process in various studies. No Pollutant 1 2 3 4 5 6 7 8 o-Chlorophenol 4-Nitrophenol Dyeing wastewater Acid Red 14 Dyeing wastewater Picloram 2,4,6Trinitrotoluene 2,6Dimethylaniline Electrodes Stainless steel Pt gauze Stainless steel Ti/RuO2/IrO2 Pt-PAN based activated carbon ber RuO2/Ti ACF Graphite Pt/Ti Carbon felt Pt Pt carbon felt Ti-RuO2/IrO2 stainless steel Experimental conditions [Pollutant] = 80 mg/L, [Fe2+] = 0.5 mg/L, electrolysis time = 60 min [Pollutant] = 200 mg/L, [H2O2] = 9.12 mmol/L, Fe(II)/H2O2 = 0.050 Oxygen sparging rate = 150 cm3/min; pH = 3; [Fe2+] = 2 mM; temperature = 20 C [Pollutant] = 200 mg/L, [Na2SO4] = 0.05 M, pH = 3, [Fe2+] = 1 mM pH = 3; oxygen sparging rate = 0.3 L/min; [Fe2+] = 15 mM [Pollutant] = 0.125 mM; [Fe3+] = 0.1 mM; [Na2SO4] = 50 mM; pH = 3 [TNT]0 = 0.2 mM, [Fe2+] = 0.2 mM [Pollutant] = 1 mM; [Fe
2+

Applied current or Removal Reference current density efciency (%) 600 mA 1A 3.2 mA/cm2 0.50 A 68 A/m2 300 mA 250 mA 10.6 A/m
2

59.12 65.0 75.2 73.3 70 100 99 91

[91] [32] [66] [51] [55] [42] [61] [77]

] = 1 mM; [H2O2] = 20 mM; pH = 2.0

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115 Table 6 Optimum Fe2+ concentrations of E-Fenton process in various studies. No 1 2 3 4 5 6 Pollutant o-Chlorophenol Dyeing wastewater Methyl red Sunset yellow FCF Acid Red 14 Dyeing wastewater Electrodes Stainless steel Pt gauze Pt-PAN-based activated carbon ber Graphite PTFE Pt RVC Pt RuO2/Ti ACF Graphite Pt/Ti Experimental conditions [Pollutant] = 80 mg/L, applied current = 60 mA, electrolysis time = 60 min Current density = 3.2 mA/cm2; oxygen sparging rate = 150 cm3/min; pH = 3; temperature = 20 C. pH = 3.0, [Na2SO4] = 0.1 M, [pollutant] = 100 mg/L, oxygen ow rate = 0.4 L/min [pollutant] = 0.2 mM, [Na2SO4] = 0.05 M, pH = 3 [pollutant] = 200 mg/L, [Na2SO4] = 0.05 M, pH = 3 pH = 3; oxygen sparging rate = 0.3 L/min; applied current density = 68 A/m2 Fe2+ concentration 2 mg/L 2 mM 0.25 mM 0.1 mM 1 mM 15 mM Removal efciency (%) 80.4 75 75 100 68.2 70 Reference [91] [66] [30] [25] [51] [55]

5.6. Hydrogen peroxide concentration and feeding mode The initial concentration of H2O2 plays an important role in the EFenton process [77]. Removal of pollutants increases with increase in H2O2 concentration. The increase in the removal efciency was due to the increase in hydroxyl radical concentration as a result of the addition of H2O2 (Eq. (1)) [77]. Zhang et al. [32] reported that efciency of hydrogen peroxide for removing organic materials in the leachate decreased with the increase of Fenton's reagent dosage. At a high dosage of H2O2, the decrease in removal efciency was due to the hydroxyl radical scavenging effect of H2O2 (Eqs. (18) and (19)) and the recombination of the hydroxyl radical (Eq. (20)) [95]. HO H2 O2 HO2 H2 O HO2 HO H2 O O2 2HO H2 O2

5.7. Distance between the electrodes In the E-Fenton process, distance between electrodes is another important factor that affects the removal of pollutants. The decrease of the distance between the electrodes leads to a decrease of the ohmic drop through the electrolyte and then an equivalent decrease of the cell voltage and energy consumption [97]. Zhang et al. [12] reported that the COD removal efciency from landll leachate remained the same for electrode distance between 1.3 and 2.1 cm. The removal efciency of E-Fenton system was less for the shorter or larger distance. This is because electro-regenerated Fe 2+ could be easily oxidized to ferric ion at the anode, when the electrodes were placed too short [12]. Longer distance causes the limiting mass transfer of ferric ion to the cathode surface that governs ferrous ion regeneration [12,98]. Atmaca [20] reported that the changes in the distance between the electrodes have an insignicant effect on treatment efciency. Use of long electrode distance in E-Fenton reactor causes a signicant increase in energy consumption [20]. 5.8. Nature of the supporting electrolyte Electrolyte improves the solution conductivity, and accelerates the electron transfer, thus beneting the E-Fenton reaction. Therefore, supporting electrolyte is necessary, especially in the solution without enough conductivity [21]. In E-Fenton process, sodium sulfate is commonly used as the supporting electrolyte. Zhou et al. [30] reported that higher Na2SO4 concentration led to higher current density, which resulted in faster and larger production of hydrogen peroxide and increases the efciency of E-Fenton system. But Diagne et al. [99] observed a faster methyl parathion degradation rate in the pres 2 ence of NO3 than that of SO4 . Daneshvar et al. [78] also reported that the change in Na2SO4 concentration from 0.05 to 0.1 M did not have any effect on H2O2 accumulation. Ghoneim et al. [25] reported that optimal Na2SO4 concentration for sunset yellow FCF is 0.05 M. But Pt-graphite PTFE electrolytic system has an optimal Na2SO4 concentration of 0.1 M for the degradation of methyl red [30]. Also the authors noticed a signicant drop in efciency of the system at 0.2 M Na2SO4 concentration. This may be due to the consumption of 2 the generated hydroxyl radical by high SO4 concentration as in Eq. (21) [30]. HO SO4 HO SO4
2

18 19 20

Improvement of E-Fenton process efciency by feeding Fenton's reagent in multiple steps or continuous mode was reported by Zhang et al. [12]. Anotai et al. [96] compared the one-step and the two-step addition with H2O2 for aniline degradation. The results indicated that the aniline oxidation for the system of one-step addition with H2O2 was similar to that of the two-step. In both cases aniline oxidation was about 95% after reacting for 60 min. The removal efciency of COD in the one-step addition with H2O2 was similar to that in the two-step. On the other hand, the TOC removal efciency and remaining Fe 2+ concentrations were not affected by the H2O2 feeding mode [96]. Effect of H2O2 addition in a single step and in continuous mode on the degradation of 4-nitrophenol was reported by Zhang et al. [32]. It has been reported that decreasing feeding time increased the initial COD removal rate. The optimum COD removal has been reached when H2O2 was applied in a single step. But for continuous mode, the concentration of H2O2 increased with decrease in feeding time during the initial period. This will cause the production of more hydroxyl radicals as in Eq. (1) and increases the efciency of E-Fenton process. The nal COD removal efciency increased with the decreasing feeding time and reached highest when feeding time was 60 min. But due to side reactions, the efciency of E-Fenton process decreases with further decrease of feeding time [32]. The concentration of hydrogen peroxide during the initial period would be higher when hydrogen peroxide was added in a single step or fed more quickly in a continuous mode, the produced hydroxyl radicals would be scavenged by hydrogen peroxide. This reaction leads to the production of hydroperoxyl radical (Eq. (18)), a species with much weaker oxidizing power compared to hydroxyl radical [32].

