Accepted Manuscript

Synthesis of magnetite from raw mill scale and its application for arsenate adsorption
from contaminated water

Muhammad Kashif Shahid, San Phearom, Young-Gyun Choi

PII: S0045-6535(18)30567-8
DOI: 10.1016/j.chemosphere.2018.03.150
Reference: CHEM 21094

To appear in: ECSN

Received Date: 8 January 2018

Revised Date: 12 March 2018
Accepted Date: 20 March 2018

Please cite this article as: Shahid, M.K., Phearom, S., Choi, Y.-G., Synthesis of magnetite from raw mill
scale and its application for arsenate adsorption from contaminated water, Chemosphere (2018), doi:
10.1016/j.chemosphere.2018.03.150.

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 ACCEPTED MANUSCRIPT

1 Synthesis of magnetite from raw mill scale and its application for
2 arsenate adsorption from contaminated water
3 Muhammad Kashif Shahida, San Phearomb and Young-Gyun Choib*
a
4 Department of Environmental & Chemical Convergence Engineering, Daegu University,
5 Daegudae-ro 201, Jillyang, Gyeongsan, Gyeongbuk, Republic of Korea

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b
6 Department of Environmental Engineering, Chungnam National University, Daejeon,
7 Republic of Korea
8 *Corresponding author, E-mail: youngchoi@cnu.ac.kr

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9 Abstract

10 The magnetite particles were chemically synthesized from the waste of hot rolling steel

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11 industry. The characterization of the synthesized magnetite was done by using Fourier
12 transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Energy

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13 Dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The synthesized
14 magnetite particles were used for the adsorptive removal of arsenate from the
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15 contaminated water. The maximum adsorption capacity of 7.69 mg was found on the
16 surface of 1 g of the magnetite. The point of zero charge for magnetite is determined at
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17 the pH 6. The adsorption capacity of magnetite particles was successfully restored with
18 alkali cleaning. Newly synthesized particles were found to be effective for arsenate
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19 removal up to 5 times with regeneration. The synthesis of magnetite from raw mill scale
20 and its application for arsenate adsorption is a cost effective and ecofriendly process.
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21 Keywords

22 Arsenic; Adsorption; Kinetics; Magnetite; Water treatment;

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23 Highlights
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24 • The raw mill scale was used to synthesize magnetite particles.

25 • Synthesized magnetite particles were utilized for arsenate removal from
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26 contaminated water.
27 • 1 g magnetite can adsorb maximum 7.69 mg of arsenate.

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28 1. Introduction

29 Arsenic (As) is a metalloid and widely known contaminant due to its poisonous and

30 cancer-causing properties. It exists in various mineral forms based on its complexation

31 with other atoms. It is placed in transition elements in the periodic table due to its variable

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32 oxidation state. Arsenite and arsenate with +3 and +5 oxidation states respectively, are

33 two main forms of arsenic. The weathering of arsenic containing minerals and

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34 geochemical reactions are the major factors causing dissolved arsenic in groundwater.

35 Moreover, in the oxidizing environment, mobilization of the arsenic is also identified as a

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36 major issue(Smedley et al., 2002; Sun et al., 2016). Serious health and environmental

37 problems are reported due to the arsenic contamination(Bassil et al., 2018; Marchant et al.,

38
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2017; Sarkar and Paul, 2016; Sarkar et al., 2008; Smith et al., 2006).
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39 Considering the high toxicity of arsenic, the acceptance limit for arsenic is set at 10 ppb
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40 by the World Health Organization (WHO). In addition to this, different countries have

41 also defined their own standards for arsenic limitation. To keep the arsenic concentration
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42 up to a standard value, different arsenic removal techniques or methods are known like
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43 membrane technology, coagulation–filtration precipitation, ion exchange and adsorption

44 (Chatterjee and De, 2017; Lata and Samadder, 2016; Maitlo et al., 2017; Mohamed et al.,
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45 2017; Molinari and Argurio, 2017; Nidheesh and Singh, 2017). Due to the low cost and

46 high effectiveness, adsorption is widely adopted method for treatment of arsenic

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47 contaminated water. A variety of metal oxides are known for the adsorptive removal of
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48 arsenic(Mohan and Pittman, 2007).

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49 In the last few years, magnetite particles have been extensively considered due to their

50 distinctive chemical and physical properties depending on the particles size and

51 morphology(Aredes et al., 2012). Although these particles were found with significant

52 biocompatibility and magnetic properties, they are also recognized for adsorptive removal

53 of arsenic from contaminated water(Farrell et al., 2014; Shipley et al., 2010, 2009).

