Journal Pre-proof

RIVER water treatment using electrocoagulation for removal of acetaminophen and

natural organic matter

Shweta Kumari, R. Naresh Kumar

PII: S0045-6535(20)32766-1
DOI: https://doi.org/10.1016/j.chemosphere.2020.128571
Reference: CHEM 128571

To appear in: ECSN

Received Date: 24 June 2020

Revised Date: 3 October 2020
Accepted Date: 5 October 2020

Please cite this article as: Kumari, S., Kumar, R.N., RIVER water treatment using electrocoagulation
for removal of acetaminophen and natural organic matter, Chemosphere, https://doi.org/10.1016/
j.chemosphere.2020.128571.

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RIVER WATER TREATMENT USING ELECTROCOAGULATION FOR

REMOVAL OF ACETAMINOPHEN AND NATURAL ORGANIC MATTER

Shweta Kumari, R. Naresh Kumar*

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Department of Civil and Environmental Engineering

Birla Institute of Technology, Mesra

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Ranchi 835215, Jharkhand
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Jharkhand, India
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*Corresponding author:

Email: rnaresh@bitmesra.ac.in

Phone: +91 9801160279

 Graphical abstract:

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Electrocoagulation

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UV254 absorbing H-bond of acetaminophen
Acetaminophen organic compounds Treatment on Al(OH)3 floc

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70
y = 1.39x + 5.91

Acetaminophen Reduction (%)

60 R² = 0.88

50

40

30

20

10

0
0 10 20 30 40 50
UV254 Absorbance Reduction (%)
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 1 River water treatment using electrocoagulation for removal of acetaminophen and

2 natural organic matter

4 Abstract

6 Electrocoagulation (EC) was assessed for removal of acetaminophen and natural organic

7 matter (measured as UV254) from river water. Process was assessed for time, electrode

8 materials, inter electrode distance, and voltage. Best conditions for removal of acetaminophen

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9 and UV254 absorbance were 60 min reaction time, aluminum-aluminum electrodes, 2 cm inter

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10 electrode distance, and 9 V. Acetaminophen tested at 1, 2, 5, 10, and 20 mg L-1 showed that

11
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treatment efficiency decreased as the concentration increased. The main mechanism for
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12 removal of acetaminophen was H bonding with Al(OH)3 flocs; this was confirmed by XRD
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13 and FT-IR spectrum. Pseudo-second order kinetics model exhibited a good fit on
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14 experimental data for acetaminophen removal at different concentrations. Univariate

15 ANOVA indicated statistically significant difference between treatments for acetaminophen

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16 removal (F2.76 = 136, P = <0.001). A significant linear correlation was found between UV254
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17 absorbance and acetaminophen removal at different concentrations. Preliminary analysis

18 suggest that EC will cost US$ 0.22/m3 for river water treatment. The lab-scale EC process

19 was compared with a full-scale water treatment plant for removal of natural organic matter.

20 Water treatment plant after multiple levels of purification was not able to fully remove UV254

21 absorbance whereas EC treatment showed good efficiency.

22

23 Keywords: Acetaminophen, UV254, Al(OH)3, reaction kinetics, water treatment

24

1
25 1. Introduction

26

27 Emerging contaminants in water have gained significant interest amongst the scientific

28 community, regulatory agencies, and public in recent times. This is mainly due to their

29 unknown environmental impacts and possible risks to human health. Pharmaceutical

30 compounds are an important group of chemicals because of their benefits to human health

31 and contribution to the reduction of human mortality. However, their improper disposal may

32 have extreme environmental impacts, such as contamination of water resources and soils

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33 (Chen et al., 2013; Starling et al., 2019). Emerging contaminants are frequently reported

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34 globally, especially in surface waters, groundwater, and drinking water which may pose

35
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serious health risks to the people (Kim et al., 2018; Aydin et al., 2019).
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36
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37 Acetaminophen (N-4-hydroxyphenyl acetamide) was chosen as a model compound to study

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38 as it is a common analgesic widely used over-the-counter drug to treat headache, pain, and

39 fever across the globe. Acetaminophen exhibits toxicity to aquatic organisms and human
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40 beings due to the presence of phenolic group (Kim et al., 2007; Su et al., 2013).
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41 Acetaminophen is consumed at 1.45×105 tons per year, it is poorly absorbed by the body

42 though it has high solubility of 12.8 g L-1. As a result, large amounts are released as waste

43 into the environment as wastewater treatment plants are often not effective for its removal

44 (Su et al., 2013: Wang et al., 2019). Lima et al. (2019) reported that 58–68% of

45 acetaminophen is excreted by humans through urine. Ingestion of a higher quantity of

46 acetaminophen can lead to fatal hepatotoxicity and nephrotoxicity due to the toxic

47 metabolites formation. Acetaminophen present in water can transform into toxic compounds

48 during chlorination in water treatment plants (Bedner and MacCrehan, 2006). Acetaminophen

49 reaches the natural environment either through direct disposal of domestic drugs, discharges

2
50 of faeces/urine, or the inappropriate treatment of the pharmaceutical industry and hospital

51 effluents (Yang et al., 2008). Considering the adverse effects of acetaminophen on the

52 environment and human health, its effective removal is necessary.

53

54 Various processes have been assessed for removal of acetaminophen from water and

55 wastewater. Adsorption (Yanyan et al., 2018; Lima et al. 2019), advanced oxidation

56 processes (Yun et al., 2019), photocatalysis (Czech and Tyszczuk-Rotko, 2018; Katal et al.,

57 2020) and sonolysis (Carine et al., 2009) are commonly studied processes. Some of these

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58 methods are effective but requires highly sophisticated setup, skilled manpower, and high

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59 costs. One promising alternative could be the use of electrochemical processes such as EC.

60
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EC works on the principle of coagulation, flotation, and electrochemistry. Contaminant
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61 removal mechanisms in EC are complex and include a combination of mechanisms such as
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62 chemical oxidation-reduction, decomposition, precipitation, adsorption, and flotation (Oden

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63 and Sari-Erkan, 2018). Numerous metals have been tested as electrodes in EC; Al, Fe, and

64 stainless steel (SS) are widely used as electrodes in water treatment due to their lower price
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65 and easy availability in comparison to other materials (Sahu et al., 2014). EC has several
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66 advantages over chemical coagulation like no need for pH adjustment, higher pollutant

67 removal, lesser sludge production, and lower operational costs (Garcia-Segura et al., 2017).

68 Compared to chemical coagulation higher treatment efficiency with EC is attributed to the

69 absence of extra anions that comes with the chemical coagulants such as chloride

70 and sulphate that may compete with cations present in solution which lowers the removal of

71 pollutants.

72

73 Conventionally, in water treatment plants coagulation-flocculation is used followed by

74 sedimentation, sand filtration, activated carbon, and disinfection. Such a treatment scheme is

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75 commonly used for water purification for public supplies. The suitability of these plants for

76 removal of emerging micropollutants such as antibiotics, steroids, painkillers, etc. remains

77 poorly understood (Rodriguez-Narvaez et al., 2017; Paucar et al., 2019). Even though the

78 presence of emerging contaminants in water, food, and its impact on human health remains a

79 research topic for further understanding, however, to improve the public perception and

80 confidence it is necessary to eliminate these pollutants. Most research on emerging

81 contaminants has originated from developed countries that recommend sophisticated and

82 expensive technologies, which may be difficult to adopt in the socio-economic settings that

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83 prevail in the developing countries. Hence, the focus should be to explore existing and new

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84 processes for removal of both conventional pollutants along with emerging contaminants. In

85
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such conditions, EC can be used to replace the conventional coagulation-flocculation units in
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86 water treatment plants. EC has been reported to be ideal for small-scale water treatment
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87 plants, which is preferred over large-scale centralised facilities, and this is particularly
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88 relevant in developing countries, where securing access to clean water remains challenging

89 (Holt et al., 2016). Small localised treatment facilities can be cost-effective with lower energy
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90 consumption compared with larger facilities and due to lower energy requirement, such
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91 facilities can also be run on renewable energy sources.