21

Efciency of 0.05 M Na2SO4, 0.05 M NaCl and 0.05 M KCl as supporting electrolyte was compared by Ghoneim et al. [25] and 2 reported that aqueous solutions with SO4 have the highest rate of decolorization of sun set yellow compared to Cl electrolytes of the same concentration. But approximately 100% removal of the azodye was achieved for all electrolytes. The time taken for the removal of dye is 120, 180 and 180 min respectively for 0.05 M Na2SO4,

10

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

0.05 M NaCl and 0.05 M KCl solution [25]. Pimentel et al. [60] compared the efciency of iron, cobalt, manganese, and copper salts to provide the metal cations as catalyst of Fenton reaction to produce hydroxyl radicals and concluded that ferrous ions were the most effective catalysts with optimum concentration of 0.1 mM. 0.1 mM of soluble FeSO4 supplied the optimum catalytic condition, allowing 100% removal of TOC of aqueous phenol solutions [60]. But during E-Fenton process, degradation of some other compounds using iron as catalyst may lead to formation of complexes and changing iron concentration in the media [60]. zcan et al. [86] reported that the production of H2O2 is lower in the case of NaCl than that of NaNO3 and NaSO4. Signicantly a faster decrease of Orange II in the NaClO4 media than in Na2SO4 or NaCl media has been noticed by Daneshvar et al. [78]. Concentration of electrolyte also affects the efciency of E-Fenton process. But Daneshvar et al. [78] reported that the concentration of supporting electrolyte does not have any effect in orange II degradation, when the NaClO4 concentration has been increased from 0.05 to 0.1 M. 6. Applications In recent years there is a great interest in the development of practical electrochemical methods for the destruction of toxic and biorefractory organic pollutants for wastewater treatment [91]. The EFenton process is widely used to treat non-biodegradable or refractory organic compounds with moderate energy costs [100]. The applications of E-Fenton process is explained below. 6.1. Dyes The dyes used in the textile dyeing and printing industries not only can impart color to water sources but also can cause environmental damage to living organisms by stopping the reoxygenation capacity of water and also blocking sunlight, thereby disturbing the natural growth activity of aquatic life [4]. Some of the dyes are also toxic and carcinogenic in nature [101]. Presence of very small amounts of dyes in water (less than 1 ppm for some dyes) is highly visible and undesirable [102]. Synthetic dyes are used extensively by several industries including textile dyeing (60%), paper (10%) and plastic matter (10%) [35]. It is estimated that 1015% of the dye is lost in the efuent during dyeing processes [103]. Presently, more than 10,000 types of different commercial dyes and pigments are available [101], and more than 7 10 5 t per year are produced worldwide [102]. E-Fenton process has been identied as a powerful tool for removal of dye from wastewater very effectively. Guivarch et al. [35] studied the degradation of the three azo dyes azobenzene, methyl orange and p-methyl red by the E-Fenton and concluded that this process is efcient for azo dye degradation, achieving an efcient removal (over 80%) of COD. The degradation mechanism begins with the azo bond cleavage and is followed by the hydroxylation of the aromatic ring [35]. A synthetic dye wastewater sample composed of yellow drimaren, Congo red and methylene blue and having an initial COD of 3782 mg O2 L 1 was successfully mineralized using E-Fenton process by Lahkimi et al. [38] with the COD abatement ratio of 89% after 10,000 C of electrical charge passed. Decolorization of acid yellow 36 in acidic aqueous medium was studied by Cruz-Gonzlez et al. [54] and reported 97.8% of acid yellow 36 removal at optimum conditions such as Fe 2+ of 0.24 mmol/L, current density of 23 mA/cm 2 and electrolysis time of 48 min. Complete mineralization of indigo carmine of 220 mg/L concentration is feasible when E-Fenton is carried out with a BDD anode [43]. The degradation of different dyes by E-Fenton oxidation was carried out successfully in a continuous reactor by Rosales et al. [27]. The reactor was very efcient for dye removal and high discoloration percentage depends on the residence time. The operational problems of the reactor were also very less [27]. Degradation of

rhodamine B in aqueous solution was evaluated by Ai et al. [36]. The study reported that degradation of rhodamine B reached 80.2% and 89.3% in 120 min at neutral pH and pH 3, respectively [36]. Zhou et al. [30] reported that the degradation of methyl red was accomplished at two different stages, and the consumption of ferrous ion and formation of hard-to-treat intermediates led to the slower degradation in the second stage. Under the optimal conditions, the initial methyl red concentration of 100 mg/L could be degraded 80% in 20 min [30]. Ghoneim et al. [25] reported that for a contact time of 120 min, complete color removal and signicant mineralization (approximately 97%) of sunset yellow FCF have been achieved. 70% TOC removal for 500 mL of a 200 mg/L Acid Red 14 after 360 min of electrolysis was reported by Wang et al. [51]. El-Desoky et al. [41] applied optimized E-Fenton system successfully for complete degradation and signicant mineralization (approximately 8590%) of Levax blue and red reactive azo-dyes in real industrial wastewater samples of textile dyeing house. The removal efciency of color from real dyeing wastewater in the cathodic chamber reached 70.6% under specied operation conditions in 150 min [55]. This study reported that the best oxygen contact mode for removing the color was the three-phase contact mode, resulting in the optimal transference of the dissolved oxygen to the electrode surface [55]. COD removal efciency from real dyeing wastewater by using Fe 2+ in combination with electrogenerated hydrogen peroxide at the polyacrylonitrile based activated carbon ber cloth cathode was studied by Wang et al. [66]. In this study, the highest COD removal efciency (75.2%) was achieved at an applied current density of 3.2 mA/cm 2. 6.2. Pesticides and herbicides Due to the extensive utilization in agricultural activities, pesticides and herbicides are widely detected in many surface water, groundwater and wastewater efuents and are among the most frequently found organic pollutants in natural waters [104,105]. Many of these pesticides are utilized in amounts over 50,000 kg/year [106]. Relatively high pesticide and herbicide contamination levels are found in groundwater and surface water: 0.10.3 g/L in US groundwater and 0.030.5 g/L in European groundwater [107,108]. Similar results have been observed in India also. The residue levels of persistent chlorinated pesticides such as HCH (hexachlorocyclo-hexane) isomers and DDT (dichlorodiphenyltrichloroethane) compound samples from the river Kaveri, Tamil Nadu, South India have been reported by Rajendran and Subramanian [109]. River Ganges in Kanpur contains high concentrations of -HCH (0.259 g/l) and malathion (2.618 g/l) [110]. -HCH, malathion and dieldrin concentrations of 0.900, 29.835 and 16.227 g/l, respectively were detected in ground water samples [110]. Sanghi et al. [111] reported that the endosulfan concentrations in the human milk were the highest and exceeded the S-HCH, chlorpyrifos, and malathion concentrations by 3.5-, 1.5-, and 8.4-fold, respectively. Similarly Jani et al. [112] reported an average concentration of alpha-HCH, gamma HCH, beta HCH, p,p-DDE (Note: DDE-Dichlorodiphenyldichloroethylene), and p,p-DDT as 17.51, 1.62, 205.48, 244.71, and 53.43 g/kg, respectively in human milk. Also dairy milk and buffalo milk from Jaipur city were contaminated with DDT and its metabolites (DDE and p,p-dichlorodiphenyldichloroethane DDD), isomers of hexachlorocyclohexane (HCH; alpha, beta, and gamma), heptachlor and its epoxide, and aldrin [113]. This situation is considered as a pervasive problem because these compounds usually have direct adverse effects on the living organisms [114]. The E-Fenton process has been proved to be powerful enough to degrade hazardous pesticides and herbicides. Yatmaz and Uzman [52] reported that E-Fenton reaction by using both Fe electrodes with supply of H2O2 is the most efcient method for the degradation of monocrotophos in acidic medium. Monocrotophos was rapidly degraded within 5 min and the energy consumption of complete degradation was 0.834 kWh/kg [52]. Boye et al. [108] reported