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54 In this study, we introduced a novel method for the synthesis of magnetite particles from

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55 the waste of steel manufacturing industry and the application of synthesized particles for

56 adsorption of arsenate As (V) from contaminated water. Mill scale is an iron waste

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57 produced during the hot rolling process of steel industries. It consists of different iron

58 oxides i.e., wustite (FeO), hematite (α-Fe2O3), and magnetite (Fe3O4) with elemental iron

59
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and variable oil and grease matters(de Buzin et al., 2014; Yavuz et al., 2009). The
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60 significant amounts of iron ores present in mill scale enhance its importance for the

61 synthesis of magnetite for the adsorptive removal of arsenate from the contaminated
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62 water. As a cost effective and ecofriendly process for the magnetite synthesis and arsenate
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63 removal is presented in this study, its contribution will be significant for the large scale
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64 operation as well as for further research and developments.

65 2. Materials and Methods

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66 2.1. Chemicals

67
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The analytical grade chemicals and reagents were used without further purification. HCl,

68
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NaOH and H2SO4 were purchased from Fisher scientific. Arsenate solution was prepared

69 from sodium arsenate, dibasic (Na2HAsO4.7H2O, MW = 312.01).

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70 2.2. Mill scale

71 Raw mill scale was obtained from “P” iron & steel company, a steel industry based in

72 Korea. It has a plate shape structure with < 20 mm diameter and produced at the surface

73 of hot-rolled steel during the cooling process. For reducing and the homogenization of

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74 mill scale particles, it was crushed with a mechanical grinder (HKP-100, Korea

75 Pulverizing Machinery Co. Ltd). The powdered mill scale was dried for 24 h and was

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76 sieved into the different sizes including > 300, 150-300, 75-150, and 45-75 µm. The mill

77 scale having 45-75 µm size was used for synthesis of the magnetite.

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78 2.3. Pretreatment of mill scale

79
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Mill scale samples carry different impurities from the steel manufacturing units which
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80 were removed by pretreatment process. The oil and grease contents were removed by

81 alkali cleaning. For 100 g of mill scale, 1 L of 0.1 N NaOH solution was used and the
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82 mixture was allowed to stir on 260 rpm for 2 h. Later the mill scale was rinsed with
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83 deionized (DI) water.

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84 Fig. 1. (a) Operational scheme of the magnetite synthesis from mill scale; (b) glass

85 reactor for the preparation of ferrous precursor

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86 2.4. Magnetite synthesis

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87 Fig. 1a presents the operational scheme for magnetite synthesis. The co-precipitation
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88 method was used for the synthesis of magnetite particles from 45-75 µm mill scale. 500

89 ml of concentrated H2SO4 was added to the pretreated mill scale (100 g) in a 2 L jacketed

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90 glass vessel furnished with a heating system, a mechanical stirrer, an exit gas tube and a

91 gas inflow port for N2 gas as shown in Fig. 1b. The mixture was kept on stirring (250 rpm)

92 for 24 h under an inert atmosphere at 70 °C. The resulting mud like mixture, known as a

93 ferrous precursor, was used to synthesize magnetite. The ferrous precursor was then

94 dissolved in deionized water and the solution was filtered with 47 mm GF/C filter

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95 (WhatmanTM, 1.2 µm pore size). 0.3 N NaOH was added to the filtrate and raised the pH

96

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of the solution up to 11. Followed by the ageing at ambient temperature, the black

97 magnetite particles were precipitated which were collected and further rinsed with

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98 deionized water and dried at 40 °C.

99 2.5. Instrumental analysis

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100 All the experiments were done in the Jar Tester (J-USRC, Jisico, Japan) at 250 rpm. The
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101 pH of the solutions was analyzed by 96pH-L2 (samsan) and the temperature was recorded

102 with analytical thermometer. The characterization of mill scale and the synthesized
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103 magnetite particles was done with Powder X-ray diffraction (XRD) by using Cu Kα

104 (λ=1.5418 Å) radiations, operated at 40 kV & 200 mA on Rigaku D/MAX-2500/PC

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105 (Rigaku Corp. Japan). The XRD-pattern of synthesized magnetite particles was compared
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106 with the Joint Committee on Powder Diffraction Standards (JCPDS) database (magnetite,

107 card no. 19-0629). Nicolet 6700 Fourier transform infrared spectrometer (ThermoVG
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108 Scientific) was used to record the FTIR spectra of the synthesized particles. The

109 morphology of mill scale and the magnetite particles was examined with Hitachi SU-70
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110 field emission scanning electron micrograph (SEM) and the elemental composition of the
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111 synthesized particles was identified with Energy Dispersive X-ray spectroscopy (EDS).

