Accepted Manuscript

Advanced Oxidation Processes for Treatment of Leachate from Hazardous Waste

Landfill: A Critical Review

Pratibha Gautam, Sunil Kumar, Snehal Lokhandwala

PII: S0959-6526(19)32489-8

DOI: 10.1016/j.jclepro.2019.117639

Article Number: 117639

Reference: JCLP 117639

To appear in: Journal of Cleaner Production

Received Date: 15 August 2018

Accepted Date: 13 July 2019

Please cite this article as: Pratibha Gautam, Sunil Kumar, Snehal Lokhandwala, Advanced
Oxidation Processes for Treatment of Leachate from Hazardous Waste Landfill: A Critical Review,
Journal of Cleaner Production (2019), doi: 10.1016/j.jclepro.2019.117639

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1 Total Word Count: 11752

2
3
4 Advanced Oxidation Processes for Treatment of Leachate from Hazardous Waste

5 Landfill: A Critical Review

6 Pratibha Gautam1,2,3, Sunil Kumar2*, Snehal Lokhandwala3

7 1Academy of Scientific and Innovative Research (AcSIR), Ghaziabad- 201002, India

8
9 2 CSIR-National Environmental Engineering Research Institute (CSIR-NEERI), Nehru Marg,
10 Nagpur 440020, India
11
12 3Department of Environmental Science & Technology, Shroff S.R. Rotary Institute of
13 Chemical Technology, Ankleshwar (Gujarat), 393135, India

14 *Corresponding author (Email): s_kumar@neeri.res.in

15 Abstract

16 Leachate produced from hazardous waste landfills (HWLs) is toxic and contain high

17 concentration of refractory organics, ammoniacal-nitrogen, heavy metals, inorganic salts and

18 organo-chloro compounds. Various Advanced Oxidation Processes (AOPs) have been

19 developed in last few decades for efficiently treating the landfill leachate and many are still

20 under development. Researchers have reviewed the performance of conventional AOPs for

21 treating leachate produced from municipal solid waste landfills (MSWLs) but as this leachate

22 is entirely different in characteristics from HWL leachate, these studies are not very useful

23 when it comes to management of HWL leachate; also, specific studies focused on HWL

24 leachate are rarely available. Present study critically reviews various AOPs involving ozone,

25 UV radiation, hydrogen peroxide, electrocoagulation and electrochemical oxidation for their

26 mechanism, treatment efficacy, advantages and limitations with a focus on HWL leachate. A

27 brief review of emerging AOPs like wet air oxidation, hydrodynamic cavitation and ultrasound

28 assisted AOPs is also discussed. This study also aims to identify the AOP which is user friendly,

29 capable to treat the HWL leachate efficiently, discourage the use of chemicals and can be
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30 operated at ambient temperature and pressure. After thorough review of different AOPs,

31 Electrocoagulation appears to be a very promising and effective AOP involving in-situ

32 generation of coagulants and converting the organic pollutants in simpler and noble compounds

33 like carbon dioxide and water. Electrocoagulation can be considered as one of the greener and

34 cleaner technology for treatment of HWL leachate, which on optimization can result in a

35 reduction of COD up to 60% along with considerable decrease in metal content in range of

36 70%-90% and has further potential of improvement and research.

37 Keywords: Hazardous waste landfill, Leachate, Advanced Oxidation Process, COD reduction

38 1.0 Introduction

39 Rapid industrialization in the last few decades has resulted in the generation of huge amount

40 of industrial solid waste, a major portion of which unfortunately ends up in the engineered

41 landfills. Heterogenous waste (produced from multiple sources) grounded in landfills (common

42 hazardous waste landfills) undergo several physicochemical changes as it is exposed to

43 different environmental conditions and results in a highly concentrated liquid extract (Yao,
44 2017) called as leachate. The characteristics of leachate depend on many operational and

45 environmental factors (Reinhart and Townsend, 1998) including characteristics of grounded

46 parent waste material, the moisture content and the age of landfill (Farrokhiet al., 2015) and

47 often characterized by the low BOD, high COD, high NH3-N, high COD/BOD5 ratio, blackish

48 or dense brown color and high redox potential. Leachate generation can also be understood as
49 transformation of pollutants from solid to liquid phase.

50 As this leachate has huge potential to contaminate the surface and subsurface water which

51 further leads to mortality of flora and fauna, its environmentally sound treatment is a

52 challenging task for sustainable environment (Sil and Kumar, 2017). Literature studies have

53 revealed information about characterization and treatment of leachate produced from municipal

54 solid waste landfills (MSWLs) to a greater extent but studies characterizing the leachate
55 produced from Hazardous waste landfills (HWLs) are very limited. Conventional biological

56 treatment processes have been extensively used for treating MSWL leachate but such
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57 conventional biological treatments are not effective for HWL leachate as it contains toxic and

58 bio-refractory compounds in the matrix and has high variability in organic loading. This led to

59 the evolution of advance oxidation process for treatment of both type of leachates. Researchers

60 have used Potassium permanganate, calcium hypochlorite, chlorine, ozone and hydrogen

61 peroxide as oxidising agents during their experiments to treat landfill leachate by converting
62 organic pollutants into less complex compounds (Forgie,1988). The main concern with

63 conventional treatment processes and many of chemical-based advanced oxidation processes

64 is that they require chemical addition that majorly converts water pollutants into solid waste

65 and involves a cycle of sludge generation and dumping as shown in Figure 1. Such processes

66 cannot be considered as a sustainable solution for leachate management as they leave a huge
67 environmental footprint.

68

69 Figure 1: Cycle of Leachate Production, Sludge Generation, and Dumping

70 Need of the hour is to opt for greener technologies/AOPs for leachate treatment which
71 eliminates or minimize the chemical consumption, produce lesser sludge, involves lesser
72 mechanical operations and easy to handle. With advancement in research, other treatment
73 techniques like Fenton's process, ozonation, UV assisted processes; electrochemical
74 oxidation, photo-assisted Fenton and electrocoagulation were developed for treating leachate.
75 The ‘later’ introduced processes are perceived as cleaner technologies as they discourage the
76 use of chemicals that ultimately result in the generation of a lesser quantity of sludge
77 comparative to other chemical based or biological processes.
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78 Current study is focused on the performance of various AOPs for treating HWL leachate with
79 their advantages and limitations so that it can be taken as a reckoner for current research work
80 going on for developing new technologies for leachate treatment. The ongoing research
81 hotspot in AOPs like hydrodynamic cavitation, electro fenton and electrocoagulation and
82 others are also discussed in detail. The review is aimed to identify a suitable AOP from all
83 available AOPs that has following benefits:
84  User friendly
85  Capable to treat the HWL leachate efficiently
86  Discourage the use of chemicals
87  Operated at ambient temperature and pressure
88  One-pot technology
89
90 2.0 Advanced Oxidation Processes (AOPs)

91 AOPs were initially proposed to treat potable water (Glaze et al., 1987), and were defined as

92 “Near ambient temperature and pressure water treatment processes involving the generation of

93 hydroxyl radicals (OH) in sufficient quantity to affect water purification”. The concept was

94 later on extended to oxidation involving sulphate radicals too. Research on AOPs is focused

95 on the reduction of recalcitrant compounds and toxic elements in leachate/wastewater, and

96 further research is going on to increase the efficiency of existing AOPs and developing newer

97 AOPs. Presently available AOPs for treating leachate/wastewater can be categorized on the

98 basis of applicable physico-chemical processes (figure 2) :