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

11

80% mineralization of herbicide 4-chlorophenoxyacetic acid. zcan et al. [44] compared the propham removal efciency of BDD, CS and Pt electrodes as anode and/or cathode at four different congurations in the E-Fenton process. The authors reported that the highest TOC removal efciency and the lowest mineralization current efciency values were observed at 500 mA in the presence of 0.2 mM Fe 3+. The best mineralization current efciency value of 81% was obtained at 100 mA in the presence of 0.2 mM Fe 3+ for 30 min treatment [44]. Edelahi et al. [46] reported 93% COD removal within 10 min by degrading diuron using E-Fenton process. This process is also efcient for imazapyr degradation and the COD removal was found to be higher than 95% [115]. The degradation of herbicide chlortoluron in aqueous medium by E-Fenton process using a carbon felt cathode and a platinum anode was studied by Abdessalem et al. [69]. Even the degradation of 0.05 mM chlortoluron happened within 4 min, 98% of TOC removal was recorded only after 8 h [69]. Similar results were also reported by zcan et al. [42] for the removal of picloram. Kaichouh et al. [116] reported that the imazaquin is degraded more quickly than the imazapyr. But 97% mineralization of each herbicide was reached after 3.5 h of treatment under optimal operating conditions of I = 0.2 A and [Fe 2+]0 = 0.1 mM [116]. E-Fenton with a Pt anode, stainless steel sheet cathode and 1 mmol/L Fe 2+ as catalyst yields the quickest and complete depollution of amitrole [49]. A comparative study of a mixture of three pesticides (chlortoluron, carbofuran and bentazon) has been investigated by Abdessalem et al. [117]. It was reported that based on cost, E-Fenton process is much more interesting than photo-Fenton process [117]. 6.3. Phenolic compounds Among the various wastes, phenolic compounds constitute a family of pollutants particularly toxic to the aquatic fauna and ora. These compounds are released in the surface water by a considerable number of industries, mainly, by pharmaceutical plants, oil reneries, coke plants, pulp, and food-processing industries and several other chemical plants [118,119]. Nitrophenols are anthropogenic, toxic, inhibitory and biorefractory organic compounds used extensively in chemical industries for the manufacture of pesticides, pharmaceuticals and synthetic dyes [120]. Chlorophenols have been detected during the manufacture of pesticides, bleaching of industrial wastewater, and chlorination of drinking water [121]. Phenolic compounds are very toxic to human health and aquatic life. Consequently, removal of them from wastewater is an environmental concern. These compounds are removed very effectively by E-Fenton process. Pimentel et al. [60] reported that total mineralization of phenol was obtained at optimum experimental conditions. The degradation of various chlorophenols by E-Fenton method was carried out by Song-hu and Xiao-hua [122]. The degradation sequence of various chlorophenols were in the following order: 2,4-dichlorophenol>2,4,6-trichlorophenol>pentachlorophenol>4-chlorophenol. This order is different from other AOP studies. The degradation pathways of chlorophenols were proposed as ortho- and para-reaction by hydroxyl attack and direct dechlorination by cathode reduction [122]. Further oxidation was preceded by hydroxyl radical. Most of the residual chlorine was left in the ring opening low molecule compounds [122]. 280.7 C electrical charge was consumed during 450 min of electrolysis to attain degradation of 4-chloro-2-methylphenol and 14.9% TOC removal and 89.3% dechlorination have been reported by Irmak et al. [62]. The kinetics of the oxidative degradation of several chlorophenols, such as monochlorophenols (2-chlorophenol and 4-chlorophenol), dichlorophenols (2,4-dichlorophenol and 2,6-dichlorophenol), trichlorophenols (2,3,5trichlorophenol and 2,4,5-trichlorophenol), 2,3,5,6-tetrachlorophenol, and pentachlorophenol by the E-Fenton process have been investigated using a carbon felt cathode [123]. It was demonstrated that the number and the position of the chlorine atoms in the aromatic ring significantly inuence the oxidation. The degradation followed a pseudo-

rst-order kinetics and the apparent rate constant follows the sequence 4-chlorophenol > 2-chlorophenol > 2,4-dichlorophenol > and 2,6-dichlorophenol >2,3,5-trichlorophenol >2,4,5-trichlorophenol >2,3, 5,6-tetrachlorophenol >pentachlorophenol. It was also observed that the mineralization rate of chlorophenols decreased with increasing the number of chlorine atoms in the aromatic ring, conrming that the more chlorinated phenols are, the more difcult to mineralize [123]. EFenton process is highly efcient for the degradation of o-chlorophenol [91]. Sankara Narayanan et al. [91] concluded that the non-availability of sufcient concentrations of ferrous ions with electrolysis time limits the efciency of the process. Under optimized conditions it is possible to achieve more than 70% degradation and addition of goethite as a catalyst did not show any signicant increase in the degradation of ochlorophenol. Irmak et al. [62] reported that in E-Fenton application, degradation of the refractory aromatic ring was quite straightforward but decomposition of all aliphatic products into carbon dioxide and water, i.e. complete mineralization is time and energy consuming. On the other hand, release of chlorine atoms from organic structure into the aqueous solution as chloride ions takes place almost simultaneously with the breaking-up of the aromatic ring. In other words, toxicity related to the organochlorine structures is diminished in the early stages of the E-Fenton treatment. Therefore, one can advise to continue to treat the aqueous system by using cheaper conventional techniques following the breakdown of aromatic structures and in situ release of most of the chlorine as chloride ions [62]. Degradation of 4-nitrophenol was carried out in batch recirculation mode by Zhang et al. [32]. It was reported that even under successful COD removal, E-Fenton process induces a synergetic effect on COD removal. Treatment of high concentration of 4nitrophenol in the undivided cell removed more than 98% of 4nitrophenol and about 13% of TOC [124]. Negligible quantity of nitrate and nitrite ions detected indicates that there is no direct release of NO2 and NO groups from 4-nitrophenol and its degradation intermediates [124]. 6.4. Leachate Landlls are ubiquitous in modern society, and the proper management of their potential environmental impact is of the highest priority [125]. Landll leachate is dened as those aqueous streams generated as a consequence of rainwater percolation through wastes, biochemical processes in the wastes' cells and the inherent water content of the wastes themselves [126]. Leachate may contain large amounts of organic matter, of which humic-type constituents are an important group, as well as ammonia-nitrogen, heavy metals and chlorinated organic and inorganic salts. The removal of organic material based on COD, biological oxygen demand and ammonium from leachate is the usual prerequisite before discharging the leachate into natural waters [126]. Only a few works on leachate treatment by E-Fenton are reported. Altin [127] reported more than 90% color removal efciency by E-Fenton process. 87% PO4P and 26% NH4N removal from landll leachate under optimum conditions was reported by Atmaca [20]. Also this study reported 72% COD and 90% color removal. Mohajeri et al. [128] achieved 94% COD removal and 95.8%color removal from landll leachate. Treatment of high strength landll leachate by E-Fenton process was studied by Zhang et al. [12]. Ti/RuO2 and IrO2 type electrodes were used as anode. They reported that the process was very fast in the rst 30 min and then slowed down till it was complete in 75 min. Atmaca [20] studied the characteristics of sludge produced from landll leachate treatment by EFenton process. The author reported that the sedimentation characteristics of the waste are fairly good [20]. 6.5. Drugs A large number of pharmaceutical drugs have been recently detected in water sources. For example chlorophene, a widespread