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112 The arsenate concentration during the experiments was analyzed with Inductively

113 Coupled Plasma Mass spectroscopy (ICP-MS) manufactured by Thermo Scientific.

114 2.6. Batch adsorption experiments

115 Batch experiments were carried out for the adsorption of arsenate on the magnetite

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116 particles synthesized from the mill scale of 45-75 µm. The adsorption experiment was

117 done by adding 1 g of magnetite in to 1 L arsenate solution of different initial

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118 concentrations i.e., 0.1, 0.5, 1, 5, 10, 20, 30, 40 and 50 mg/L. The solutions were allowed

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119 to stir at 250 rpm for 24 h. Temperature was kept at 20 ºC and the pH of the solution was

120 adjusted at 6 with 0.1 N NaOH and 0.1 N HCl. Samples were collected and filtered prior

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121 to the analysis of arsenate concentration with ICP-MS. All the experiments were carried
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122 out in triplicates.

123 The specific amount of arsenate adsorbed on the magnetite particles was calculated from
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124 the following equation,

‫ܥ‬௜ − ‫ܥ‬௘ (1)

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‫=ݍ‬ ܸ
݉
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‫ܥ‬௜ − ‫ܥ‬௘ (2)

%Removal = (100)
‫ܥ‬௜

125
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126 where q is the adsorption amount (mg/g) in the solid at equilibrium, Ci and Ce are the

127 initial and equilibrium concentrations of arsenate (mg/L), respectively, V is the volume
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128 (mL) of the aqueous solutions, and m is the mass (g) of adsorbent used in the experiments.
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129 For the kinetic study, experiments were carried out with 10 mg/L initial concentration of
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130 arsenate and 1 g/L magnetite concentration. Temperature was controlled at 20 ºC and the

131 pH was maintained at 6. The mixture was kept on stirring (250 rpm) for 24 h and the

132 samples were collected 21 times (sampling interval is 0.5-2.0 h) after startup.

133 The effect of pH on the arsenate adsorption was evaluated by varying pH of the

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134 arsenate solutions having 10 mg/L concentration. The pH of the solutions was adjusted

135 to 2, 3, 4, 5, 6, 7, 8, 9, and 10 by adding appropriate amount of either 0.1 N NaOH or 0.1

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136 N HCl. The magnetite (1 g/L) was added to the solutions and the mixtures were stirred

137 (250 rpm) at 20 °C for 4 h. The samples were collected after 4 h and filtered prior to

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138 analysis of ionic concentration. To understand the effect of ionic strength on arsenate

139 removal, the ionic strength of the solutions was adjusted with addition of appropriate

140
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amounts of NaCl to make the final concentrations of NaCl at 0.01, 0.1, and 1 M. The
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141 point of zero charge (PZC) was measured by pH drift method.
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142 The magnetite particles used for the arsenate adsorption were dried at room temperature

143 for 48 h. The absorbed amount of arsenate was desorbed from the magnetite with 0.1 N
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144 NaOH. The magnetite particles were added in 0.1 N NaOH and the mixture was allowed
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145 to stir (250 rpm) for 2 h.

146 3. Results and discussion

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147 3.1. Characterization of mill scale and magnetite

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148 Magnetite particles were synthesized from the mill scale having size range between 45-75
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149 µm. The collected mill scale samples were found to constitute magnetite, hematite and

150 wustite (Fig. 2). As the raw mill scale generally constitutes iron oxides (SI: Table S1), it
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151 was used to prepare magnetite with co-precipitation method using ferrous precursors

152 obtained from acid digestion of mill scale. In an earlier study, the comparative elemental

153 constituents of mill scale and mill scale-derived ferrous precursor indicated a significant

154 increase in the iron contents of the ferrous precursor while the amount of other elements

155 was found to decrease(Legodi and de Waal, 2006). This finding indicates that the iron

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156 contents can be increased in the product (ferrous precursor) with the acid digestion of mill

157

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scale.

158 The mud like mixture constitutes major percentage of ferrous compound (FeSO4·H2O)

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159 and less quantity of ferric compounds including 3Fe2O3·8SO3·2H2O, FeOHSO4, and α-

160 FeOOH. The obtained ferrous precursor was utilized for the synthesis of magnetite

161
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particles. The product was found to be water soluble and the dark green precipitate was
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162 perceived when 0.3 N NaOH was added to the filtrate. This behavior was observed

163 because of the Fe(OH)2 present in the system, and that the major sharer of iron in the mud
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164 like mixture is in form of Fe2+(Nauer et al., 1985). Generally, the acid digestion of mill
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165 scale is required to assist the transformation of iron oxides to ferrous ions in an aqueous
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166 solution(Li, 1999). On adding the base to filtrate, the obtained dark green precipitate is

167 expected to constitute Fe3+, Fe2+, SO42- and OH- (Ismail et al., 1996). With increasing
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168 solution ageing time, the color of precipitate changed from dark green to black. The bulk

169 solution was turned in to black color after 4 h.