99
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Advance Oxidation
Processes (AOPs)

Ozone based Chemical Based Processes based on Photoassisted

Miscllaneous
Processes Process electricity Processes

*Ozone in Alkaline * Fenton Oxidation * Electrochemical * Photoassisted Fenton * Wet Air Oxidation
medium Process Oxidation Process * Hydrodynamic
* Ozone with * Persulfate with heat * Electrocoagulation * Persulfate with UV cavitation
Hydrogen peroxide * Persulfate with Fe(II) * Electrofenton * Ozone with UV *Ultrasound assisted
* Ozone with UV and * Persulfate oxidation * Peroxide with UV processes
Hydrogen peroxide * Photocatalysis * Catalyst Assisted
* Catalytic Ozonation * Photoelectrochemical Processes
100

101 Figure 2: Advanced Oxidation Processes

102 AOPs used conventionally are also classified as homogeneous and heterogeneous processes

103 depending upon occurring in single phase or using heterogeneous catalysts like carbon

104 materials, metal supported catalysts or semiconductors like oxides of Titanium, Zinc, and

105 Tungsten (Bapuponnusami and Muthukumar, 2014). Some examples of homogeneous

106 processes are O3, O3 + H2O2, wet peroxide oxidation, photo-Fenton and others whereas

107 heterogeneous processes involve catalytic wet peroxide oxidation (CWPO), catalytic ozonation

108 and others.

109 The efficiency of AOP depend on generated hydroxyl radicals having oxidation potential in

110 the range 2.8 V to 1.95 V (pH = 0 to 14) versus Standard Calomel electrode (Reference

111 electrode). These hydroxyl radicals act as the most reactive oxidizing agent in leachate

112 treatment. Figure 3 represents the oxidation potential of some common oxidizing agents

113 (Oliveira et al., 2014).

114
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Flourine 3.06

OXIDISING AGENTS
Hydroxyl radical 2.8
Oxygen (diatomic) 2.42
Ozone 2.08
Hydrogen peroxide 1.78
Hypochlorite 1.49
Chlorine 1.36
Chlorine dioxide 1.27
Oxygen (molecular) 1.23

0 0.5 1 1.5 2 2.5 3 3.5

OXIDATION POTENTIAL (E0) (V)
115

116 Figure 3: Oxidation Potential of Various Oxidizing Agents (E0) (V)

117 Hydroxyl radical is non-selective and react rapidly with many species having rate constants in

118 the range 108 – 1010 M-1 s-1. Reactive radicals attack the organic pollutants in four ways, i.e.,

119 abstraction of hydrogen, transferring an electron, the addition of radicals and radical

120 combination (Solarchem Environmental Systems, 1994). Alkyl free radical (R) or Alcohol (R-

121 OH) is produced by the reaction of OH with organic compounds which might react with O2

122 and get transformed to organic peroxyl radicals (ROO). More reactive species like hydrogen

123 peroxide and superoxide are formed during further reactions,which can degrade recalcitrant

124 organics such as phenolic and organochloro compounds. It converts the complex organic

125 compounds into more biodegradable compounds which are easily removed in biological

126 treatment. OH having a very short lifetime needs generation in situ by combination of

127 oxidizing agents, irradiation, and catalysts (Huang C et al., 1993). Figure 4 shows

128 characteristics of hydroxyl radical.

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Non-
Selective
Strong
oxidant Reacts
Rapidly
(E⁰ = 2.8 V)

OH
Short Life
Harmless
Time

Converts
Pollutants Produced
to CO2 In-situ
& H2O
129

130 Figure 4: Characteristics of Hydroxyl Radical

131 On initiation of free radical by H2O2 or ozone, a complex cascade of oxidative reactions occur

132 in the solution and the activated radicals degrade the target compounds rapidly. The kinetic

133 rate of degradation by AOPs depend on pollutant concentration, reactants, temperature and

134 presence of different scavengers like bicarbonate ion (Hoigne, 1997).

135 It has also been observed that AOPs when combined with biological treatment (as pre or

136 posttreatment) can give better COD reduction in comparison to any standalone technology

137 under similar conditions. Membrane Bioreactors (MBRs) have emerged to be a promising

138 advanced biological treatment process. As reported by Ioannou and Fata-Kassions (2013),

139 COD removal of around 70% was achieved on treatment of waste water with solar photo-fenton

140 process which was pre-treated by MBR, wherein the major COD removal (58%) was achieved

141 in first 30 minutes of solar treatment. But the major limitation of membrane bioreactor is the

142 membrane fouling problem which depends on microbial population structure and microbial

143 cell density. It was reported that nitrifying activated sludge, developed at low C/N ratio,

144 significantly decreased the fouling problem and increased nitrifying efficiency (Sepehri and

145 Sarrafzadeh, 2018)

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146 2.1. Ozone-based Advanced Oxidation Process

147 Hazardous landfill leachate can be effectively treated with ozone as it has high oxidative power

148 (E0 = 2.08 V) (Figure 3). Ozone alters the molecular structure of the organic compounds and

149 oxidize them to more biodegradable compounds to be removed by biological treatment. AOPs

150 based on ozone extensively reduce COD and BOD in leachate (Table 1). Rivas et al. (2003)

151 achieved 30% reduction in COD using ozone dose as 1.3 to 1.5 g O3/ g of COD for one hour

152 whereas Hagman et al.(2008) achieved 22% reduction in COD at pH 8-9 using 4 g/L O3.

153 Table 1: O3 Treatment of Leachates

Initial Initial pH Colour BOD5/COD % % O3 dosage Ref

COD BOD5 MgPt After reduction removal as g/l

(mg/l) (mg/l) Co/l) treatment in COD in colour

6500 500 8.1 12,000 0.5 15 90 1.2 (Murray and

Parsons, 2004)*

3460 150 8.2 5300 - 48 87 3.0 (Silva et al.,

2004)*

500 10 -- 0.2 50 -- 0.5 mg (Haapea et al.,

O3/mg of 2002) **

COD

154 *: Municipal landfill **: Hazardous waste landfill

155 Wang et al. (2004) in his study on landfill leachate reported that when 12.5 g O3/L was added

156 to leachate, the alkalinity was found to decrease from 4,030 mg/L (as CaCO3) to 2,900mg/L

157 and the amount of NH3 oxidized to NO3 − was 309 mg N/L. Ozone oxidation is pH dependent

158 and can proceed via following two mechanisms (Kurniawan et al., 2006):

159  Molecular ozone reactions (direct electrophilic attack on the recalcitrant pollutants)

160  Generation of OH radical (indirect attack due to decomposition of ozone)

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161 a. Molecular Ozone Reactions

162 These reactions are known to be extremely selective and are restricted to aliphatic compounds

163 like ethylene & dichloroethylene, and aromatic compounds like BTX and specific functional

164 groups (Langlais et al., 1991). They proceed via cycloaddition, nucleophilic reaction or

165 electrophilic reactions as shown in Table 2.

166 Table 2: Molecular Ozone Reactions (Bailey and Trahanovsky, 1978)

Type of Reaction Target Functional Group /Molecule Product

Cyclo addition Unsaturated compounds Carbonyl compounds (aldehydes

(C=C, C=C-O-R) or ketones) and H2O2

Electrophilic Aromatics substituted with electron Quinoid (e.g., pyridoxine), and

reaction donor groups like –OH, -NH2 aliphatic products with carbonyl

and carboxyl functions.