12 Table 7 Various pollutants removed by E-Fenton process. No 1 Pollutant/purpose Aniline

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

Research highlights After 6 h of electrolysis at 100 mA 68% of TOC removal achieved. A fast aniline mineralization Ammonium ions (7580% of initial nitrogen) were generated More than 50% of COD removal efciency E-Fenton method is effective in treating this wastewater Optimum parameters were: pH 4, 1.8 h reaction time, 0.6 mM of Fe2+ and 3.7 mA/cm2 of current density 55% TOC removal Up to 64.5% of running costs can be cut when E-Fenton used 100% current efciency in solutions polluted by organic substances Nearly complete decomposition of nitrotoluenes under the optimal conditions of electrode potential = 6 V, T = 303 K, O2 = 100 mL/min and iron(II) = 15 mg/L. After 5 min electrolysis, 70 and 99% of the initial TNT content were degraded for 60 and 250 mA current intensity values Minimum 22% of aromatic rings were cleaved at TNT disappearance time 35% of initial material reached the last step before mineralization, 60% TOC removal efciency Oxalic acid was the major intermediate detected from 2,6-dimethylaniline degradation Around 50% COD reduction 95% nonylphenol polyethoxylate removal was achieved in 5 min for aqueous solution and 10 min for wastewater treatment 88% COD was reduced in 50 min COD was reduced by 6070% within 10 min Over 70% COD removal for pH 3. At a neutral pH, greater than 60% COD removal Sulde concentration in the tannery industry wastewater was almost 100% removed in 10 min 64% of TOC removal

Reference [131]

2 3

Petrochemical wastewater Biological coking wastewater

[132] [79]

5 6

Industrial wastewater containing morpholine and diethylethanolamine, as well as sodium salts of naphthalene sulfonic acid and of ethylenediamine tetraacetic acid Dinitrotoluenes and 2,4,6-trinitrotoluene 2,4,6-Trinitrotoluene

[133]

[80] [61]

7 8

2,6-Dimethylaniline Nonylphenol polyethoxylate

[77] [134]

9 10

COD reduction of rayon industry wastewater COD reduction of leather tanning industry wastewaters

[59] [29]

11

Benzene sulfonic acid

[135]

broad-spectrum antimicrobial pharmaceutical has been detected at concentrations up to 50 mg/L in activated sludge sewage systems and up to 10 mg/L in sewage treatment plant efuents and rivers [39]. This pollution is originated from emission from production sites, direct disposal of over plus drugs in households, excretion after drug administration to humans and animals and treatments throughout the water in sh and other animal farms [129]. Some of the drugs are carcinogenic and mutagenic [130]. To avoid the dangerous health effects of such pollutants, potent oxidation methods are needed to remove drugs and their metabolites from wastewaters [56]. E-Fenton is one of such powerful tool for removing drugs from wastewater. The catalytic behavior of the Fe 3+/Fe 2+ system in the E-Fenton degradation of the antimicrobial drug chlorophene mainly depends on the cathode [39]. The authors reported that that EFenton is a viable environmentally friendly technology for the remediation of wastewaters containing chlorophene. The removal efciency of chlorophene by Pt/O2 diffusion, BDD/O2 diffusion, BDD/carbon felt and Pt/carbon felt E-Fenton systems was compared. Maximum removal of chlorophene is in the order of Pt/carbon felt system followed by BDD/carbon felt, BDD/O2 diffusion and Pt/O2 diffusion systems [39]. Isarain-Chvez et al. [47] used two-electrode cells with a Pt or boron-doped diamond anode and an air-diffusion cathode for H2O2 electrogeneration, and four-electrode combined cells containing the above pair of electrodes coupled in parallel to a Pt anode and a carbon-felt cathode, to degrade the pharmaceutical blocker atenolol by E-Fenton. Compared with the single cells, the corresponding novel four-electrode combined systems enhance strongly the mineralization rate of atenolol in E-Fenton. Because of the fast Fe 2+ regeneration at the carbon-felt cathode favoring: (i) the production of more amounts of OH from Fenton's reaction that destroy more rapidly aromatic pollutants and (ii) the formation of Fe(II) complexes with nal carboxylic acids such as oxalic and oxamic, which are more quickly oxidized with OH [47]. Solutions of about 0.25 mM of the -blocker metoprolol tartrate (100 mg/L total organic carbon) with 0.5 mM Fe 2+ in the presence and absence of 0.1 mM Cu 2+ with pH 3.0 have been degraded under single and combined E-Fenton

conditions [56]. The study reported that the combined cell was much more potent than the single one by the larger OH generation from the continuous Fe 2+ regeneration at the carbon felt cathode, accelerating the oxidation of organics. Total mineralization was feasible using the combined cell in the presence of 0.1 mM Cu 2+, because of the parallel quick oxidation of Cu(II) carboxylate complexes by OH [56]. 6.6. Others Many other pollutant degradation was carried out successfully by E-Fenton process. The details are given in Table 7. From Table 7, it is very clear that E-Fenton is a very powerful and environmentally friendly tool for wastewater treatment. 7. Degradation pathway of organic pollutants One of the main advantages of E-Fenton process is the complete mineralization and degradation of organic compounds. High performance liquid chromatography (HPLC) analysis and Gas chromatographymass spectrometry (GCMS) of electrolyzed wastewater revealed the formation of different oxidation products. The decay kinetics for initial pollutants can be monitored by reversed-phase HPLC. The proposed reaction sequence for the degradation of dye Acid Red 97 using carbon felt cathode and Pt anode [40] is shown in Fig. 6. The oxidation of Acid Red 97 under the action of OH gives 1,2-naphthalenediol, 1,1-biphenyl-4-amino-4-ol, 2-naphthalenol diazonium and 2-naphthalenol by the reduction of azo bonds. These products undergo further oxidation and release 2,3-dihydroxy-1,4naphthalenedion, phthalic anhydride, 1,2-benzenedicarboxylic acid, phthaldehyde, 3-hydroxy-1,2-benzenedicarboxylic acid, 4-aminobenzoic acid and 2-formyl-benzoic acid. During this reaction most of the nitrogen element went away from the dye structure as + NO3 and NH4 ions or nitrogen. After that gradual cleavage of aromatic ring occurs, and this leads to the formation of CO2 as nal product [40].