92

93 Numerous organic micropollutants are entering the aquatic systems and often it is not

94 possible to sample and analyse all these emerging contaminants for monitoring and removal,

95 mainly due to requirement of highly skilled manpower and cost-intensive analytical

96 procedures. To overcome these analytical obstacles, there are reports of using natural organic

97 matter (measured as UV254 absorbance) as a surrogate for organic micropollutants present in

98 water (Bahr et al., 2007; Wittmer et al., 2015). Reduction in absorption at 254 nm wavelength

99 can be utilised as an important parameter to monitor the removal of organic micropollutants

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100 as UV absorbing compounds are concomitantly removed in water treatment process (Jekel et

101 al., 2015). A good correlation between reduction in UV254 absorbance and several organic

102 micropollutants has been reported (Zietzschmann et al., 2014; Mailler et al., 2015; Altmann

103 et al., 2016). UV254 absorbance can be easily used for real-time online monitoring and it

104 offers better process control not only for organic micropollutants removal but also for dosing

105 of adsorbents and coagulants in water treatment (Wert et al., 2009; Altmann et al., 2016;

106 Beauchamp et al., 2020).

107

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108 Regarding the electrocoagulation conditions, the present work aims to assess the effect of

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109 various parameters on river water treatment. Various process parameters studied include

110
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reaction time, voltage, types of electrode (aluminium, iron, and stainless steel), inter electrode
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111 distance, and initial concentration of acetaminophen. Mechanism of acetaminophen removal
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112 with Al as an electrode was studied and the data was statistically analysed using univariate
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113 ANOVA and correlation-regression tests. Reaction kinetics for acetaminophen removal with

114 EC was also performed. Another important aspect of the present study was to assess the
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115 possible positive correlation of decrease of UV254 absorbance with acetaminophen in EC. The
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116 present study also assessed the efficiency of a full-scale water treatment plant for removing

117 the organic micropollutants and results are compared with the lab-scale EC process.

118

119 To the best of our knowledge acetaminophen removal using aluminium as an electrode and

120 river water as substrate in EC has not been reported yet. Up to now there are only few

121 published works which studied the potential of EC for removal of acetaminophen. In a study,

122 acetaminophen synthetic solution at 1 mg L-1 was assessed (Govindan et al., 2020) and in

123 another, groundwater was assessed at 40 mg L-1 acetaminophen along with ibuprofen

124 (Negarestani et al., 2020). Majority of the studies on EC has focused on synthetic water or

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125 pure solutions with target compounds, and the literature on surface/ground water are

126 comparatively less.

127

128 2. Materials and methods

129

130 2.1 River water

131

132 The river water was collected from the inlet of a water treatment plant which is located at a

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133 university campus for its residents. Grab sampling method was used for water sampling.

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134 Water samples were collected daily for physico-chemical analyses and EC experiments.

135
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Acetaminophen was not detected in the river water; hence, the samples were spiked with
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136 known concentrations to study its removal by EC. For EC, the acetaminophen stock solution
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137 was prepared by dissolving 0.2 g of acetaminophen (Sigma Aldrich) in 1 L fresh river water.
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138 From this stock solution, acetaminophen at 1, 2, 5, 10, and 20 mg L-1 was prepared for EC

139 treatment.
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140
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141 2.2 Electrocoagulation setup

142

143 EC was carried out in a borosilicate glass vessel of 1 L total volume. The setup was a bench-

144 scale EC with 0.9 L working volume. Different types of electrodes such as iron, stainless

145 steel, and aluminium were used, all the electrodes used in EC had the same dimensions (6.3

146 cm x 7.9 cm). A direct current power supply unit (Make: Aplab, India) was used which can

147 provide voltage of 0–32 V and current of 0–5 A. Direct current power unit was connected to

148 the electrodes to work at the required voltage. Metal plates as electrodes were arranged in

149 parallel to serve as anode and cathode in the EC reactor. During EC, a magnetic stirrer was

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150 used to agitate the contents of the reactor. EC experiments were conducted at room

151 temperature without pH adjustment or electrolytes addition, supporting electrolytes were not

152 added mainly to avoid the artificial increase of electrical conductivity of river water, as the

153 main goal of this study was to understand the EC performance in natural conditions.

154

155 2.3 Acetaminophen removal using electrocoagulation

156

157 EC experiments were first conducted to assess the reaction time needed for effective removal

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158 of contaminants from river water without the addition of acetaminophen. For process

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159 assessment, experiments were conducted with river water for 225 min where samples were

160
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collected at every 15 min interval for physico-chemical analyses. Aluminium as anode and
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161 stainless steel as cathode was kept at 4 cm inter electrode distance in the EC reactor. Voltage
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162 during this experiment was set at 12 V. Process time required was assessed by recording pH,
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163 electrical conductivity, and UV254 absorbance in river water. The selected process variables

164 were voltage, types of electrodes, inter electrode distance, and acetaminophen concentration.
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165 Acetaminophen removal experiments were carried out based on the best conditions (120 min
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166 reaction time, 9 V, Al-Al, 2 cm inter electrode distance). To assess the phase transformation

167 of acetaminophen and other contaminants present in river water, sludge samples were

168 collected from the EC reactor after the treatment. Sludge volume generated following EC was

169 determined using a measuring cylinder after 30 min of sedimentation.

170

171 2.4 Monitoring of water treatment plant for removal of organic micropollutants

172 The treatment plant monitored takes water from the Jumar river and works on physico-

173 chemical processes for water purification. The water treatment plant has a maximum capacity

174 of 1.92 million liters per day (MLD) and an average treatment level of 80,000 L h-1. The

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175 water treatment plant was monitored from 27/01/2020 to 18/02/2020 (n = 15 days) for

176 assessing the removal of organic micropollutants. For this purpose, samples were collected

177 from the inlet, lamella clarifier, sand filter, and activated carbon filter of water treatment

178 plant.

179 2.5 Physico-chemical analyses of river water and electrocoagulation samples

180

181 Water physico-chemical analyses was performed using the procedures described in the

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182 standard methods (APHA, 2005). Samples from the EC reactor were analysed for pH,

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183 electrical conductivity, chemical oxygen demand, UV254, and acetaminophen concentration. A

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multi-parameter water quality meter (Make: Oakton, USA) was used for pH and electrical
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185 conductivity measurement. Acetaminophen was analysed on membrane filtered water
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186 samples by using the procedure detailed in the literature (Yanyan et al., 2017). For UV254

187 absorbance measurement, samples were filtered using membrane filters and readings were
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188 recorded using UV-Vis spectrophotometer (Make: Shmiadzu, Japan). For analysis of sludge
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189 produced following EC, the residue was dried at 105 °C in an oven. X-ray diffraction
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190 spectroscopy was utilised to determine the phase changes and crystalline structure of EC

191 sludge using Cu Kα X-radiation (λ=1.5418 Å), at 40 kV and 30 mA (Make: Rigaku, Japan -

192 Model: Smart Lab 9 kW). Sludge was also analysed using Fourier Transform Infrared (FTIR)

193 spectroscopy in transmission mode from 4000 to 450 cm−1 (Make: Shimadzu, Japan - Model:

194 IR-Prestige 21).

195

196 2.6 Electrocoagulation process reaction kinetics and cost estimation

197

198 Faraday’s law can be applied to get the quantity of metal hydroxides that gets generated in

199 EC (Ganesan et al., 2012). Hence removal of pollutants can be modelled using the adsorption

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200 concept as the coagulant can be quantified for a set time. The best-fit kinetic model was

201 identified based on the linear regression correlation coefficient values (R2 ). Reaction kinetics

202 of acetaminophen with EC was examined at different concentrations. Pseudo-kinetic models

203 were applied to understand the association between the extent of adsorption per unit mass of

204 aluminum hydroxide generated during EC as adsorbent and time (Wu et al., 2019). The

205 pseudo-first order Lagergran model applied is expressed as.