Nucleophilic Molecular sites having electron deficit Aromatic and aliphatic products

reactions

167

168 b. OH Radical Reactions

169 OH radical generated by ozonation using hydrogen peroxide is efficient to degrade organic

170 contaminants in the wastewater and dosage optimization may yield higher rate constant. pH,

171 UV light, the concentration of ozone and radical scavenger concentration affect the stability of

172 dissolved ozone (Tomivasu, 1985). Reactions 1-19 for two mechanisms as presented in Table

173 3 explains ozone decomposition.

174 Table 3: Mechanism of Decomposition of Aqueous Ozone (Tomivasu et al., 1985; Weiss,

175 1935; Staehelin et al., 1984; Grasso,1987; Clemens and Urs, 2012)

Mechanism proposed by Hoigné, Mechanism proposed by Gordon, Tomiyasu, and

Staehelin, and Buhler Fukutomi

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O3+ OH − → HO2+ O2 − (1) O3+ OH − → HO2+ O2 − (10)

HO2↔O2− + H + (2) HO

2+ O3 →O3− + HO2 (11)

O3+ O2− → O − + O2 (3) HO OH − ↔ O2 − + H2O (12)

3 2+

O − (4) (13)
3 + H + ↔ HO3 O −
2 + O3 →O3− + O2

HO OH
(5) O −
(14)
3→ + O2 3 + H2O → OH + O2 + OH −
(6) (15)
OH + O3→ HO4 O − + OH →O2− + HO2
3
(7) (16)
HO HO O − + OH → O3+ OH –
4→ 2+ O2 3
(8)
HO  OH (17)
4+ HO4→ H2O2+ 2O3 +O3 →HO2 + O2
(9)
HO
4+
HO
3→ H2O2+ O3+ O2 OH + CO3–2→ OH − + CO3– (18)

Note: [ Reaction at pH = 8.0 – 9.0] CO –+ O3 → CO2 + O2− + O2

3 (19)
[ 1 mol of O3 yield 1 mol of OH] Note: The two intermediates HO3 and HO4 are not

proposed in this mechanism

177 If pH of the reaction exceeds 9.0, the ozone-resistant compounds called hydroxyl radical

178 scavengers resist oxidation. The carbonate ions formed from bicarbonate ions as shown in

179 reaction 20 and 21, act as scavengers and reduce the rate (kinetic) of oxidation (Kurniawan et

180 al., 2006).

181 CO3–2+ OH →OH – +CO3– (20)

182 HCO3–+OH →OH – +HCO3 (21)

183 2.1.1 Ozone and Hydrogen Peroxide (Peroxon)

184 Ozone and Hydrogen peroxide react as shown in reactions 22 to 28, in a complex set of

185 reactions to give OH radicals (Langlais et al., 1991). The final product of these reactions are

186 two hydroxyl radicals involving one H2O2 and two O3 molecules (Schulte et al., 1995).

187 H2O2 + H2O ↔HO2–+ H3O + (22)

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188 O3 + HO2–→ OH +O2− + O2 (23)

189 O −+ H+ ↔ HO2 (24)

2

190 O −+ O3→ O − + O2 (25)

2 3

191 O − + H + ↔ HO3 (26)

3

192 HO →OH + O2 (27)

3

193 H2O2 + 2O3 → 2OH + 3O2 (28)

194 The reaction pH for peroxon process is in the range of 8 to 8.4. As the dose of ozone increases,

195 alkalinity tends to decrease . Hydrogen peroxide assisted ozonation give better reduction in

196 COD. Refractory compounds can be oxidized by the introduction of the radical system as it

197 allows getting benefits of molecular ozone reactions (selective) before the process gets

198 converted to free radical attack (non-selective). It is reported that at initial pH of 7, ozone

199 application at 5.6 gm O3/ hr for 60 min, followed by H2O2 at a rate of 400 mg/l gave 72% COD

200 reduction and BOD5/COD ratio increased from 0.01 to 0.24(Cortez et al., 2011). Tizaoui et

201 al.(2007) observed 40-50% oxidation of initial COD in a tailor-made O3 batch reactor with 50

202 min of operation. During his experiments, he found a slight change of pH (< 0.4) and the

203 average pH remained at about 8.7. Ozonation generally decreases the pH values to acidic range

204 due to the formation of carboxylic acids but here it was not observed may be due to presence

205 of high amount of bicarbonates in leachate which buffer the pH by reacting with acids.

206 The efficiency of Ozone/H2O2 treatment has been studied by many researchers and the results

207 obtained are presented in Table 4.

208 Table 4: O3/H2O2 Treatment of Leachates

Initial Initial pH BOD5/COD % O3 H2O2 Ref

COD BOD5 post- reduction dosage Dosage

(mg/l) treatment in COD as g/l as g/l

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5230 800 8.7 0.7 48 -- 2 (Weiss, 1935)*

2000 - - - 95 3.5 0.4 (Wable et al., 2011)*

1360 <5 8.4 0.32 93 1.5 0.3 (Cortezet al.,

2011)**

2000 160 8.4 0.13 92 1.5 0.3 (Tizaouiet

al.,2007)**

500 -- 10 0.2 37 0.5 mg 3.2 mol (Haapea et al.,

O3/mg of /mol O3 2002) ***

COD

209 *: industrial wastewater**: Leachate from municipal landfill***: Hazardous waste landfill

210 2.1.2. Ozone with UV

211 Ozone radiated by UV light can also be a good source of hydroxyl radicals (OH). Radiation

212 of UV light in the range 200-300 nm wavelength is absorbed by ozone with a maximum

213 absorbance at 253.7nm (Langlais et al., 1991). Due to UV radiation, an oxygen atom as O (1D)

214 and an oxygen molecule is released which reacts to form two hydroxyl radicals as shown in

215 reactions 29 and 30 (McGrath and Norris, 1960):

216 O3+hυ (UV radiation) → O2+ O(1D) (29)

217 O(1D)+H2O → 2 OH (30)

218 Photolysis with ozone enhance the number of hydroxyl ions generation. It causes the formation

219 of H2O2, which proves that a combination of UV with ozonation is more effective than

220 individual processes. This method may be used for degrading such compounds that are resistant

221 to ozone alone (Roche et al., 1994). Chen et al.(2007) achieved very effective mineralization

222 of TOC with UV radiation of 96W and ozone dosage of 3.8 g/hr.

223 The following parameters may deteriorate the impact of ozone-based AOPs:
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224  High concentrations of ammonia and Nitrate/Nitrite in leachate (Yunho and Gunten,

225 2010)

226  Significant foaming in diffusive ozone gas reactors (Cooper, 2004)

227 The COD removal efficiency of this process is low although the reaction pH was within the

228 range of 7.8 to 8.0. Lesser efficiency may be due to high pH, high background absorbance and

229 low radiation intensity (Bigot et al. 1994). The efficiency of the generation of hydroxyl radical

230 can be increased by incorporating UV in Peroxon that is referred as photolytic peroxon process.

231 The photolysis of ozone and hydrogen peroxide molecules accelerates their decomposition. An

232 improved version of the O3/UV process is photocatalytic ozonation that involves Fe+2 as a

233 catalyst (Kurniawan et al., 2006).