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115

13

8. Conclusions The application of E-Fenton on organic pollutant removal from wastewater has received increased attention in the last decade. Different types of electrolytic reactors were used for E-Fenton study. Efciencies of various anode and cathode were evaluated and compared. This process is very much dependent on pH, oxygen sparging rate, temperature of solution, applied current density, Fe 2+ concentration, hydrogen peroxide concentration and feeding mode, distance between the electrodes and nature of the supporting electrolyte. Removal of various organic pollutants including dyes, drugs, herbicides and pesticides, leachate, phenolic compounds etc. by this process was evaluated. Overall, E-Fenton process is a promising technology for applications in wastewater treatment. Acknowledgments The authors are thankful to K. Sharath, Ranjith Kumar and T.G. Parameswaran for the great support. References
[1] H. Choi, S.R. Al-Abed, D.D. Dionysiou, E. Stathatos, P. Lianos, TiO2 based advanced oxidation nanotechnologies for water purication and reuse, Sustainability Sci. Eng. 2 (2010) 229254. [2] W.H. Glaze, Drinking-water treatment with ozone, Environ. Sci. Technol. 21 (1987) 224230. [3] A.S. Stasinakis, Use of selected advanced oxidation processes (AOPs) for wastewater treatment a mini review, Global NEST 10 (2008) 376385. [4] S.B. Wang, A comparative study of Fenton and Fenton-like reaction kinetics in decolourisation of wastewater, Dyes Pigm. 76 (2008) 714720. [5] H.J. Fenton, Oxidative properties of the H2O2/Fe2+ system and its application, J. Chem. Soc. 65 (1884) 889899. [6] J. Kochany, E. Lipczynska-Kochany, Utilization of landll leachate parameters for pretreatment by Fenton reaction and struvite precipitationa comparative study, J. Hazard. Mater. 166 (2009) 248254. [7] Y.W. Kang, K.Y. Hwang, Effects of reaction conditions on the oxidation efciency in the Fenton process, Water Res. 34 (2000) 27862790. [8] W.Z. Tang, Physicochemical Treatment of Hazardous Wastes, Lewis Publishers, Boca Raton, Fla, USA, 2003. [9] E. Neyens, J. Baeyens, A review of classic Fenton's peroxidation as an advanced oxidation technique, J. Hazard. Mater. 98 (2003) 3350. [10] J. Ma, W. Song, C. Chen, W. Ma, J. Zhao, Y. Tang, Fenton degradation of organic compounds promoted by dyes under visible irradiation, Environ. Sci. Technol. 395 (2005) 58105815. [11] F. Lcking, H. Kser, M. Jank, A. Ritter, Iron powder, graphite and activated carbon as catalysts for the oxidation of 4-chlorophenol with hydrogen peroxide in aqueous solution, Water Res. 32 (1998) 26072614. [12] H. Zhang, D. Zhang, J. Zhou, Removal of COD from landll leachate by electroFenton method, J. Hazard. Mater. 135 (2006) 106111. [13] M.C. Lu, H. Zhang, Y.Y. Huang, S.Y. Wang, Inuence of inorganic ions on the mineralization of 2, 4-dinitrophenol by the Fenton reaction, Fresenius Environ. Bull. 14 (2005) 101104. [14] J.H. Ramirez, C.A. Costa, L.M. Madeira, G. Mata, M.A. Vicente, M.L. RojasCervantes, A.J. Lpez-Peinado, R.M. Martn-Aranda, Fenton-like oxidation of Orange II solutions using heterogeneous catalysts based on saponite clay, Appl. Catal., B 71 (2007) 4456. [15] A.. Gotvajn, J. Zagorc-Konan, Combination of Fenton and biological oxidation for treatment of heavily polluted fermentation waste broth, Acta Chim. Slov. 52 (2005) 131137. [16] J. Deng, J. Jiang, Y. Zhang, X. Lin, C. Du, Y. Xiong, FeVO4 as a highly active heterogeneous Fenton-like catalyst towards the degradation of Orange II, Appl. Catal., B 84 (3) (2008) 468473. [17] W. Li, Q. Zhou, T. Hua, Removal of organic matter from landll leachate by advanced oxidation processes: a review, Int. J. Chem. Eng. (2010) 110. [18] E. Brillas, I. Sires, M.A. Oturan, Electro-Fenton process and related electrochemical technologies based on Fenton's reaction chemistry, Chem. Rev. 109 (2009) 65706631. [19] J. Li, Z. Ai, L. Zhang, Design of a neutral electro-Fenton system with Fe@Fe2O3/ACF composite cathode for wastewater treatment, J. Hazard. Mater. 164 (2009) 1825. [20] E. Atmaca, Treatment of landll leachate by using electro-Fenton method, J. Hazard. Mater. 163 (2009) 109114. [21] J. Cheng-chun, Z. Jia-fa, Progress and prospect in electro-Fenton process for wastewater treatment, J. Zhejiang Univ. Sci. A 8 (7) (2007) 11181125. [22] E. Brillas, M.A. Banos, S. Camps, C. Arias, P.L. Cabot, J.A. Garrido, R.M. Rodrguez, Catalytic effect of Fe2+, Cu2+ and UVA light on the electrochemical degradation of nitrobenzene using an oxygen-diffusion cathode, New J. Chem. 28 (2004) 314322.

[23] B. Gzmen, M.A. Oturan, N. Oturan, O. Erbatur, Indirect electrochemical treatment of bisphenol A in water via electrochemically generated Fenton's reagent, Environ. Sci. Technol. 37 (2003) 37163723. [24] J.M. Peralta-Hernndez, Y. Meas-Vong, F.J. Rodrguez, T.W. Chapman, M.I. Maldonado, L.A. Godnez, In situ electrochemical and photo-electrochemical generation of the Fenton reagent: a potentially important new water treatment technology, Water Res. 40 (2006) 17541762. [25] M.M. Ghoneim, H.S. El-Desoky, N.M. Zidan, Electro-Fenton oxidation of Sunset Yellow FCF azo-dye in aqueous solutions, Desalination 274 (2011) 2230. [26] Z.M. Qiang, Removal of selected hazardous organic compounds by electroFenton oxidation process, PhD Thesis, Proquest Information and Learning Company, the United States, 2002 1020. [27] E. Rosales, M. Pazos, M.A. Longo, M.A. Sanromn, Electro-Fenton decoloration of dyes in a continuous reactor: a promising technology in colored wastewater treatment, Chem. Eng. J. 155 (2009) 6267. [28] D. Prabhakaran, T. Kannadasan, C. Ahmed Basha, Treatability of resin efuents by electrochemical oxidation using batch recirculation reactor, Int. J. Environ. Sci. Technol. 6 (3) (2009) 491498. [29] U. Kurt, O. Apaydin, M. Talha Gonullu, Reduction of COD in wastewater from an organized tannery industrial region by electro-Fenton process, J. Hazard. Mater. 143 (2007) 3340. [30] M. Zhou, Q. Yu, L. Lei, G. Barton, Electro-Fenton method for the removal of methyl red in an efcient electrochemical system, Sep. Purif. Technol. 573 (2007) 380387. [31] S. Yuan, Y. Fan, Y. Zhang, M. Tong, P. Liao, Pd-Catalytic in situ generation of H2O2 from H2 and O2 produced by water electrolysis for the efcient electro-Fenton degradation of Rhodamine B, Environ. Sci. Technol. 45 (19) (2011) 85148520. [32] H. Zhang, C. Fei, D. Zhang, F. Tang, Degradation of 4-nitrophenol in aqueous medium by electro-Fenton method, J. Hazard. Mater. 145 (2007) 227232. [33] M. Panizza, G. Cerisola, Direct and mediated anodic oxidation of organic pollutants, Chem. Rev. 109 (2009) 65416569. [34] A.R. Khataee, V. Vatanpour, A.R. Amani Ghadim, Decolorization of C.I. Acid Blue 9 solution by UV/nano-TiO2, Fenton, Fenton-like, electro-Fenton and electrocoagulation processes: a comparative study, J. Hazard. Mater. 161 (2009) 12251233. [35] E. Guivarch, S. Trevin, C. Lahitte, M.A. Oturan, Degradation of azo dyes in water by electro-Fenton process, Environ. Chem. Lett. 1 (2003) 3844. [36] Z. Ai, H. Xiao, T. Mei, J. Liu, L. Zhang, K. Deng, J. Qiu, Electro-Fenton degradation of Rhodamine B based on a composite cathode of Cu2O nanocubes and carbon nanotubes, J. Phys. Chem. C 112 (2008) 1192911935. [37] I. Siminiceanu, C.I. Alexandru, E. Brillas, Energy saving by the intensication of the electro-Fenton process for water treatment using boron doped diamond electrode, Chem. Eng. Trans. 21 (2010) 7984. [38] A. Lahkimi, M.A. Oturan, N. Oturan, M. Chaouch, Removal of textile dyes from water by the electro-Fenton process, Environ. Chem. Lett. 5 (2007) 3539. [39] I. Sirs, J.A. Garrido, R.M. Rodrguez, E. Brillas, N. Oturan, M.A. Oturan, Catalytic behavior of the Fe3+/Fe2+ system in the electro-Fenton degradation of the antimicrobial chlorophene, Appl. Catal., B 72 (2007) 382394. [40] B. Kayan, B. Gzmen, M. Demirel, A.M. Gizir, Degradation of Acid Red 97 dye in aqueous medium using wet oxidation and electro-Fenton techniques, J. Hazard. Mater. 177 (2010) 95102. [41] H.S. El-Desoky, M.M. Ghoneim, R. El-Sheikh, N.M. Zidan, Oxidation of Levax CA reactive azo-dyes in industrial wastewater of textile dyeing by electrogenerated Fenton's reagent, J. Hazard. Mater. 175 (2010) 858865. [42] A. Ozcan, Y. Sahin, A.S. Koparal, M.A. Oturan, Degradation of picloram by the electro-Fenton process, J. Hazard. Mater. 153 (2008) 718727. [43] C. Flox, S. Ammar, C. Arias, E. Brillas, A.V. Vargas-Zavala, R. Abdelhedi, ElectroFenton and photoelectro-Fenton degradation of indigo carmine in acidic aqueous medium, Appl. Catal., B 67 (2006) 93104. [44] A. Ozcan, Y. Sahin, A.S. Koparal, M.A. Oturan, A comparative study on the efciency of electro-Fenton process in the removal of propham from water, Appl. Catal., B 89 (2009) 620626. [45] N. Oturan, M. Zhou, M.A. Oturan, Metomyl degradation by electro-Fenton and electro-Fenton-like processes: a kinetics study of the effect of the nature and concentration of some transition metal ions as catalyst, J. Phys. Chem. A 114 (2010) 1060510611. [46] M.C. Edelahi, N. Oturan, M.A. Oturan, Y. Padellec, A. Bermond, K.E. Kacemi, Degradation of diuron by the electro-Fenton process, Environ. Chem. Lett. 1 (2004) 233236. [47] E. Isarain-Chvez, C. Arias, P.L. Cabot, F. Centellas, R.M. Rodrguez, Mineralization of the drug -blocker atenolol by electro-Fenton and photoelectro-Fenton using an air-diffusion cathode for H2O2 electrogeneration combined with a carbon-felt cathode for Fe2+ regeneration, Appl. Catal., B 96 (2010) 361369. [48] N. Borrs, R. Oliver, C. Arias, E. Brillas, Degradation of atrazine by electrochemical advanced oxidation processes using a boron-doped diamond anode, J. Phys. Chem. A 114 (2010) 66136621. [49] A.D. Pozzo, C. Merli, I. Sirs, J.A. Garrido, R.M. Rodriguez, E. Brillas, Removal of the herbicide amitrole from water by anodic oxidation and electro-Fenton, Environ. Chem. Lett. 3 (2005) 711. [50] Y.H. Huang, Y.F. Huang, P.S. Chang, C.Y. Chen, Comparative study of oxidation of dye-Reactive Black B by different advanced oxidation processes: Fenton, electroFenton and photo-Fenton, J. Hazard. Mater. 154 (2008) 655662. [51] A. Wang, J. Qu, J. Ru, H. Liu, J. Ge, Mineralization of an azo dye Acid Red 14 by electro-Fenton's reagent using an activated carbon ber cathode, Dyes Pigm. 65 (2005) 227233. [52] H.C. Yatmaz, Y. Uzman, Degradation of pesticide monochrotophos from aqueous solutions by electrochemical methods, Int. J. Electrochem. Sci. 4 (2009) 614626.