206

207 log − = log − (1)

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208

209 The pseudo-second order model applied is expressed as:-p

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210 = + (2)
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211

212 where qt and qe (mg g-1) are the amount of acetaminophen adsorbed on EC products at any
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213 time t and at equilibrium, t is EC time, k1 (min-1) is the rate constant of the pseudo-first-order,
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214 and k2 (min.g.mg-1) is the rate constant of the pseudo-second-order.

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215

216 To estimate the process costs, energy consumption, electrode consumption, and operating

217 costs were evaluated. The operating cost of EC involves electrode materials, energy, and

218 chemicals (Can et al., 2006). The most important factors that influences the operating cost of

219 EC are electrical energy and electrode material consumption (Daneshvar et al., 2006). These

220 parameters were calculated according to Eq. (3):

221

222 ! = " #$% +& ' ( #)* (3)

223

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224 Where, Cenergy and Celectrode is the cost of energy and electrode materials needed for river

225 water treatment. Unit prices coefficients a and b were used as per the current market price in

226 India: a is electrical energy cost of US$ 0.082 per kWh for Jharkhand rural region and b is

227 US$ 2. Electrical energy demand was estimated using Eq. (4) (Daneshvar et al., 2006).

228

+×-× ./
229 " #$% = 0
(4)

230

Where, U is voltage (V), i is current (A), t is treatment time (h), v is volume (m3) of water

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231

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232 used for treatment. Electrode consumption can be calculated as per Eq. (5).

233

-×12 × ./
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234 ' ( #)* = (5)
3×0×4
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235
236 Where, Celectrode is the electrode consumption (kg m-3), Mw is molecular mass of aluminium
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237 (26.98 g mol-1), z is the number of electrons transferred (aluminium 3) and F is Faraday’s

238 constant (96,487 C mol-1).

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239
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240 2.7 Data processing and statistical analyses

241 EC experiments were carried out in triplicate and average of all the readings recorded were

242 used for interpretation of results. UV254 absorbance and acetaminophen at different

243 concentrations were tested using single-factor ANOVA and if statistically significant

244 differences were obtained, the variances within the groups were assessed by using the post

245 hoc Tukey test. Correlation-regression analysis was performed between UV254 and

246 acetaminophen to understand the relationship between their removal processes. Statistical

247 analyses were carried out using Microsoft Excel enabled with a data analysis tool pack.

248 Statistical analyses were performed at a confidence level of 95% and variances were accepted

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249 as significant when p≤0.05. The removal efficiency of UV254 and acetaminophen was

250 calculated using Eq. (6).

<= > <?

251 5 6 7 8 9%; = × 100 (6)
<=

252
253 Where Ci and C0 are initial and final absorbance/concentration in river water.

254

255 3. Results and discussion

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256

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257 Mean (n=10, ±S.D.) values of water quality parameters in Jumar river are presented in Table

258 -p
SM1. Considerable rainfall occurs in Ranchi, Jharkhand during monsoon (June to

September), and little rainfall occurs during summer (March to May) and winter (November
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259

260 to February). Jumar river receives heavy industrial and municipal waste discharge. There is
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261 low rainfall during non-monsoon period which limits the dilution effects on pollutants and
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262 lack of flow in the river (due to closing of sluice gates at the nearby dam) results to very poor
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263 water quality which persists till the onset of monsoon. The following are the main
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264 characteristics of river water: pH (7.1±1.1), electrical conductivity (0.61±0.11) mS cm-1, TSS

265 (110±24) mg L-1, UV254 (0.23±0.07) cm-1, turbidity (50±34) NTU and COD (290±50) mg L-1.

266 High COD indicate the polluted nature of Jumar river along with UV254 absorbance which

267 signifies the presence of organic micropollutants. River water was dark in colour and highly

268 turbid and during the study period never appeared visibly clean.

269

270 3.1 River water treatment using electrocoagulation

271

272 EC is affected by process influencing parameters such as reaction time, voltage, electrode

273 materials, inter electrode spacing, and concentration of pollutants. pH plays an important role

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274 in the removal of pollutants during EC. There was a rapid increase in pH during EC, after that

275 the increase in pH was marginal (Fig. SM 1). During time assessment experiments, pH

276 increased from 6.6 to 7.8. pH increase during EC is due to formation of OH− ions and

277 evolution of H2 gas (Garcia-Segura et al., 2017). Electrical conductivity decreased from 560

278 to 400 µS cm-1. pH and electrical conductivity can be easily monitored to obtain quick

279 information on EC. COD removal increased up to 120 min and afterwards it was almost

280 similar till the end of the experiment. COD removal correlated well with the decrease in

281 electrical conductivity in EC (Fig. SM 1).

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282

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283 UV254 absorbance decreased sharply up to 45 min and later its removal was gradual (Fig. SM

284
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1). The maximum reduction efficiency of UV254 was 65% during assessment of electrolysis
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285 time needed for treatment. The maximum removal of UV254 occurred at 120 min and further
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286 treatment duration did not improved the removal efficiency. Longer EC time favours higher
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287 production of complex aluminium species due to anode dissolution and hydrogen evolution at

288 cathode. Both these lead to high contaminants removal due to coagulation and flotation
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289 (Ensano et al., 2018). A similar result of 62% UV254 absorbance removal has been reported
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290 for EC of bilge water (Akarsu et al., 2016). Those authors reported that 90 min reaction time,

291 pH 6.3, and a potential of 15 V was effective for removal of UV254 absorbance.