234 2.1.3. Ozone with Persulfate

235 The efficiency of ozonation can be enhanced by combining ozone with a strong oxidant like

236 S2O8-2 (persulfate). The hydroxyl radicals formed during ozonation process work as initiator to

237 produce SO4−(Abu Amr et al., 2013a). At pH ranging from 2-7, the persulphate ions react with

238 water to form hydrogen sulphate ions and hydrogen peroxide that lead to increase HO2-

239 producing of more hydroxyl radicals in the system (Zhao et al., 2013). The mechanism involved

240 is as follows (Abu Amr et al., 2013b):

241 S2O8 -2 + 2H2O → 2HSO4 - + H2O2 (31)

242 S2O8 -2+ OH−→ SO4-2 + SO4 −+ ½ O2 + H+ (32)

243 SO4-2 + OH − → SO4 − +OH− (33)

244 Abu Amr et al.(2013b) optimized the treatment of landfill leachate by incorporating persulfate

245 ions in ozonation, and achieved higher efficiencies in the reduction of COD (72%), colour

246 (96%) and ammoniacal nitrogen (76%). He also reported that the combined method is more

247 efficient than individual species. The effect of Ozone /persulfate method was also found
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248 appropriate in post-treatment wherein the refractory organics were not removed by biological

249 treatments.

250 2.1.4. Catalytic Ozonation

251 Catalyst can be an addon to decrease the reaction time in ozonation. Catalytic ozonation can

252 quickly remove organic pollutants as catalysts improve the oxidizing power of ozone (Zequan

253 et al., 2012). Catalytic ozonation can be classified into two sub-techniques:

254 (a) Homogenous catalytic ozonation: Ozone is decomposed by transition metal ions via

255 either generation of free radicals or oxidation of complex formed between an organic

256 molecule and the catalyst.

257 (b) Heterogeneous catalytic ozonation: Several metal oxides of Mn, Ti, Al, Fe and Ce,

258 metals like Cu, Pt ,Ru on supports like TiO2 , SiO2, and activated carbon are used for

259 this ozonation. (Jacek, 2013)

260 The advantages of catalytic ozonation are as follows:

261  Enhances ozone consumption
262  Increases efficiency of ozonation by controlling radical generation
263  Hydroxyl radical generation at lower pH
264  Promote surface reactions between the adsorbed ozone and pollutants (Amir et al.,
265 2014)
266 Disadvantages of Ozone based AOPs

267 Ozone treatment standalone cannot meet the discharge standards as leachate is a complex

268 matrix with high organic content. To achieve reduction in COD, high ozone dose has to

269 applied, which make this process energy intensive. All the ozone-based AOPs involve ozone

270 mass transfer from gas to a liquid that is very low as some ozone is lost in the off-gas exiting

271 the ozone reactor. Efforts to enhance the ozone mass transfer efficiency (Gamal and Smith,

272 2001) are in process, but ozonation still proves to be a good option only for pre or post-

273 treatment of leachate.

274
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275

276 2.2 Fenton Oxidation Process

277 Fenton (1884) reported over a hundred years ago that maleic acid could be oxidized using the

278 Fenton process. Fe (II) ions readily get oxidized into Fe(III) in a fraction of minutes in the

279 presence of excess H2O2. The mechanism of this reaction (Harber and Weiss, 1934) shows the

280 activation of H2O2 in the presence of Fe+2 ions to form hydroxyl radicals that oxidize the organic

281 compounds in leachate as shown in reactions 34-40 below:

282 H2O2+ Fe 2+ → Fe 3+ + OH+ OH − (34)

283 H2O2+ Fe 3+ → Fe 2+ + H ++ HO2 (35)

284 H2O2+ OH → H2O + HO2 (36)

285 Fe 2+ + OH →Fe 3+ + OH – (37)

286 Fe 3+ + HO2 → Fe 2+ + O2H + (38)

287 Fe 2+ + HO2 + H + → Fe 3+ + H2O2 (39)

288 2HO2 → H2O2 + O2 (40)

289 Fenton process proceed through the following stages (Bigda, 1995):

290 a. Adjustment of pH

291 b. Oxidation Process

292 c. Neutralization and Coagulation

293 d. Precipitation

294 Fe(OH)3 precipitated has to be removed and is cost intensive. For Fenton process, pH is an

295 important parameter as it controls production of hydroxyl radicals and ferrous ion

296 concentration. Roudi et al. (2018) found maximum removal of COD at pH=3 and [Fe+2] = 1000

297 mg/l, which decreased with increase in pH. It was concluded that the pH value has to be in

298 acidic range to generate maximum hydroxyl radicals to achieve maximum oxidation of organic

299 compound. The organic substances present in leachate are removed at oxidation and
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300 coagulation stages. Oxidation takes place because of hydroxyl radical, whereas coagulation

301 takes place due to the occurrence of ferric hydroxo-complexes (Tang, 2003). The

302 H2O2/Fe+2ratio is primarily responsible for coagulation or oxidation to predominate (Neyens

303 and Baeyens, 2003). Lower ratio promotes coagulation, and higher promotes oxidation. For a

304 biologically stabilized leachate, Lau et al. (2001) reported 80% and 20% COD removal by

305 coagulation and oxidation. For a semi-aerobic landfill site in Malaysia, maximum reduction in

306 COD (58.1%) and colour (78.3%) was achieved at pH=3, [H2O2]=1020 mg/l, [Fe+2]= 560 mg/l,

307 molar ratio of H2O2 / Fe+2 = 3, reaction time of 120 minutes and agitation rate equals to 400

308 rpm (Mohajeri et al., 2010). Fenton process followed by ozone treatment enhanced the

309 reduction in COD, colour and ammoniacal nitrogen to 87%, 100% and 22% for landfill leachate

310 at an optimum dosage of Fe+2 and H2O2 as 2800 and 1700 mg/l(Aziz and Abu Amr, 2015).

311 Singa et al. (2018a) achieved maximum COD removal of 56.49% under optimum experimental

312 conditions as pH=3, H2O2/Fe2+ molar ratio = 3 and reaction time = 150 minutes when treating

313 leachate from hazardous landfill site. Table 5 shows the advantages and disadvantages of

314 Fenton oxidation process :

315 Table 5: Advantages and Disadvantages of Fenton oxidation process

Advantages Disadvantages

(a) Activation of Hydrogen peroxide (a) Fe+2 ions are consumed more as compared to
does not need energy. regenerated.
(b) Easy of operation and less (b) Narrow operation pH range between pH 2-3.
maintenance and inexpensive Fenton’s (c) High amount of chemicals and manpower is
reagent required for sludge treatment at the end of
(c) Short reaction time treatment
(d) Being homogenous in nature does not (d) Oxidants are wasted as few iron species
involve any mass transfer formed are very complex in nature (Sun et
al, 2009)
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316

317 2.3 Photo assisted Fenton Process / Photo-Fenton Process

318 Higher concentration of hydroxyl radicals can be obtained by this process. By radiation with

319 visible light or near UV, photolysis of Fe(OH)2+ (Iron hydroxyl complex) and Fe(C2O4)33- (Iron

320 oxalate complex) occur rapidly as per the reaction given in equation 41:

321 Fe(OH)2+ + hυ→ Fe2+ + OH (41)

322 The quantum yield (in above reaction) of Fe(OH)2+ was 0.017 + 0.003 at 360nm and 0.04+

323 0.04 at 313nm, at pH=4 and temperature 293K (Faust and Hoigne, 1990). The Iron oxalate

324 complexes as shown in reactions 42 to 44 are photoreactive and give an enhanced quantum

325 yield of 1.2 at 313nm in the presence of 1kW high-pressure mercury UV lamp keeping

326 exposure time as 1.5 to 6 min (Hatchard and Parker, 1956).