14

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115 [82] M. Umar, H.A. Aziz, M.S. Yusoff, Trends in the use of Fenton, electro-Fenton and photo-Fenton for the treatment of landll leachate, Waste Manage. 30 (2010) 21132121. [83] H. Zhang, H.J. Choi, C.P. Huang, Optimization of Fenton process for the treatment of landll leachate, J. Hazard. Mater. B125 (2005) 166174. [84] Y. Wu, S. Zhou, F. Qin, K. Zheng, X. Ye, Modeling the oxidation kinetics of Fenton's process on the degradation of humic acid, J. Hazard. Mater. 179 (13) (2010) 533539. [85] P.F. Khamaruddin, M. Azmi Bustam, A. Aziz Omar, Using Fenton's reagents for the degradation of diisopropanolamine: effect of temperature and pH, International Conference on Environment and Industrial Innovation IPCBEE, Singapore, 12, 2011. [86] A. zcan, Y. Sahin, A.S. Koparal, M.A. Oturan, Carbon sponge as a new cathode material for the electro-Fenton process: comparison with carbon felt cathode and application to degradation of synthetic dye basic blue 3 in aqueous medium, J. Electroanal. Chem. 616 (2008) 7178. [87] B.H. Hameed, T.W. Lee, Degradation of malachite green in aqueous solution by Fenton process, J. Hazard. Mater. 164 (2009) 468472. [88] V. Homem, A. Alves, L. Santos, Amoxicillin degradation at ppb levels by Fenton's oxidation using design of experiments, Sci. Total Environ. 408 (2010) 62726280. [89] J.A. Zazo, G. Pliego, S. Blasco, J.A. Casas, J.J. Rodriguez, Intensication of the Fenton process by increasing the temperature, Ind. Eng. Chem. Res. 50 (2011) 866870. [90] J.H. Sun, S.P. Sun, G.L. Wang, L.P. Qiao, Degradation of azo dye Amido black 10B in aqueous solution by Fenton oxidation process, Dyes Pigm. 74 (2007) 647652. [91] T.S.N. Sankara Narayanan, G. Magesh, N. Rajendran, Degradation of Ochlorophenol from aqueous solution by electro-Fenton process, Fresenius Environ. Bull. 12 (7) (2003) 776780. [92] F. Zhang, G.M. Li, X.H. Zhao, H.K. Hu, J.W. Huang, Study status and progress in wastewater treatment by electro-Fenton method, Ind. Water Treat. 24 (2004) 913. [93] M. Panizza, G. Cerisola, Removal of organic pollutants from industrial wastewater by electrogenerated Fenton's reagent, Water Res. 35 (2001) 39873992. [94] M. Perez, F. Torrades, J.A. Garcia-Hortal, X. Domenech, J. Peral, Removal of organic contaminants in paper pulp treatment efuents under Fenton and photoFenton conditions, Appl. Catal., B 36 (2002) 6374. [95] M. Muruganandham, M. Swaminathan, Decolourisation of reactive orange 4 by Fenton and photo-Fenton oxidation technology, Dyes Pigm. 63 (2004) 315321. [96] J. Anotai, C.C. Su, Y.C. Tsai, M.C. Lu, Effect of hydrogen peroxide on aniline oxidation by electro-Fenton and uidized-bed Fenton processes, J. Hazard. Mater. 183 (2010) 888893. [97] E. Fockedey, A.V. Lierde, Coupling of anodic and cathodic reactions for phenol electro-oxidation using three-dimensional electrodes, Water Res. 36 (16) (2002) 41694175. [98] Z.M. Qiang, J.H. Chang, C.P. Huang, Electrochemical regeneration of Fe2+ in Fenton oxidation processes, Water Res. 37 (2003) 13081319. [99] M. Diagne, N. Oturan, M.A. Oturan, Removal of methyl parathion from water by electrochemically generated Fenton's reagent, Chemosphere 66 (2007) 841848. [100] E. Brillas, J. Casado, Aniline degradation by electro-Fenton and peroxicoagulation processes using a ow reactor for wastewater treatment, Chemosphere 47 (3) (2002) 241248. [101] Z. Eren, F.N. Acar, Adsorption of Reactive Black 5 from an aqueous solution: equilibrium and kinetic studies, Desalination 194 (2006) 110. [102] G. Crini, Non-conventional low-cost adsorbents for dye removal: a review, Bioresour. Technol. 97 (2006) 10611085. [103] J. Bandara, C. Morrison, J. Kiwi, C. Pulgarin, P. Peringer, Degradation/decoloration of concentrated solutions of Orange II. Kinetics and quantum yield for sunlight induced reactions via Fenton type reagents, J. Photochem. Photobiol., A 99 (1996) 5766. [104] S.D. Richardson, A.D. Thruston, T.W. Collette, K.S. Patterson, J. Lykins, J.C. Ireland, Identication of TiO2/UV disinfection byproducts in drinking water, Environ. Sci. Technol. 30 (1996) 33273334. [105] T. Kowalkowski, M. Gadzala-Kopciuch, R. Kosobucki, K. Krupczynska, T. Ligor, B. Buszewski, Organic and inorganic pollution of the Vistula River basin, J. Environ. Sci. Health., Part A 42 (2007) 421426. [106] D. Barcelo, Environmental protection agency and other methods for the determination of priority pesticides and their transformation products in water, J. Chromatogr. A 643 (1993) 117143. [107] J.J. Aaron, M.A. Oturan, New photochemical and electrochemical methods for the degradation of pesticides in aqueous media environmental applications, Turk. J. Chem. 25 (2001) 509520. [108] B. Boye, M.M. Dieng, E. Brillas, Degradation of herbicide 4-chlorophenoxyacetic acid by advanced electrochemical oxidation methods, Environ. Sci. Technol. 36 (13) (2002) 30303035. [109] R.B. Rajendran, A. Subramanian, Pesticide residues in water from river Kaveri, South India, Chem. Ecol. 13 (4) (1997) 223236. [110] N. Sankararamakrishnan, A.K. Sharma, R. Sanghi, Organochlorine and organophosphorous pesticide residues in ground water and surface waters of Kanpur, Uttar Pradesh, India, Environ. Int. 31 (1) (2005) 113120. [111] R. Sanghi, M.K.K. Pillai, T.R. Jayalekshmi, A. Nair, Organochlorine and organophosphorus pesticide residues in breast milk from Bhopal, Madhya Pradesh, India, Hum. Exp. Toxicol. 22 (2003) 7376.