292

293 3.2 Effect of interelectrode distance and different electrode combinations

294

295 Inter-electrode distance and electrode materials plays significant role in EC process

296 efficiency and cost. Reduction of the ohmic potential of an EC cell is directly proportional to

297 the inter electrode spacing applied. Electrode spacing affects energy consumption during

298 electrolysis especially when water electrical conductivity is low (Drouiche et al., 2011). The

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299 spacing between electrodes was kept at 2, 3, and 4 cm in the present work. These electrode

300 distances were evaluated for different electrode combinations as anode and cathode: Fe-Fe,

301 Fe-Al, Al-Fe, Al-SS, Al-Al.

302

303 Fig. SM 2 shows the highest removal efficiency at 2 cm interelectrode distance. pH increased

304 with all the electrode combinations tested at 2, 3, and 4 cm electrode spacing in EC (Fig. SM

305 2, Fig. SM 3, and Fig. SM 4). pH at the end of treatment was in the range of 7.8 to 7.9 at 2

306 cm electrode spacing, 7.9 to 8.1 at 3 cm electrode spacing, and 7.6 to 8.0 at 4 cm electrode

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307 spacing. Similarly, electrical conductivity after treatment was 406 to 460 µS cm-1 at 2 cm

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308 electrode spacing, 370 to 456 µS/cm at 3 cm electrode spacing, and 390 to 480 µS cm-1 at 4

309
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cm electrode spacing (Fig. SM 2, Fig. SM 3, and Fig. SM 4). UV254 absorbance reduction
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310 efficiency ranged from 33 to 82% at 2 cm electrode spacing, 62 to 72% at 3 cm electrode
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311 spacing, and 51 to 71% at 4 cm electrode spacing (Fig. SM 2c, Fig. SM 3c, and Fig. SM 4c).
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312 COD removal efficiency was 75 to 83% at 2 cm electrode spacing, 60 to 80% at 3 cm

313 electrode spacing and 70 to 74% at 4 cm electrode spacing. Fig. SM 2, Fig. SM 3, and Fig.
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314 SM 4 shows that COD decreased with increase in treatment time. Zaied et al. (2009) also
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315 reported that there was a 50% reduction in COD at 60 min and 66% after 90 min with Al

316 electrode. Of all the electrode combinations tested, Al-Al exhibited the highest removal

317 efficiency for both UV254 absorbance and COD removal at 2 cm electrode distance compared

318 to other electrode spacing applied. Overall, Al as an anode was more effective compared to

319 Fe at all electrode spacing assessed.

320

321 3.3 Effect of voltage

322

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323 An important parameter that affects EC efficiency is the voltage. Voltage is a parameter that

324 can be precisely controlled in EC compared to current density as it changes with water

325 quality. Voltage influences coagulants release from anode and bubble generation at cathode

326 and plays an important role in mass transfer during EC. This was the main reason that in this

327 study voltage was chosen as a controlling parameter.

328

329 Fig. SM 5 shows that pH and EC did not have any considerable variances at a different

330 voltage tested. UV254 absorbance reduction efficiency was 95% at 9 V followed by 18, 12 and

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331 6 V. COD removal efficiency was 78% at 9 V followed by 12, 18 and 6 V. At 12 and 18 V,

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332 both UV254 and COD reduction was almost similar, whereas at 6 V it was comparatively low.

333
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An increase in voltage increases the amount of oxidized metal. This generates more
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334 hydroxide flocs and reagent species which is responsible for enhancing the removal efficacy
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335 of pollutants. Kabdaşlı et al. (2012) reported that when the applied voltage increases, H2
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336 bubble density produced during EC also increases, and their size decreases, this enhances

337 pollutant removal efficiency.

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338
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339 The amount of sludge generated during EC at different voltage is shown in Fig. SM 6. It is

340 evident that sludge volume increased at high voltage. There was a gradual increase in sludge

341 volume till 12 V, after that rapid increase in sludge volume occurred at 18 V. This was due to

342 the increase in voltage that influences current density, and this in turn resulted in higher

343 electrode consumption. Higher metal constituents generated due to an increase in voltage

344 reacts with impurities present in water which forms complexes and either floats or

345 precipitates, leading to an increase in sludge volume. Papadopoulos et al. (2019) reported that

346 sludge volume during wastewater treatment with EC mainly depends on current density,

347 reaction time, initial pH, and type of electrode materials.

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348

349 3.4 Acetaminophen and UV254 absorbance removal using electrocoagulation

350

351 To assess the effect of concentration of acetaminophen on its removal efficiency, five

352 different doses 1, 2, 5, 10, and 20 mg L-1 were assessed (Fig. 1). EC conditions applied for

353 acetaminophen removal were 9 V, Al-Al, 2 cm electrode spacing, and reaction time 120 min.

354 pH increase ranged from 7.5 to 8.2 at different concentrations of acetaminophen. UV254

355 absorbance reduction efficiency was 43, 58, 34, 47 and 22% at 1, 2, 5, 10 and 20 mg L-1,

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356 respectively at different acetaminophen concentration. Maximum acetaminophen removal of

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357 60% occurred at 1 mg L-1 followed by 35, 42, 27 and 23% at 2, 5, 10, and 20 mg L-1,

358
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respectively. Most of the acetaminophen removal occurred by 60 min reaction time. From
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359 Fig. 1, it can be observed that EC can be used for removal of water containing acetaminophen
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360 at low concentration but at higher concentrations, it cannot be effectively applied. Possible
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361 reactions that may occur during EC are shown below. The detailed mechanism of

362 acetaminophen and UV254 removal is discussed in the coming sections.

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363
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364 Probable reactions during EC

D >
365 B8 → B8 +3 (1)
D
366 B8 → B8 FD + >
(2)

367 G → 2G D + 2 >
+ (3)

>
368 2G + 2 → G ↑ + 2 G> (4)
D
369 B8 + G > → B89 G; (5)

370

371 The hypothesis suggested that due to low hydrophobicity of acetaminophen (Pow – 0.46), it

372 can be removed mainly by the mechanisms of charge neutralization and adsorption on

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373 settling flocs in EC. Acetaminophen contains phenolic group whose ionization is dependent

374 on pH and pKa. For instance, pKa of acetaminophen is 9.38, which indicates that up to 90%

375 of acetaminophen will occur in protonated form at circumneutral pH and at basic pH, phenol

376 group protons are lost leading to the existence of deprotonated form (Bernal et al., 2017).

377 From the Log P value and pKa value of acetaminophen, it can be inferred that in EC both

378 charge neutralization and adsorption on precipitating flocs would be dominant mechanisms

379 and this will be dependent on pH of EC. The former will occur as pH increases to >7 but

380 remains at <9 and later would be the dominant mechanism at neutral pH.

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381

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382 EC solution pH was always >7 in present work and it was not adjusted at the start or during

383
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the process (see Fig. 1). EC solution pH supports the formation of monomeric and polymeric
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384 aluminium species. Al ions in aqueous solution present a complicated equilibrium and
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385 depending on pH a variety of monomeric species exists such as Al(OH)2+, Al(OH)2+,

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386 Al(OH)3 and Al(OH)-4 (Gregory and Duan, 2001); the latter species are dominant at alkaline

387 pH. Al(OH)3 concentration is independent of medium pH whereas the concentration of other
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388 species decreases with an increase in pH (Garcia-Segura et al., 2017). At an appropriate pH,
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389 Al3+ ions are transformed first as Al(OH)3 and later polymerized as Aln(OH)3n (Drouiche et

390 al., 2011). These Al species mainly Al(OH)3 played an important role in floc formation and

391 precipitation of acetaminophen during EC. As with acetaminophen, a major mechanism for

392 UV254 reduction during EC is attributed to the formation of Al(OH)3 flocs and adsorption of

393 organic pollutants on these at pH >7. This mechanism would be the dominant one compared

394 to the charge neutralization mainly due to pH in EC. Acetaminophen removal in the present

395 study agrees to the mechanisms of entrapment and adsorption to Al(OH)3 flocs which

396 dominate at neutral pH. Present findings are well supported by the literature where major

397 pathways of organic pollutant removal in EC indicate either one or combinations of

16
398 following: charge neutralization, complexation, entrapment, adsorption, and flotation

399 (Garcia-Segura et al., 2017).