327 Fe(C2O4)3−3+ hυ→ Fe2+ + 2C2O4−2 +C2O4− (42)

328 C O − + Fe(C2O4)3−3→ Fe2+ + 3C2O4−2 + 2CO2 (43)

2 4

329 C O − + O2→ O2-+ 2CO2 (44)

2 4

330 Kim et al. (1998) concluded that at an inlet COD of 1150 mg/l, about 70% reduction in COD

331 is obtained at pH=3.2 and 500W radiation wherein the dosage of Fe+2 and H2O2 was 72 mg/l

332 and 1.15 mg/l. Hermosilla et al.(2009) achieved 70% reduction in COD of leachate from a

333 young landfill in Spain. Singa et al. (2018c) reported 68% reduction in COD of leachate from

334 hazardous waste landfill using 16W UV lamp and under operating conditions as molar ratio

335 (H2O2/Fe2+) = 3.0 and reaction time = 90 min. The advantage of UV assisted fenton process is

336 “lesser generation of sludge” as the iron consumed is very less. When Fenton and Photo-Fenton

337 process were compared, it was observed that photo-Fenton process produced 25 times lesser

338 sludge volume consuming 32 times lesser iron and yielding the same COD removal efficiency
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339 than the traditional Fenton treatment. The disadvantages which limit the application of UV

340 assisted AOPs are :

341 (a) Contaminants or Suspended solids with high absorbance (Bigot et al., 1994) can block or

342 absorb UV rays and reduce its effectiveness

343 (b) Medium or high pressure UV lamps (200-300nm) are required for full application of this

344 technology causing high energy consumption and small effective diameter for a Ozonation

345 reactor (Geenens et al., 1999)

346 (c) Oxalates which are sparingly soluble, forms a scale layer on UV lamps due to high

347 concentration of carbonate and bicarbonate concentrations reducing their effectiveness

348 (Steensen, 1997)

349 (d) During H2O2/UV process, if the landfill leachate has high background absorbance or high

350 particle concentration, the UV absorbance on hydrogen peroxide will be less, producing fewer

351 hydroxyl radicals

352 (e) Ozone bubbles causes foam which blocks UV penetration inside the matrix and results in

353 less efficiency of peroxone process (Bigot et al., 1994)

354 2.4 Electro-fenton Process

355 Fenton process has some major disadvantages and to overcome those, Electro-fenton process

356 (E-Fenton) can be applied which involve electrochemical modifications in Fenton process. Fe+2

357 ions are steadily generated at anode in E-Fenton process which reduces the iron sludge

358 production (Eq. 45). Hydrogen peroxide can also be generated in situ by air-purging the reactor

359 and using proper cathode (Eq. 46) (Atmaca, 2009). This lead to no external addition of

360 Hydrogen peroxide making the process economically favorable.

361 Fe 3+ + e− → Fe2+ (45)

362 O2 + 2H + + 2e- → H2O (46)

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363 E-fenton process can be operationalized via four different routes (Khajouei et al., 2018) :

364 (a) Fenton reagents may be added externally

365 (b) Fe +2 ions can be generated electrochemically at sacrificial iron anode and H2O2 can

366 be added externally

367 (c) Both H2O2 and Fe+2 are produced electrochemically at sacrificial anode and cathode

368 (d) Fe+2 ions can be generated electrically by reduction of Ferric hydroxide or ferric

369 sulphate sludge and H2O2 can be added externally

370 Khajouei et al. (2018) on his study on treatment of composite leachate achieved reduction

371 of 63.4% in COD, 78.7% in BOD and 99.3% in PO4 – P under optimum conditions as initial

372 pH =3, [H2O2 ] = 0.25 M, electric current = 3 A and reaction time = 100 min). During the

373 process NO3–N concentration increased from 24.12 mg / L to 40.03 mg/L possibly due to

374 the oxidation of NH3–N and NO2–N in the wastewater to NO3–N. Table 6 shows the

375 advantages and disadvantages of Electro fenton process :

376 Table 6: Advantages and Disadvantages of E-fenton process

Advantages Disadvantages

(a) Electro Fenton process need very less energy (a) Cost of treatment increases due to
compared to Photo Fenton and other oxidation installation of iron extraction system is to
technologies that utilize O3 or ultraviolet. remove residual iron from the treated

(b) Electro Fenton & Fenton processes yield water.

no vapor emissions and need no off-gas (b) A very low pH (<4) environment is
treatment or air permits. necessary to keep iron in solution. pH

(c) The process is carried out at room adjustment before and after treatment will
temperature and pressure and has high treatment be needed. which will increase the
efficiency operational & maintenance costs.

(d) When reactions take place in homogeneous

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phase, then there are no mass transfer

limitations.

377

378 2.5 Electrochemical Oxidation

379 Electrochemical oxidation is a widely used approach for reduction of organic load in leachates.

380 This process involves bipolar electrochemical reactors that are easy to operate and control.

381 Process of electrochemical oxidation can have two approaches i.e indirect oxidation (oxidation

382 through the mediator) and direct oxidation (oxidation at anode surface) (Figure 5).

383
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RECALCITRANT
COMPOUNDS
OXIDANTS
INDIRECT
OXIDATION
OXIDATION
INTERMEDIATES REACTIONS
PRODUCTS ON
OXIDATION

ELECTRODE

S O L U T I O N P H A S E

RECALCITRANT
COMPOUNDS

DIRECT
OXIDATION

PRODUCTS ON
OXIDATION

ELECTRONS
ANODE

S O L U T I O N P H A S E
384

385 Figure 5: Approaches for Electrochemical Oxidation (Deng and Englehardt, 2007)

386 The species generated at anode in indirect oxidation can be H2O2 (Brillas et al.,1996), Ozone

387 (El-Shal et al., 1994), Chlorine and hypochlorite (Vlyssides et al., 2003) and metal mediators

388 for example Ag+2(Farmer et al., 1992) which are presumed to be responsible for oxidising

389 pollutants. Direct oxidation involves electrochemical conversion (involving chemisorbed

390 “active oxygen” which is oxygen in the oxide lattice MOx+1 and electrochemical combustion

391 (involving physisorbed “active oxygen” as adsorbed hydroxyl radical (Comninellis, 1994) as

392 shown in reactions 47 and 48:

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393 R + MOx+1 → RO + MOx------ Electrochemical conversion (47)

394 R + MOx (OH)z→ CO2 + zH+ + ze+ + MOx, ------ Electrochemical combustion (48)

395 (Where R is Organic compound and z is number of adsorbed hydroxyl radicals)

396 For leachate from the hazardous landfill site, indirect oxidation may be more prevalent

397 involving chlorine/hypochlorite produced through chlorine (present in leachate or added

398 externally) oxidation at the anode (Chiang et al., 1995). Direct oxidation may also oxidize

399 organic pollutants at the anode to some extent (Li et al., 2001) as shown in reactions 49-55:

400 2Cl− →Cl2 + 2e− (49)

401 6HOCl + 3H2O → 2ClO3+ 12H+ + 4Cl−+ 1.5O2 + 6e− (50) At anode

402 2H2O → 4H+ + O2 + 4e− (51)

403

404 Cl2+ H2O→ HOCl + H+ + Cl− (52)

405 HOCl→ H++ OCl− (53) Bulk reactions

406

407 2H2O+2e−→H2+2OH− (54) At Cathode

408 OCl−+H2O+2e−→ Cl−+ 2OH− (55)

409 Hypochlorite ion generated above is a very strong oxidant. Chiang et al.(1995) found that an

410 increase in current density, the efficiency of COD reduction and ammoniacal nitrogen also

411 increases. This was true only in case of indirect oxidation as for direct oxidation; at same charge

412 loading, current density does not have a direct correlation with pollutant removal efficiency

413 (Murphy et al., 1992). Chiang et al.(1995) suggested indirect oxidation as the dominant process

414 for electrochemical oxidation involving series of reactions similar to “breakpoint reactions”

415 (White, 1986). Cossu et al. (1998 ) reported that the pseudo-first-order rate constant only had

416 a slight increase at pH 3 as compared to pH 8.3. In electro-oxidation, the most significant

417 controlling parameter is pH as compared to Chloride concentration, temperature, sulphate

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418 concentration and applied voltage. Theoretically, the COD removal efficiency is enhanced by

419 acidic and alkaline conditions in electrochemical oxidation. Acidic conditions decrease the

420 concentration of carbonates and bicarbonates which scavenges hydroxyl radical generated at

421 anode increasing oxidation rate. Alkaline conditions boosts redox circulation of formed ClO-

422 to enhance indirect oxidation. Wang et al.(2000).