[53] J. Ruiz, C. Arias, E. Brillas, A. Hernndez-Ramrez, J.M. Peralta-Hernndez, Mineralization of Acid Yellow 36 azo dye by electro-Fenton and solar photoelectro-Fenton processes with a boron-doped diamond anode, Chemosphere 82 (2011) 495501. [54] K. Cruz-Gonzlez, O. Torres-Lpez, A. Garca-Len, J.L. Guzmn-Mar, L.H. Reyes, A. Hernndez-Ramrez, J.M. Peralta-Hernndez, Determination of optimum operating parameters for Acid Yellow 36 decolorization by electro-Fenton process using BDD cathode, Chem. Eng. J. 160 (2010) 199206. [55] C.T. Wang, J.L. Hu, W.L. Chou, Y.M. Kuo, Removal of color from real dyeing wastewater by electro-Fenton technology using a three-dimensional graphite cathode, J. Hazard. Mater. 152 (2008) 601606. [56] E. Isarain-Chavez, J.A. Garrido, R.M. Rodrguez, F. Centellas, C. Arias, P.L. Cabot, E. Brillas, Mineralization of metoprolol by electro-Fenton and photoelectro-Fenton processes, J. Phys. Chem. A 115 (2011) 12341242. [57] A. Dirany, S.E. Aaron, N. Oturan, I. Sirs, M.A. Oturan, J.J. Aaron, Study of the toxicity of sulfamethoxazole and its degradation products in water by a bioluminescence method during application of the electro-Fenton treatment, Anal. Bioanal. Chem. 400 (2011) 353360. [58] B. Ramesh Babu, K. Seeni Meera, P. Venkatesan, D. Sunandha, Removal of fatty acids from palm oil efuent by combined electro-Fenton and biological oxidation process, Water Air Soil Pollut. 211 (2010) 203210. [59] P. Ghosh, A.N. Samanta, S. Ray, Reduction of COD and removal of Zn2+ from rayon industry wastewater by combined electro-Fenton treatment and chemical precipitation, Desalination 266 (2011) 213217. [60] M. Pimentel, N. Oturan, M. Dezotti, M.A. Oturan, Phenol degradation by advanced electrochemical oxidation process electro-Fenton using a carbon felt cathode, Appl. Catal., B 83 (2008) 140149. [61] K. Ayoub, S. Nelieu, E.D. Hullebusch, J. Labanowski, I. Schmitz-Afonso, A. Bermond, M. Cassir, Electro-Fenton removal of TNT: evidences of the electrochemical reduction contribution, Appl. Catal., B 104 (2011) 169176. [62] S. Irmak, H.I. Yavuz, O. Erbatur, Degradation of 4-chloro-2-methylphenol in aqueous solution by electro-Fenton and photoelectro-Fenton processes, Appl. Catal., B 63 (2006) 243248. [63] B. Balci, M.A. Oturan, N. Oturan, I. Sires, Decontamination of aqueous glyphosate, (aminomethyl) phosphonic acid, and glufosinate solutions by electro-Fenton -like process with Mn2+ as the catalyst, J. Agric. Food Chem. 57 (2009) 48884894. [64] Y. Fan, Z. Ai, L. Zhang, Design of an electro-Fenton system with a novel sandwich lm cathode for wastewater treatment, J. Hazard. Mater. 176 (2010) 678684. [65] Z. Ai, T. Mei, J. Liu, J. Li, F. Jia, L. Zhang, J. Qiu, Fe@Fe2O3 core-shell nanowires as an iron reagent. 3. Their combination with CNTs as an effective oxygen-fed gas diffusion electrode in a neutral electro-Fenton system, J. Phys. Chem. C 111 (2007) 1479914803. [66] C.T. Wang, W.L. Chou, M.H. Chung, Y.M. Kuo, COD removal from real dyeing wastewater by electro-Fenton technology using an activated carbon ber cathode, Desalination 253 (2010) 129134. [67] S. Hammami, N. Bellakhal, N. Oturan, M.A. Oturan, M. Dachraoui, Degradation of Acid Orange 7 by electrochemically generated OH radicals in acidic aqueous medium using a boron doped diamond or platinum anode: a mechanistic study, Chemosphere 73 (2008) 678684. [68] M. Sudoh, H. Kitaguchi, K. Koide, Electrochemical production of hydrogen peroxide by reduction of oxygen, J. Chem. Eng. Jpn. 18 (1985) 409414. [69] A.K. Abdessalem, N. Oturan, N. Bellakhal, M. Dachraoui, M.A. Oturan, Experimental design methodology applied to electro-Fenton treatment for degradation of herbicide chlortoluron, Appl. Catal., B 78 (2008) 334341. [70] G.V. Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH/O) in aqueous solution, J. Phys. Chem. Data Ref. 17 (1988) 513886. [71] M.A. Oturan, N. Oturan, C. Lahitte, S. Trevin, Production of hydroxyl radicals by electrochemically assisted Fenton's reagent. Application to the mineralization of an organic micropollutant, the pentachlorophenol, Electroanal. Chem. 507 (2001) 96102. [72] J.H. Ramirez, F.M. Duarte, F.G. Martins, C.A. Costa, L.M. Madeira, Modelling of the synthetic dye Orange II degradation using Fenton's reagent: from batch to continuous reactor operation, Chem. Eng. J. 148 (2008) 394404. [73] J.J. Pignatello, Dark and photoassisted iron (3+)-catalyzed degradation of chlorophenoxy herbicides by hydrogen peroxide, Environ. Sci. Technol. 26 (1992) 944951. [74] H. Shemer, K.G. Linden, Degradation and by-product formation of diazinon in water during UV and UV/H2O2 treatment, J. Hazard. Mater. 136 (2006) 553559. [75] Q. Wang, A.T. Lemley, Kinetic model and optimization of 2,4-D degradation by anodic Fenton treatment, Environ. Sci. Technol. 35 (2001) 45094514. [76] M.Y.A. Mollah, R. Schennach, J.R. Parga, D.L. Cocke, Electrocoagulation (EC) science and applications, J. Hazard. Mater. 84 (2001) 2941. [77] W.P. Ting, M.C. Lu, Y.H. Huang, Kinetics of 2,6-dimethylaniline degradation by electro-Fenton process, J. Hazard. Mater. 161 (2009) 14841490. [78] N. Daneshvar, S. Aber, V. Vatanpour, M.H. Rasoulifard, Electro-Fenton treatment of dye solution containing Orange II: inuence of operational parameters, J. Electroanal. Chem. 615 (2008) 165174. [79] X. Zhu, J. Tian, R. Liu, L. Chen, Optimization of Fenton and electro-Fenton oxidation of biologically treated coking wastewater using response surface methodology, Sep. Purif. Technol. 81 (2011) 444450. [80] W.S. Chen, S.Z. Lin, Destruction of nitrotoluenes in wastewater by electroFenton oxidation, J. Hazard. Mater. 168 (2009) 15621568. [81] A.M.F.M. Guedes, L.M.P. Madeira, R.A.R. Boaventura, C.A.V. Costa, Fenton oxidation of cork cooking wastewateroverall kinetic analysis, Water Res. 37 (13) (2003) 30613069.