400

401 The X-ray diffraction spectrum of acetaminophen and sludge generated through EC after

402 treatment for 120 min using aluminium electrode is presented in Fig. 2a. The 2θ scan was

403 done at 10 to 70 °. In untreated acetaminophen, there were many peaks but after treatment,

404 only three peaks could be observed. Shallow diffraction peaks observed indicate that the

405 sludge was amorphous, or it was very poorly crystalline. The peaks after treatment in sludge

of
406 at 2θ=20, 26, 36, were due to the presence of Al(OH)3 (ICDD database) corresponding to

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407 crystal facets of (120), (012) and (131), respectively (Thakur and Mondal, 2017). No new

408
-p
compounds were detected from the XRD spectrum of EC sludge. The results confirm that
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409 acetaminophen was attached to aluminium hydroxide precipitate complexes in EC.
lP

410
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411 FT-IR spectrum provides useful insights onto surface chemistry and EC generated sludge’s

412 functional groups through absorption bands and peaks. Fig. 2b shows the peaks of infrared
ur

413 spectra of acetaminophen before and after treatment using aluminium electrode. Significant
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414 structural changes occurred, and the disruption of bonds could be observed from the data. The

415 significant peaks were reduced, this indicates that acetaminophen was removed effectively in

416 EC. Significant deformations of peaks occurred at 3325 and 3163 cm-1, which correspond to

417 the hydroxyl group. The peak at 1443 cm−1, could be due to the formation of H bond with Al

418 hydroxide precipitates. It has been reported that oxygen in the acetaminophen carbonyl group

419 has a free electron pair which can serve as an acceptor for hydrogen bond (Quesada et al.,

420 2019). Further, deformation of the peak at 1233 cm-1 (C-O bond) in acetaminophen, indicate

421 H bond formation as the main mechanism for adsorption reaction. Other peaks at 3691 and

422 3618 cm−1 indicate O-H stretching which were due to adsorbed water molecules (Gomes et

17
423 al., 2007). The peak at 3441 cm−1 was due to N-H bond stretching showing the presence of a

424 primary amine. The peak at 1631 cm−1 can be attributed to N-H bending, peaks at 1103 and

425 1033 cm−1 were due to the presence of C-O groups and C-N stretching. FT-IR analysis

426 confirmed that no new bonds existed in the precipitate from EC treatment. FT-IR data

427 supported that pollutants in river water were associated to aluminium hydroxide complexes.

428

429 3.5 Reaction kinetics of acetaminophen removal in electrocoagulation

430

of
431 The pseudo-first and second-order kinetic models were applied to obtain the EC adsorption

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432 rate, equilibrium adsorption capacity, and adsorption mechanism (Wu et al., 2019;

433
-p
Khatibikamal et al., 2010). The plot of log (qe-qt) versus t gives a linear relationship for
re
434 pseudo- first order Lagergren model, from the plot’s slope and intercept respective k1 and qe
lP

435 can be estimated. The plots showed poor correlation coefficient (R2) values and indicated that
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436 the experimental data did not fit well with the pseudo-first-order model.

437
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438 The plots t/qt versus time (t) shows the straight lines (Fig. SM 7). The pseudo-second order
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439 kinetic parameters (qe and k2) were calculated from the slope and intercept of the plots. The

440 correlation coefficient (R2) of the pseudo-second order kinetic model was high. Table 1

441 shows the experimental and computed qe value obtained from the pseudo-second -order

442 kinetic model. These results indicate that the adsorption data obeyed pseudo-second order

443 kinetic model. Pseudo-second order kinetics model considers that chemisorption is the rate

444 limiting step which involves valency forces either through sharing or exchange of electrons

445 with the adsorbent (Aly et al., 2014).

446
447 Operating cost was calculated using Eq. (3), (4), and (5) to US$ 0.22/m3 for river water

448 treatment. Since no additional chemicals were used neither for adjusting pH nor for

18
449 increasing electrical conductivity, thus, chemical consumption cost was zero. Similar costs

450 have been reported by Thakur and Mondal (2017) for water treatment with EC.

451
452 3.6 Statistical analyses of acetaminophen and UV254 absorbance removal

453

454 Univariate ANOVA test showed statistically significant difference between the treatments

455 (F2.76 = 136, P = <0.001) for acetaminophen removal. Post hoc t-Test assessed for differences

456 within the treatment indicated that acetaminophen removal was statistically significant at

of
457 lower concentration (1 and 2 mg L-1) compared to other treatments. At 5 mg L-1

ro
458 acetaminophen removal was statistically significant to 10 mg L-1 and 20 mg L-1. Statistically

459 -p
insignificant acetaminophen removal was observed between 10 mg L-1 and 20 mg L-1.
re
460 ANOVA test on UV254 absorbance reduction also exhibited that there was a significant
lP

461 difference between the treatments (F2.76 = 186, P = <0.001). However, post hoc t-Test

462 assessed for differences within the treatment showed that at 1 mg L-1 concentration, UV254
na

463 absorbance reduction was statistically insignificant compared to 2 mg L-1. Other than this
ur

464 result with EC for UV254 absorbance reduction at 1 mg L-1, both the lower doses tested (1 and
Jo

465 2 mg L-1) were statistically significant compared to all the treatments. There was a

466 statistically insignificant difference between 5 and 10 mg L-1 treatment whereas it was

467 significant between 5 and 20 mg L-1. There was statistically significant difference between 10

468 and 20 mg L-1 treatment for UV254 absorbance reduction. These results highlight that EC can

469 be effective for treatment up to 2 mg L-1 acetaminophen concentration and the process

470 efficiency was significantly affected when the concentration exceeded 5 mg L-1.

471

472 A linear correlation was found between UV254 absorbance reduction and acetaminophen

473 reduction at different concentrations with EC (Fig. 3). There was significant positive

474 correlation between UV254 absorbance reduction and acetaminophen removal at 1 mg L-1 (R2

19
475 = 0.88, n = 3, P <0.05) and 2 mg/L (R2 = 0.97, n = 3, P <0.05). At 5 mg L-1 concentration,

476 though there was positive correlation between UV254 absorbance reduction and

477 acetaminophen, it was statistically insignificant (R2 = 0.74, n = 3, P>0.05). Statistically

478 significant positive correlation existed between acetaminophen and UV254 absorbance

479 removal at 10 mg L-1 (R2 = 0.89, n = 3, P<0.05) and 20 mg/L (R2 = 0.77, n = 3, P <0.05). At

480 higher concentrations (10 and 20 mg L-1), once UV254 absorbance removal reached ~20%,

481 acetaminophen removal also occurred to similar levels. Wert et al. (2009) reported that UV254

482 absorbance serves as a good surrogate with good linear correlation to track the removal of

of
483 pharmaceutical compounds such as carbamazepine, meprobamate, dilantin, primidone,

ro
484 atenolol, and iopromide during wastewater treatment by ozonation. Strong correlations

485
-p
between UV absorbance and acetaminophen shows that this approach can be used to monitor
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486 the efficacy of water treatment plant for removal of several emerging organic contaminants.
lP

487 Such an approach could be useful considering the sampling and analysis requirements of
na

488 emerging organic contaminants that are often complicated, costly and time-consuming.

489 However, it must be noted that there might be differences in this approach due to site-specific
ur

490 conditions, hence, it is important to understand the linkages between UV254 and specific
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491 pharmaceutical compounds.