423 There are different opinion pertaining to the kinetics of electrochemical oxidation. Chiang et

424 al.(1995) proposed a pseudo-first-order kinetic rate constant and zero order kinetic rate constant

425 for COD and NH3-N removal. Moraes et al.(2005) proposed pseudo-second-order kinetics for

426 COD and TOC profiles. Li et al.(2001) suggested that during the first hour of the reaction for

427 predominating indirect oxidation reaction only 30%COD is removed and most of the

428 ammoniacal nitrogen is removed, whereas remaining 70% began to decline post sequential

429 batch reactor. It is evident that the removal of ammoniacal nitrogen is greater when indirect

430 oxidation is in dominance whereas the reduction of COD is more in direct oxidation (Marinci

431 and Leitz, 1978).

432 Electrochemical oxidation is a very efficient method for removing pollutants (specifically

433 organic) from leachate of hazardous waste landfill. It is reported that current density, pH, anode

434 materials, chloride concentration, and the electrolyte added influences the removal efficiency

435 of pollutants in the electrochemical oxidation process. Some of the commonly used materials

436 for anode are Iron, Aluminium, Ternary Sn-Pd-Ru oxide coated titanium (SPR), titanium

437 coated with SnO2 (SnO2/Ti), titanium coated with PbO2 (PbO2/Ti) graphite, Ru-Ti oxide (DSA)

438 or titanium coated by binary oxide, Boron-doped diamond (B/Diamond) and others. The COD

439 removal efficiency for an experiment using these electrode follows the sequence

440 B/Diamond>SPR>DSA>PbO2/Ti>graphite>Fe=Al (Chiang et al., 1995). The dominance of

441 electrochemical oxidation for treating leachate can be seen in various research, some of which

442 are listed in Table 7.

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443

444 Table 7: Treatment using Electrochemical Oxidation

Electrode used as Current density / % Reduction in Reference

Anode Electrolyte voltage &

reaction time COD BOD5 TOC Colour NH3-N

Oxide coated 116mA/cm2 73 57 86 49 (Vlyssideset

Titanium al., 2003) *

Graphite Carbon 79.9 mA/cm2, 68 70 - 84 -- (Bashir et al.,

2 hrs 2009)**

Ti/IrO2–RuO2 32 mA/cm2, 95 -- 65 -- -- (Turroa et al.

(HClO4) 3 hrs , 2011)**

Graphite-PVC 15 V 87 97 (Mussa et al.,

(NaCl) 1 hr& 45 min 2015)**

Boron Doped 15 amp, 3 hrs 90 - - - - (Papastavrou

Diamond et al,2009)**

Boron Doped 15–90 mA/cm2, - - - - 100 (Cabeza et.

Diamond 6 hrs al, 2007) **

Ti/RuO2 45 mA/cm2 82.38 - - - - (Singa et al.,

(Fe/H2O2) 2.5 hrs 2018b) ***

445 *: industrial wastewater**: Leachate from municipal landfill***: Hazardous waste landfill

446 It is visible that electrochemical oxidation proves to be more significant in removing colour in

447 comparison to COD. The major advantage of this AOP is that the organic pollutants are

448 converted into carbon dioxide and water which means unlike other treatment processes;

449 contaminants from one phase are not just transformed to another phase.
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450 Electrochemical oxidation operates at ambient temperature and pressure conditions that

451 prevents discharge and volatilization of unreacted wastes. The process can be discontinued

452 cutting the power supply that makes it easy to control (Grimm et al., 1998).

453 Electrochemical oxidation although having efficacy in treating landfill leachate, have major

454 disadvantage of being energy-intensive process and formation of chlorinated organics. Also,

455 high efficiencies of pollutant removal is achieved with highly expensive metallic electrodes

456 such as Boron doped Diamond and Ti/IrO2–RuO2 which results in high operating costs. This

457 is the reason that it is more favoured as a finishing step or as an auxiliary unit in emergencies

458 (Cossu et al., 1998).

459 2.6 Electrocoagulation

460 2.6.1. General Principle and Mechanism

461
462 Electrocoagulation (EC) is a process based on metal dissolution of a coagulant produced in situ

463 from a sacrificial anode followed by formation of hydrogen gas and hydroxyl ion at the cathode

464 resulting in destabilization of pollutants in the liquid wastewater (Bouhezila et al., 2011).In

465 spite of knowing the mechanism and principles, the electrocoagulation technique could not be

466 extended to the industrial environment that makes it as enigmatic technology (Moreno-Casillas

467 et al., 2007). Three processes are involved in electrocoagulation namely; electrochemistry,

468 coagulation, and floatation. The process of electrocoagulation involve following steps (Garg

469 and Prasad, 2016):

470  Electrolytic oxidation of the sacrificial anode

471  Coagulant formation in situ

472  Destabilization and subsequent adsorption of pollutants on coagulants as colloids

473  Aggregation of colloidal pollutants forming flocs and removal by sedimentation and

474 floatation.
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475 For landfill leachate, electrocoagulation also involves electrolysis, ionization, hydrolysis,

476 information of free radicals, which can bring major changes in the properties (physical and

477 chemical) of leachate. These reactive and excited states help to remove contaminants easily

478 from leachate (Hassan et al., 2016). The basic reactions that occur in an EC cell are shown

479 below in reactions 56-60:

480

481 At anode

482 M(solid)→M n+ (aqueous) + n e− (56)

483 2H2O (liquid)→ 4H +(aqueous)+ O2(g) + 4 e− (57)

484 At cathode

485 M n+ (aqueous) + n e− → M(solid) (58)

486 2H2O (liquid) + 2 e− → 2OH− + H2 (gas) (59)

487 In solution

488 M n+ (aqueous) + nOH− → M(OH)n (solid) (60)

489 Previous research on the application of electrocoagulation in the treatment of leachate is

490 presented in Table 8.