PV. Nidheesh, R. Gandhimathi / Desalination 299 (2012) 115 [112] J.P. Jani, J.S. Patel, M.P. Shah, S.K. Gupta, S.K. Kashyap, Levels of organochlorine pesticides in human milk in Ahmedabad, India, Int. Arch. Occup. Environ. Health 60 (1988) 111113. [113] P.J. John, N. Bakore, P. Bhatnagar, Assessment of organochlorine pesticide residue levels in dairy milk and buffalo milk from Jaipur City, Rajasthan, India, Environ. Int. 26 (4) (2001) 231236. [114] D.W. Kolpin, E.M. Thurman, D.A. Goolsby, Occurrence of selected pesticides and their metabolites in near-surface aquifers of the Midwestern United States, Environ. Sci. Technol. 30 (1) (1996) 335340. [115] G. Kaichouh, N. Oturan, M.A. Oturan, K.E. Kacemi, A.E. Hourch, Degradation of the herbicide imazapyr by Fenton reactions, Environ. Chem. Lett. 2 (2004) 3133. [116] G. Kaichouh, N. Oturan, M.A. Oturan, A.E. Hourch, K.E. Kacemi, Mineralization of herbicides imazapyr and imazaquin in aqueous medium by Fenton, photoFenton and electro-Fenton processes, Environ. Technol. 29 (2008) 489496. [117] A.K. Abdessalem, N. Bellakhal, N. Oturan, M. Dachraoui, M.A. Oturan, Treatment of a mixture of three pesticides by photo- and electro-Fenton processes, Desalination 250 (2010) 450455. [118] F.J. Rivas, F.J. Beltrn, O. Gimeno, P. Alvarez, Treatment of brines by combined Fenton's reagent-aerobic biodegradation II. Process modeling, J. Hazard. Mater. B96 (2003) 259276. [119] W. Gernjak, T. Krutzler, A. Glaser, S. Malato, J. Caceres, R. Bauer, A.R. FernandezAlba, Photo-Fenton treatment of water containing natural phenolic pollutants, Chemosphere 50 (2003) 7178. [120] V. Kavitha, K. Palanivelu, Degradation of nitrophenols by Fenton and photoFenton processes, J. Photochem. Photobiol., A 170 (2005) 8395. [121] A. Smeds, R. Franzen, L. Kronberg, Occurrence of some chlorinated enol lactones and cyclopentene-1,3-diones in chlorinated waters, Environ. Sci. Technol. 29 (7) (1995) 18391844. [122] Y. Song-hu, L. Xiao-hua, Comparison treatment of various chlorophenols by electro-Fenton method: relationship between chlorine content and degradation, J. Hazard. Mater. B118 (2005) 8592. [123] N. Oturan, M. Panizza, M.A. Oturan, Cold incineration of chlorophenols in aqueous solution by advanced electrochemical process electro-Fenton. Effect of

15

[124] [125] [126]

[127] [128]

[129] [130] [131]

[132] [133]

[134]

[135]

number and position of chlorine atoms on the degradation kinetics, J. Phys. Chem. A 113 (2009) 1098810993. S. Yuan, M. Tian, Y. Cui, L. Lin, X. Lu, Treatment of nitrophenols by cathode reduction and electro-Fenton methods, J. Hazard. Mater. B137 (2006) 573580. B. Schroth, G. Sposito, Effect of landll leachate organic acids on trace metal adsorption by kaolinite, Environ. Sci. Technol. 32 (1998) 14041408. A. Papastavrou, D. Mantzavinos, E. Diamadopoulos, A comparative treatment of stabilized landll leachate: coagulation and activated carbon adsorption vs. electrochemical oxidation, Environ. Technol. 30 (14) (2009) 15471553. A. Altin, An alternative type of photoelectro-Fenton process for the treatment of landll leachate, Sep. Purif. Technol. 61 (2008) 391397. S. Mohajeri, H.A. Aziz, M.H. Isa, M.A. Zahed, M.N. Adlan, Statistical optimization of process parameters for landll leachate treatment using electro-Fenton technique, J. Hazard. Mater. 176 (2010) 749758. A.I. Balcioglu, M. tker, Treatment of pharmaceutical wastewater containing antibiotics by O3 and O3/H2O2 processes, Chemosphere 50 (2003) 8595. T.A. Yamarik, Safety assessment of dichlorophene and chlorophene, Int. J. Toxicol. 23 (2004) 127. E. Brillas, E. Mur, R. Sauleda, L. Sanchez, J. Peral, X. Domenech, J. Casado, Aniline mineralization by AOP's: anodic oxidation, photocatalysis, electro-Fenton and photoelectro-Fenton processes, Appl. Catal., B 16 (1998) 3142. W.P. Ting, Y.H. Huang, M.C. Lu, Catalytic treatment of petrochemical wastewater by electro-assisted Fenton technologies, React. Kinet. Catal. Lett. 92 (1) (2007) 4148. G.R. Agladze, G.S. Tsurtsumia, B.I. Jung, J.S. Kim, G. Gorelishvili, Comparative study of chemical and electrochemical Fenton treatment of organic pollutants in wastewater, J. Appl. Electrochem. 37 (2007) 985990. A.F. Martins, M.L. Wilde, T.G. Vasconcelos, D.M. Henriques, Nonylphenol polyethoxylate degradation by means of electrocoagulation and electrochemical Fenton, Sep. Purif. Technol. 50 (2006) 249255. W.P. Ting, M.C. Lu, Y.H. Huang, The reactor design and comparison of Fenton, electro-Fenton and photoelectro-Fenton processes for mineralization of benzene sulfonic acid (BSA), J. Hazard. Mater. 156 (2008) 421427.