492

493 3.7 Comparison of electrocoagulation with a water treatment plant for removal of UV254

494 absorbance from river water

495

496 The lab-based EC process for river water treatment was compared with a full-scale water

497 treatment plant for removal of natural organic matter. UV254 absorbance varied from 0.11 to

498 0.31 during the study period of January and February 2020 (Fig. 4). The first step at water

499 treatment plant is addition of different chemicals in the following order: prechlorination +

20
500 polyaluminium chloride + polyelectrolyte + lime, this is followed by mixing and clarification

501 in lamella clarifiers. Water post clarification gets filtered through multi-grade sand filters and

502 activated carbon filters. Filtered water is chlorinated before supply to the public. At the water

503 treatment plant, coagulation-flocculation + sedimentation (lamella clarifier) was only able to

504 slightly reduce the UV254 absorbance from river water (Fig. 4 and Table SM 2). The clarified

505 water passes though multi-grade sand filters and activated carbon filters where most of the

506 UV254 absorbance removal occurred (Table SM 2). River water even after the activated

507 carbon filtration had some UV254 absorbance, which could be due to the presence of low

of
508 molecular weight natural organic matter.

ro
509

510
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There are limited studies where UV254 absorbance at water treatment plants were assessed
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511 which follows a similar treatment scheme thereby limiting further detailed comparison and
lP

512 discussion of present study results. However, a study by Matilainen et al. (2002) reported the
na

513 removal of natural organic matter at various stages of water purification in a treatment plant

514 of capacity (55,000 m3 d-1) by measuring TOC, UV254, KMnO4-number, and high-
ur

515 performance size exclusion chromatography peaks. Those authors reported UV254 absorbance
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516 that ranged between 0.136 and 0.103 from a lake in Finland, which served as a source of

517 water for the treatment plant. Matilainen et al. (2002) also found that higher molecular weight

518 organic matter was easily removed in coagulation and clarification than low molecular weight

519 matter, and the majority of UV254 absorbance removal occurred in activated carbon filters.

520

521 Lower natural organic matter removal in the present study after coagulation-flocculation in

522 water treatment plant could be due to pre-chlorination unit and high organic matter present in

523 river water which may form disinfection byproducts, thereby lowering the treatment

524 efficiency. However, in lab-based EC treatment there was no pre-chlorination step compared

21
525 to water treatment plant. Further studies on the role of pre-chlorination followed by EC

526 treatment may provide more information on this hypothesis. From Fig. SM 2c and Fig. 4, it is

527 clear that after multiple levels of treatment in the water treatment plant similar natural organic

528 matter removal could be obtained with EC alone, although, this is a batch mode operation at

529 laboratory level (UV254 absorbance reduced from initial 0.15 to 0.06 after 1 h of EC). Results

530 (see Table SM 3) are promising to explore the viability of integrating EC with water

531 treatment plants before filtration units mainly for removal of organic micropollutants.

532

of
533 4. Conclusions

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534

535
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EC was assessed for removal of acetaminophen and natural organic matter measured as
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536 UV254 absorbance. EC conditions in the batch mode were 60 min reaction time, Al-Al
lP

537 electrodes, 2 cm interelectrode distance and 9 V. Acetaminophen and UV254 absorbance

na

538 removal was significant at lower concentrations compared to higher concentrations. The

539 major mechanism for removal of acetaminophen was H bonding on Al(OH)3 flocs followed
ur

540 by consequent settlement, which was also validated through XRD and FT-IR analyses.
Jo

541 Reaction kinetics of acetaminophen in EC showed good fit with pseudo-second order model.

542 The operating cost for river water treatment using EC was US$ 0.22/m3. Correlation-

543 regression analysis indicated that UV254 can be a good surrogate for monitoring the removal

544 of acetaminophen. The comparative analysis of natural organic matter removal at an

545 operational full-scale water treatment plant showed the presence of UV254 absorbance after

546 treatment, though at a low concentration. UV254 absorbance removal observed at the water

547 treatment plant was lower than that recorded with lab-scale EC process. Results indicate that

548 there is a high potential for EC to be used for removal of acetaminophen and organic

549 micropollutants in river water treatment.

22
550

551 CRediT Authorship Contribution Statement

552

553 Shweta Kumari: Data curation, Formal analysis, Investigation, Methodology, Visualization,

554 Software, Validation, Writing - original draft

555

556 R. Naresh Kumar: Conceptualization, Project administration, Resources, Supervision,

557 Writing - original draft, Writing - review & editing

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558

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559 Declaration of Competing Interest

560
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561 The authors have no conflict of interest to declare.
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562
na

563 Acknowledgments

564
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565 Authors are thankful to Birla Institute of Technology, Mesra, Ranchi for providing necessary
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566 facilities for this research. Support from the central instrumentation facility, Birla Institute of

567 Technology, Mesra is thankfully acknowledged. Shweta Kumari also thank the institute

568 fellowship scheme offered by the Institute for her doctoral research.

569

570 References

571

572 Akarsu, C., Ozay, Y., Dizge, N., Gulsen, H.E., Ates, H., Gozmen, B., Turabik, M., 2016.

573 Electrocoagulation and nanofiltration integrated process application in purification of bilge

574 water using response surface methodology. Water Sci. Tech. 74, 564–579.

23
575

576 Aly, Z., Graulet, A., Scales, N., Hanley, T., 2014. Removal of aluminium from aqueous

577 solutions using PAN-based adsorbents: characterisation, kinetics, equilibrium and

578 thermodynamic studies. Environ. Sci. Poll. Res. 21, 3972–3986

579

580 APHA, AWWA, WEF 2005. Standard Methods for the examination of water and wastewater,

581 20th Ed. APHA, AWWA, WEF.

582

of
583 Altmann, J., Massa, L., Sperlich, A., Regina, G., Jekel, M., 2016. UV254 absorbance as real-

ro
584 time monitoring and control parameter for micropollutant removal in advanced wastewater

585
-p
treatment with powdered activated carbon. Water Res. 94, 240–245.
re
586
lP

587 Aydin, S., Aydin, M.E., Ulvi, A., 2019. Monitoring the release of anti-inflammatory and
na

588 analgesic pharmaceuticals in the receiving environment. Environ. Sci. Poll. Res. 26, 36887–

589 36902.
ur

590
Jo

591 Bahr, C., Schumacher, J., Ernst, M., Luck, F., Heinzmann, B., Jekel, M., 2007. SUVA as

592 control parameter for the effective ozonation of organic pollutants in secondary effluent.

593 Water Sci. Technol. 55, 267–274.

594

595 Beauchamp, N., Bouchard, C., Dorea, C., Rodriguez, M., 2020. Ultraviolet absorbance

596 monitoring for removal of DBP-precursor in waters with variable quality: Enhanced

597 coagulation revisited. Sci. Total Environ. 717, 137225

598

24
599 Bedner, M., MacCrehan, W.A., 2006. Transformation of Acetaminophen by Chlorination

600 Produces the Toxicants 1,4-benzoquinone and N-acetyl-p-benzoquinone Imine. Environ. Sci.

601 Technol., 40, 516–522.

602

603 Bener, S., Bulca, O., Palas, B., Tekin, G., Atalay, S., Ersöz, G., 2019. Electrocoagulation

604 process for the efficient removal of total organic carbon from real textile wastewater: effect

605 of conditions and kinetic study. Proc. Saf. Environ. Prot. 129, 47–54.

606

of
607 Bernal, V., Erto, A., Giraldo, L., Moreno-Piraján, J.C., 2017. Effect of solution pH on the

ro
608 adsorption of paracetamol on chemically modified activated carbons. Molecules 22, 1032.