491 Table 8: Treatment of Leachate using Electrocoagulation

Electrodes pH Current Time of Coagulant % Reduction in Reference

density/ reaction dosage

voltage (min) COD Colour (others)

Iron 6.5 4.98 90 2319 93 -- 39 (Li X et al.,

(NaCl) mA/cm2 (NH3–N) 2011)

Charcoal 8.65 10V 120 1.5% 82 -- 69 (Jummahet al.,

composite (w/v) (NH3–N) 2015)

electrode
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Iron 6.0 60 30 NA 81 72 -- (Kashaniet al.,

mA/cm2 2012)

Aluminium 5.8 9V 35 NA 96 -- 97 (Shivayoginath

(Turbidity) and Watawati,

2013)

Iron 8.0 40V 90 NA 86.9 -- 93.7 (Hassaniet al.,

(Turbidity) 2016)

Aluminium 4.0 10 V 100 NA 74 -- -- (Jotinet al.,

2012)

Aluminum NA 166.6 150 NA 78.24 -- 98 (Rabahi et al.,

mA/cm2 (Turbidity) 2016)

Iron 7.73 1 amp 60 NA 45.1 82.7 -- (Huda et al.,

(NaCl) 2017)

Mg based <7 10 30 NA 53 85 -- (Oumaret al.,

mA/cm2 2016)

Iron 7 7V 20 NA 60 -- 95(Ni),99.6(Zn),98(Pb) (Bhagawan et

97.2 (Cu),73 (Fe) al., 2017)*

492 *: Hazardous waste landfill, All others : Leachate from municipal landfill

493 2.6.2 Process Parameters

494 2.6.2.1 Current Density

495 Current density play a vital role in electrocoagulation and determines the amount of metal

496 dissolved, i.e., coagulant dosage, bubble generation rates and influence dominant removal

497 mechanism for the system. At low current density, sedimentation dominates whereas floatation

498 is dominant at higher current density. Current density influences the mixing of the solution and

499 mass transfer between bulk and electrodes (Holt et al., 2005). Literature reveals a wide range
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500 of applied current density from 1-100 mAmp/cm2 which differs from case to case and on the

501 type of wastewater. A logical analysis should be done to correlate applied current density and

502 pollutant removal as the amount of metal ion dissolved or deposited is directly proportional to

503 the current applied which can be derived from Faraday’s law (Mollah et al., 2001) and is shown

504 in equation 59:

505 W = J * t * (M/n) * F (59)

506 Where W: Quantity of electrode material dissolved (g of M/cm2)
507 J: Applied current density (mA/cm2)
508 t : Time of electrolysis (s)
509 M:Relative molar mass of electrode material
510 n: number of electrons in a redox reaction
511 F: Faraday’s constant (96,500 coulombs/mol)
512 Chen et al. (2004) suggested an optimum current density of 20-25 Amp/m2 for the operation
513 of the EC system for a longer time without maintenance.
514 2.6.2.2 Type of Electrodes

515 The electrodes generally used for EC are iron and aluminium. The coagulant ions of these

516 metals lead to aggregation of particles in water and are removed by flotation, sedimentation or

517 filtration process. Iron, when used as an electrode, involve more complex reactions due to the

518 interaction of two ions Fe+2 and Fe+3 but has an advantage over aluminum regarding lower

519 dosage, higher range of pH for operation, low toxicity and formation of heavier flocs (Liu X et

520 al., 2012). Steel electrodes can also be a probable alternative to iron and aluminium electrodes,

521 but in comparison to steel electrodes, the electrocoagulation is found to be enhanced at

522 aluminium surfaces due to the formation of dispersed aluminium-hydroxide complexes (Hulser

523 et al.,1996). Copper electrode can also be used in the EC process where the copper ions

524 produced may also have antimicrobial effects. It is reported that for pH>7, the process yield

525 Cu (OH)2 and CuO which are produced from Cu2+ ions and can act as coagulants (Barrera-Diaz

526 et al., 2014).

527 2.6.2.3 Type of Electrolyte and Concentration

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528 Sodium chloride (strong electrolyte) is employed to increase the conductivity of

529 wastewater/leachate under treatment as the conductivity has a direct relation with Faradic yield

530 and cell voltage which ultimately counts for energy consumption and cost effectiveness of EC

531 cell.

532 Along with increasing conductivity, the presence of chloride ions reduces the adverse effects

533 caused by bicarbonate and sulphate anions as these ions may lead to the formation of calcium

534 salts forming an insulating layer on cathode increasing the ohmic resistance. Presence of NaCl

535 during electrocoagulation may lead to the formation of hypochlorite ion and hypochlorous acid

536 at pH< 11, which act as in situ formed oxidizing agent and increases the pollutant removal

537 efficiency (Liu et al., 1997). An excess amount of NaCl may lead to ‘corrosion pitting,’ i.e.,

538 overconsumption of aluminium electrode.

539 2.6.2.4 pH of the Solution

540 In solution, several hydroxides of ions generated at sacrificial anode are formed depending on

541 pH of aqueous medium which are polyhydroxides compounds or polyhydroxy metallic

542 compounds, such as [M (H2O)6]3+, [M(H2O)5(OH)]2+, [M(H2O)4(OH)2]2+ (Duan and Gregory,

543 2003). The amorphous structures of these hydroxide compounds have large superficial areas,

544 positive charges, and hydrophobic properties promoting their interaction with organic

545 molecules and provide active sites for adsorption and cause coagulation (Zayas et al., 2007).

546 Electrocoagulation shows a buffering effect due to balance between consumption and

547 formation of hydroxyl ions.

548 2.6.3 Electroflotation

549 One of the effective ways of separating pollutants in EC is by flotation through gas bubbles

550 whereby increasing the size of bubbles, yield of the separation can be increased. The

551 production rate and the size of the bubbles can be controlled by producing the bubbles

552 electrically (Ren et al., 2014 a). This type of flotation caused due to electrically produced
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553 bubbles is referred as Electro-flotation (EF). The position and structure of the electrode,

554 voltage, current density, pH and electrode material affect the operation of this process (Sarkar

555 et al., 2010). In the EF process, corrosion resistant electrode should be used. The pollutant in

556 Electro-flotation process floats with the bubbles with oxygen and hydrogen gas produced at

557 anode and cathode (Vu et al., 2014).

558 Advantages of Electrocoagulation

559 Electrocoagulation is beneficial as it gives clear, colourless and odourless, potable treated

560 product and has simple equipment (Labonowski et al., 2010). As compared to chemical flocs,

561 much stable and larger acid resistant flocs containing less bound water are obtained which

562 membranes can easily filter. The wastewater produced is also having less TDS as compared to

563 chemical treatment resulting in lower water recovery cost during the reuse process (Oricho et

564 al., 2008).Electrocoagulation proves to be a cleaner and greener approach towards leachate

565 treatment because of the following advantages:

566  Electrocoagulation is “a green technology” as there is no addition of chemicals.

567  Costs for treatment in EC systems are low as no big sedimentation and mixing pools

568 are required.

569  EC promotes advanced flocculation process as the colloidal particles flocculateeasily

570 due to an electric field generated in the electrochemical cell.

571  Due to the simple design, the maintenance cost is low for EC systems.

572  In comparison to conventional coagulation systems, the quantity of sludge produced

573 in EC systems is low and of better quality with hydrophobic solid content.

574  The hydrogen bubbles produced at cathode may eventually carry the solids to the top

575 where they can be collected and removed with lesser energy consumption

576 (electroflotation).
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577  EC produces the wastewater with less TDS content, and if this water is reused, the

578 lower TDS contributes to lower water recovery cost.

579  pH control is not mandatory except for extreme conditions.

580  The process takes place at room temperature and atmospheric pressure.

581  Being a greener initiative, even a solar unit attached to the unit is enough to carry the

582 EC process.

583 Disadvantages of Electrocoagulation

584 Electrocoagulation process has some drawbacks like energy intensive, electrode passivation

585 and formation of chlorinated organics. If the leachate has high humic and fulvic acid contents,

586 there are chances of formation of trihalomethanes generating bad odour (Mollah et al.,

587 2001).Because of its high operating costs, it is more favoured as a finishing step or as an

588 auxiliary unit in emergencies (Cossu et al., 1998).