609
-p
re
610 Can, O.T., Kobya, M., Demirbas, E., Bayramoglu, M., 2006. Treatment of the textile
lP

611 wastewater by combined electrocoagulation, Chemosphere 62, 181–187.

na

612

613 Carine, J., Ulises-Javier, J., Anne-Marie, W., Delmas H., 2009. Sonolysis of levodopa and
ur

614 paracetamol in aqueous solutions. J. Water Proc. Eng. 33, 10110.

Jo

615

616 Chen, W., Xu, J., Lu, S., Jiao, W., Wu, L., Chang, A.C., 2013. Fates and transport of PPCPs

617 in soil receiving reclaimed water irrigation, Chemosphere 93, 2621–2630.

618

619 Czech, B., Tyszczuk-Rotko, K., 2018 Visible-light-driven photocatalytic removal of

620 acetaminophen from water using a novel MWCNT-TiO2-SiO2 photocatalysts. Sep. Purif.

621 Technol. 206, 343–355.

622

25
623 Daneshvar, N., Oladegaragoze, A., Djafarzadeh, N., 2006. Decolorization of basic dye

624 solutions by electrocoagulation: an investigation of the effect of operational parameters. J.

625 Hazard. Mater. 129, 116–122.

626

627 Drouiche, N., Aoudj. S., Lounici. H., Mahmoudi. H., Ghaffour, N., Goosen. M.F.A. 2011.

628 Development of an empirical model for fluoride removal from photovoltaic wastewater by

629 electrocoagulation process. Desalin. Water Treat. 29, 96–102.

630

of
631 Ensano, B.M.B., Borea, L., Naddeo, V., Belgiorno, V., de Luna, M.D.G., Balakrishnan, M.,

ro
632 Ballesteros, F.C., 2019. Applicability of the electrocoagulation process in treating real

633
-p
municipal wastewater containing pharmaceutical active compounds. J. Hazard. Mater. 361,
re
634 367–373.
lP

635
na

636 Garcia-Segura, S., Eiband, M.M.S.G., de Meloa, J.V., Martínez-Huitle, C.A., 2017.

637 Electrocoagulation and advanced electrocoagulation processes: A general review about the
ur

638 fundamentals, emerging applications, and its association with other technologies. J.
Jo

639 Electroanal. Chem. 801, 267–299.

640

641 Gregory, J., Duan, J., 2001. Hydrolyzing metal salts as coagulants. Pure Appl. Chem. 73,

642 2017–2026.

643

644 Jekel, M., Dott, W., Bergmann, A., Dunnbier, U., Grinb, R., Haist-Gulde, B., Hamscher, G.,

645 Letzel, M., Licha, T., Lyko, S., Miehe, U., Sacher, F., Scheurer, M., Schmidt, C.K.,

646 Reemtsma, T., Ruhl, A.S., 2015. Selection of organic process and source indicator substances

647 for the anthropogenically influenced water cycle. Chemosphere 125, 155–167.

26
648

649 Ganesan, P., Lakhsmi J., Sozhan, G., Vasudevan, S., 2012. Removal of manganese from

650 water by electrocoagulation: adsorption, kinetics and thermodynamic studies. Can. J. Chem.

651 Eng. 9999, 1–11.

652
653 Gomes, J.A.G., Daida, P., Kesmez, M., Weir, M., Moreno, H., Parga, J.R., Irwin, G.,

654 McWhinney, H., Grady, T., Peterson, E., Cocke, D.L., 2007. Arsenic removal by

655 electrocoagulation using combined Al-Fe electrode system and characterization of products.

of
656 J. Hazard. Mater. 139, 220–231.

ro
657

658 -p
Govindan, K., Angelin, A., Kalpana, M., Rangarajan, M., Shankar, P., Jang, A., 2020.
re
659 Electrocoagulants characteristics and application of electrocoagulation for micropollutant
lP

660 removal and transformation mechanism. ACS Appl. Mater. Interfaces, 12, 1775–1788.

661
na

662 Holt, P.K., Barton, G.W., Mitchell, C.A., 2005. The future for electrocoagulation as a
ur

663 localised water treatment technology. Chemosphere 59, 355–367.

Jo

664

665 Kabdaşlı, I., Arslan-Alaton, I., Ölmez-Hancı, T., Tünay, O., 2012. Electrocoagulation

666 applications for industrial wastewaters: a critical review, Environ. Tech. Rev. 1, 2–45.

667

668 Katal, R., Farahani, M.H.D.A., Jiangyong, H., 2020. Degradation of acetaminophen in a

669 photocatalytic (batch and continuous system) and photoelectrocatalytic process by

670 application of faceted-TiO2. Sep. Purif. Tech. 230, 115859.

671

27
672 Kim, Y., Choi, K., Jung, J., Park, Kim, S.G., Park, J., 2007. Aquatic toxicity of

673 acetaminophen, carbamazepine, cimetidine, diltiazem and six major sulfonamides, and their

674 potential ecological risks in Korea. Environ. Int. 33, 370–375.

675

676 Kim, S., Chu, K.H., Al-Hamadani, Y.A.J., Park, C.M., Jang, M., Kim, D.H., Yu, M., Heo, J.,

677 Yoon, Y., 2018. Removal of contaminants of emerging concern by membranes in water and

678 wastewater: a review. Chem. Eng. J. 335, 896–914.

679

of
680 Lima, D.R., Hosseini-Bandegharaei, A., Thue, P.S., Lima, E.C., de Albuquerque, Y.R.T., dos

ro
681 Reis, G.S., Umpierres, C.S., Dias, S.L.P., Tran, H.N., 2019. Efficient acetaminophen removal

682
-p
from water and hospital effluents treatment by activated carbons derived from Brazil
re
683 nutshells. Coll. Surf. A 583, 123966.
lP

684
na

685 Mailler, R., Gasperi, J., Coquet, Y., Deshayes, S., Zedek, S., Cren-Olive, C., Cartiser, N.,

686 Eudes, V., Bressy, A., Caupos, E., Moilleron, R., Chebbo, G., Rocher, V. 2015. Study of a
ur

687 large scale powdered activated carbon pilot: removals of a wide range of emerging and
Jo

688 priority micropollutants from wastewater treatment plant effluents. Water Res. 72, 315–330.

689

690 Matilainen, A., Lindqvist, N., Korhonen, S., Tuhkanen, T. 2002. Removal of NOM in the

691 different stages of the water treatment process. Environ. Int. 28 457– 465.

692

693 Mena, V.F., Betancor-Abreu., A, Gonzalez, S., Delgado S., Souto, R.M., Santana, J.J., 2019.

694 Fluoride removal from natural volcanic underground water by an electrocoagulation process:

695 Parametric and cost evaluations. J. Environ. Manage. 246, 472–483

696

28
697 Negarestani, M, Motamedi, M., Kashtiaray, A., Khadir, A., Sillanpaa, M. 2020. Simultaneous

698 removal of acetaminophen and ibuprofen from underground water by an electrocoagulation

699 unit: Operational parameters and kinetics. Groundwater Sust. Dev. 11, 100474

700

701 Oden, M.K., Sari-Erkan, H., 2018. Treatment of metal plating wastewater using iron

702 electrode by electrocoagulation process: Optimization and process performance. Proc. Saf.

703 Environ. Prot. 119, 207–217.

704

of
705 Papadopoulous, K.P., Argyriou, R., Economou, C.N., Charalampous, N., Dailianis, S.,

ro
706 Tatoulis, T.I., Tekerlekopoulou, A.G., Vayenas, D.V., 2019. Treatment of printing ink

707
-p
wastewater using electrocoagulation. J. Environ. Manage. 237, 442–448.
re
708
lP

709 Paucar, N.E., Kim, I., Tanaka, H., Sato, C., 2019. Ozone treatment process for the removal of
na

710 pharmaceuticals and personal care products in wastewater. Ozone: Sci. Eng. 41, 3–16.