589 Following are the areas that require more research and development to establish

590 electrocoagulation as a technically viable and economically feasible solution for treating

591 leachate from Hazardous waste landfill:

592  There is a need to develop hybrid electrodes to reduce the frequency of periodic

593 replacement of sacrificial electrodes.

594  Research to use non-chlorinated electrolyte like sodium sulphate as supporting

595 electrolyte to overcome the toxicity arising due to the formation of chlorinated

596 compounds due to the use of NaCl as an electrolyte.

597  EC lacks a widely accepted mathematical/kinetic model to study its kinetics.

598 2.7 Other AOP Processes

599 Hydrodynamic cavitation (HC) is used for the treatment of landfill leachate where liquid is

600 passed through an orifice plate or nozzle due to which the kinetic energy of liquid is increased

601 at the expense of pressure (Gogateet al., 2008). Free radicals, which are highly reactive, are
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602 formed because of microbubbles formation and subsequent collapse due to pressure field

603 variations in the solution phase. The simple design of HC yields low maintenance cost as well

604 as no off-gas treatment. Chakinala et al.(2008) applied HC along with advanced Fenton process

605 in wastewater and noticed 60-80% removal of TOC. Applications of HC in leachate treatment

606 has not given very promising results with a reduction in COD less than 10% (Korniluk and

607 Ozonek, 2011). The process can be made more effective by changing the experimental set-ups

608 with higher pressure or a different arrangement of holes on the orifice plates or by combining

609 with other AOPs.

610 The ultrasound-assisted process produce localized microenvironments with high energy in the

611 medium. It can have a synergistic effect (Lakshmi and Sivashanmugam, 2013). Its combination

612 with electrochemical process enhance their performance (Ren et al., 2014 b). When combined

613 with electrocoagulation, enhances flocculation due to intense mixing and can generate radicals

614 which enhance the process through chemical polishing of the surface of flocs(Ren et al., 2013).

615 Afsharnial et al. (2018) achieved 98% reduction of COD and about 68% of TSS of fresh

616 leachate (30 V, 60min) using iron and copper electrodes simultaneously in Sono

617 electrocoagulation process.

618 Wet air oxidation (WAO) is a promising AOP especially used for reduction of aqueous

619 pollution loading in leachate when it is necessary to treat in low volumes. The process involve

620 oxidation of the pollutants using oxygen at high temperature (450-590K) and pressure (2-15

621 MPa) assuring wet conditions of the reaction. The WAO simplifies the organic waste streams

622 that are “too dilute to incinerate” or “too concentrated for biological treatment” to more

623 biodegradable streams and completely converts to organic pollutants to carbon dioxide and

624 water (Goi et al., 2006). This AOP is cost-effective for leachate treatment with COD

625 concentration ranging from 10,000 - 100,000 mg/l and not viable for COD concentration less

626 than 5000 mg/l (Kolaczkowski et al., 1999). The operational cost may be reduced by lowering
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627 airflow rate, pressure, and temperature but reduction in COD will vary. Karimi et al. (2013 )

628 reported that wet air oxidation is very effective in oxidizing high concentrations of organic

629 matter to obtain reduction of more than 35% COD , 38% BOD, 53.3% of NH4-N and 56.4-

630 73.9% NO3-N in leachate treatment.

631 2.8 Comparison of AOP process under review

632 Treatment of leachate with different advance oxidation process has following two outcomes :

633 (a) Organic substances present in leachate are oxidized to their highest stable oxidation states

634 (b) Biodegradability of recalcitrant compounds is enhanced so as to be compatible with

635 subsequent biological treatment

636 The comparison of various AOP’s performance can be evaluated on above two aspects. Figure

637 6 shows outstanding treatment performance of AOPs reviewed specifically for treatment of

638 HWL leachate:

90.00

80.00

70.00
% Reduction in COD

60.00

50.00

40.00

30.00

20.00

10.00

0.00
Ozone O3/ H2O2 O3 / Fenton Photo E-fenton EO EC
persulfate fenton
AOP
639

640 Figure 6 : Comparison of AOP for Leachate from Hazardous waste landfill

641 Above graph show maximum reduction of COD when the leachate from HWL is treated by

642 Electrochemical oxidation. But, as discussed previously this AOP has major disadvantage of
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643 having high operational costs due to involvement of expensive electrodes. Electrocoagulation

644 give moderate reduction is COD is still preferable as being cost effective and does not involve

645 any chemicals as compared to other AOPs.

646 3.0 Conclusion

647 Growing industrialization resulted in the higher solid waste (organic as well as inorganic)

648 generation being grounded at the hazardous waste landfill site, and predictions have indicated

649 an upward trend in waste generation quantity as well as leachate generation in the coming two

650 decades. For abatement of refractory and toxic pollutants from leachate, AOPs have emerged

651 as powerful tools. Different AOP techniques involving Ozone, Fenton, UV, and others have

652 been developed for appropriate treatment problems. Ozone has a complex impact on leachate

653 and increases its biodegradability but is required in high dosage making it energy intensive.

654 Reduction in COD and colour as close to 90% and 85% is achieved in studies involving Ozone

655 along with Hydrogen peroxide or persulfate. Industrial wastewaters can be effectively treated

656 with Fenton’s process to obtain considerable decrease in COD and colour. Quantitatively, the

657 Photo-Fenton process proved to be more beneficial than the Fenton process for a reduction in

658 COD, but high sludge generation, narrow operating pH range, and higher chemical dosages

659 make the process unfeasible. Literature about cleaner technologies like Electrochemical

660 oxidation explained this method to be more selective and effective in COD reduction wherein

661 using varieties of electrodes including Ti/IrO2–RuO2 which provides significant reduction

662 (above 90%) in COD, and it can be considered as one of the alternatives conventional chemical-

663 based AOPs. But this process is highly energy intensive and involve expensive electrodes

664 which limits its applicability. Optionally, Electrocoagulation appears to be a promising AOP

665 for leachate treatment which can efficiently reduce COD, BOD, turbidity, metals and color

666 from leachate. For electrocoagulation variable electrodes gave variable reduction efficiencies

667 but the maximum reduction of 60% was obtained for leachate from hazardous waste landfill
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668 when the system was operated for 20 min with initial pH of 7. The electrode material used was

669 iron with electrode reaction area of 40 cm2, applied voltage of 7 V and electrode spacing of 1

670 cm. Iron electrodes are found to be most ideal electrodes, compared to aluminium and SS

671 electrodes. In similar conditions % removal of metal was also found to be 95, 99.6, 98, 97.2,

672 and 73 of Ni, Zn, Cu, Pb, Cu, and Fe along with 13.4% of bio hydrogen. Lower environmental

673 footprint, economical operation, simple set-up, low sludge volume, ambient reaction

674 conditions, and no chemical dosing are the major factors, which proved EC as a greener,

675 cleaner, cheaper and faster way for treatment of leachate from a hazardous landfill site. Future

676 research must focus in filling the gap for AOPs in focussed areas, such as the development of

677 rate expressions based on the mechanism (kinetic modeling), characterization of every

678 component present in leachate, identification of scale-up parameters and economic viability.

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Highlights

 Necessity of AOPs for treating leachate from hazardous waste landfill

 Mechanism of various AOPs along with their limitations critically reviewed
 Extensive datasheet compiled for leachate treatment efficiency of various AOPs
 AOPs: Research hot spot to treat hazardous waste landfill leachate
 Electrocoagulation: A cleaner process comparative to chemical based AOPs