711
ur

712 Quesada, H.B., Cusioli, L.F., Bezerra, C.D.O., Baptista, A.T. Nishi, L., Gomes, R.G.,
Jo

713 Bergamasco, R., 2019. Acetaminophen adsorption using a low-cost adsorbent prepared from

714 modified residues of Moringa oleifera Lam. seed husks. J. Chem. Technol. Biotechnol. 94,

715 3147–3157.

716

717 Rodriguez-Narvaez, O.M. Peralta-Hernandez, J.M., Goonetilleke, A., Bandala, E.R., 2017.

718 Treatment technologies for emerging contaminants in water: A review. Chem. Eng. J.

719 323, 361–380.

720

29
721 Sahu, O., Mazumdar, B., Chaudhari, P.K., 2014. Treatment of wastewater by

722 electrocoagulation: a review. Environ, Sci, Pollut, Res, 21, 2397–2413.

723

724 Starling, M.C.V.M., Amorim, C.C., Leão, M.M.D., 2019. Occurrence, control and fate of

725 contaminants of emerging concern in environmental compartments in Brazil. J. Hazard.

726 Mater. 372, 17–36.

727

728 Su, C.-C., Cada, C.A., Dalida, M.L.P., Lu, M.-C. 2013. Effect of UV light on acetaminophen

of
729 degradation in the electro-Fenton process. Sep. Purif. Technol. 120, 43-51.

ro
730

731
-p
Thakur, L.S., Mondal, P., 2017. Simultaneous arsenic and fluoride removal from synthetic
re
732 and real groundwater by electrocoagulation process: Parametric and cost evaluation. J.
lP

733 Environ. Manage. 190, 102–112.

na

734

735 Wang, H., Liu, Y., Jiang, J.Q., 2016. Reaction kinetics and oxidation product formation in the
ur

736 degradation of acetaminophen by ferrate (VI). Chemosphere 155, 583–590.

Jo

737

738 Wert, E.C., Rosario-Ortiz, F.L., Snyder, S.S., 2009. Using ultraviolet absorbance and color to

739 assess pharmaceutical oxidation during ozonation of wastewater. Environ. Sci. Technol. 43,

740 4858–4863.

741

742 Wittmer, A., Heisele, A., McArdell, C.S., Bohler, M., Longree, P., Siegrist, H., 2015.

743 Decreased UV absorbance as an indicator of micropollutant removal efficiency in wastewater

744 treated with ozone. Water Sci. Technol. 71, 980–985.

745

30
746 Yang, L., Yu, L.E., Ray, M.B., 2008. Degradation of paracetamol in aqueous solutions by

747 TiO2 photocatalysis. Water Res. 42, 3480–3488.

748

749 Yanyan, L., Kurniawan, T.A., Ying, Z., Albadarin, A.B., Walker, G. 2017. Enhanced

750 photocatalytic degradation of acetaminophen from wastewater using

751 WO3/TiO2/SiO2 composite under UV–VIS irradiation. J. Mol. Liq. 243, 761–770.

752

753 Yun, W.C., Lin, K.Y.A., Tong, W.C., Lin, Y.F., Du, Y. 2019. Enhanced degradation of

of
754 paracetamol in water using sulfate radical-based advanced oxidation processes catalyzed by

ro
755 3-dimensional Co3O4 nanoflower. Chem. Eng. J. 373, 1329–1337.

756
-p
re
757 Zaied, M., Bellakhal, N., 2009. Electrocoagulation treatment of black liquor from paper
lP

758 industry. J. Hazard. Mater. 163, 995–1000.

na

759

760 Zietzschmann, F., Altmann, J., Ruhl, A.S., Dünnbier, U., Dommisch, I., Sperlich, A., Meinel,
ur

761 F., Jekel, M., 2014. Estimating organic micro-pollutant removal potential of activated
Jo

762 carbons using UV absorption and carbon characteristics. Water Res. 56, 48–55.

31
Table 1. Pseudo second order kinetic parameters of acetaminophen removal with EC at

different concentration

qe, experimental qe, calculated k2 (min g mg-1) R2

Acetaminophen
(mg) (mg)

1 mg L-1 12.4 13.0 0.543 0.989

2 mg L-1 14.4 13.3 0.014 0.981

5 mg L-1 40.8 41.3 0.002 0.936

10 mg L-1 52.3 53.2 0.001 0.932

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20 mg L-1 88.6 86.9 0.0089 0.954

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 70 40
Acetaminophen Reduction (%) y = 1.39x + 5.91 y = 0.62x - 2.89
35

Acetaminophen Reduction (%)

60 R² = 0.88 R² = 0.97
30
50
25
40
20
30
15
20
10
10 a 5 b
0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70
UV254 Absorbance Reduction (%) UV254 Absorbance Reduction (%)

50 30
45 y = 0.61x + 22.83 y = 0.44x + 7.51
Acetaminophen Reduction (%)

Acetaminophen Reduction (%)

R² = 0.74 25 R² = 0.89
40
35
20
30
25 15

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10
15
10

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5 c d
0 0
0 10 20 30 40 0 10 20 30 40 50
UV254 Absorbance Reduction (%)

25
-p UV254 Absorbance Reduction (%)
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y = 1.51x - 11.05
Acetaminophen Reduction (%)

R² = 0.77
20
lP

15

10
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5
e
0
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0 5 10 15 20 25
UV254 Absorbance Reduction (%)
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 UV254 Absorbance (cm-1)

0
0.05
0.1
0.15
0.2
0.25
0.3
0.35

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LC

ACF
Raw
Fig. 1: Variations (mean n=3, ±S.D.) in a, pH b, UV254 and c, acetaminophen removal

efficiency during EC of river water. (EC Conditions: 9 V, Al-Al, 2 cm inter electrode

distance)

Fig. 2. Acetaminophen a, XRD spectrum and b, FTIR spectrum before ( ) and after ( ) EC

at 1 mg L-1 concentration (EC Conditions: 9 V, Al-Al, 2 cm inter electrode distance)

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Fig. 3. Linear correlation plots between acetaminophen reduction (%) and UV254 absorbance

reduction (%) with EC at a, 1 mg L-1, b, 2 mg L-1, c, 5 mg L-1, d, 10 mg L-1 and e 20 mg L-1

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concentration (EC Conditions: 9 V, Al-Al, 2 cm inter electrode distance)
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Fig. 4. Variations in UV254 absorbance at different stages of water treatment plant

(LC - Lamella Clarifier, SF - Sand Filter, ACF - Activated Carbon)

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Highlights:

• Electrocoagulation effectively removed acetaminophen at 1 mg L-1

• Main removal mechanism was H bonding of acetaminophen on Al(OH)3 flocs
• Acetaminophen removal shows good correlation with UV254 absorbance removal
• Conventional water treatment plant is unable to remove UV254 absorbance completely
• Electrocoagulation can be suitable replacement for coagulation-flocculation

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The authors have no conflict of interest to declare.

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CRediT Authorship Contribution Statement

Shweta Kumari: Data curation, Formal analysis, Investigation, Methodology, Visualization,

Software, Validation, Writing - original draft

R. Naresh Kumar: Conceptualization, Project administration, Resources, Supervision,

Writing - original draft, Writing - review & editing

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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