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170 Fig. 2. XRD pattern of raw mill scale (XRD pattern of synthesized magnetite and
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171 reference JCPDS 19-0629 is presented in sub section)

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172 The XRD pattern of the magnetite was compared and found in consistence with the

173 reference pattern (JCPDS file, No. 19-0629) as shown in Fig. 2. The specific peaks of

174 magnetite i.e., (220), (311), (400), (422), (511) and (440) were found in consistence with

175 earlier study and confirmed the formation of magnetite(Yean et al., 2005).

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176 Fig. 3. SEM micrograph of mill scale and the synthesized magnetite particles

177 The morphological examination of the magnetite particles indicated the aggregation of

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178 pseudo-cubic crystals as shown in Fig 3. The aggregated crystals were found in uniform

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179 and regular symmetry and the size of particles was found to be in the range of 10<d<50

180 µm. Particles were found with 92 m2/g surface area which is greater than that of

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181 commercially available magnetite (75 m2/g). The higher surface area can significantly
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182 increase the adsorption due to the availability of maximum adsorption sites(Keyhanian et

183 al., 2016).

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184 Fig. 4. EDS spectra of the synthesized magnetite particles

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185 The elemental composition of the magnetite particles is also confirmed by EDS analysis
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186 (Fig. 4). EDS spectra shows that the synthesized particles constitute O and Fe with 66 and

187 34% atomic proportion respectively. The higher atomic proportion of O in magnetite
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188 shows the existence of higher number of adsorption sites. The adsorption mechanism for

189 arsenate on magnetite particles is well defined in earlier studies (Freitas et al., 2016; Han
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190 et al., 2016; Liu et al., 2015).

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191 Fig. 5. FTIR spectra of the synthesized magnetite particles

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192 The FTIR spectra of the synthesized magnetite is presented in Fig. 5. The strong

193 adsorption band at 500 cm-1 specifies the presence of Fe-O bands of magnetite(Bruce et

194 al., 2004). The wide adsorption band between 3600-3000 cm-1 indicates the stretching

195 vibrations for OH which might be a result of physical adsorption of water molecule.

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196 3.2. Adsorption isotherm

197 The adsorption isotherm for the magnetite particles is shown in Fig. 6a. As the

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198 experiment starts, the quick adsorption was observed for all the solutions due to the

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199 maximum availability of adsorption sites and hence, the diffusion of arsenate initiated

200 from the inner pores of the adsorbent layer. Within decreasing an arsenate concentration

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201 in the solution, the diffusion rate also decreased and finally no further diffusion was
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202 observed and hence, adsorption reaction attained the equilibrium state. It was observed

203 that the solutions having low arsenate concentration reached at equilibrium state much
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204 faster than that of the solutions with higher arsenate concentration. The maximum

205 adsorption was found about 7.69 mg of arsenate on the surface of 1 g of magnetite. In
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206 another study, the surface precipitation was also witnessed, once the adsorption sites are
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207 fully occupied(Aredes et al., 2012).

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208 Fig. 6. (a) Adsorption isotherm of magnetite particles; (b) Kinetic of magnetite particles.

209 Bars denote the standard deviation; (c) Effect of pH and ionic strength on arsenate
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210 adsorption by magnetite particles. Bars denote the standard deviation.

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211 3.3. Adsorption kinetic

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212 Fig. 6b shows the time-dependence equilibrium adsorption capacity of magnetite for the

213 adsorption of arsenate. It was observed that the adsorption of arsenate on the magnetite

214 was very fast for initial 4 h and then the system attained a steady state and no prominent

215 change in adsorption was observed. Initially, the arsenate occupied all the available

216 adsorption sites and then arsenate anion started to diffuse through the internal pores of the

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217 magnetite and hence, this diffusion of the arsenate into the magnetite directed the reaction

218

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adsorption kinetics. The diffusion rate is directly associated with the arsenate

219 concentration in the solution. As the arsenate concentration decreases in the solution, the

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220 diffusion rate decreases and finally results in equilibrium conditions. Arsenate forms the

221 monodentate complex at low surface coverage and when the high surface coverage

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222 conditions are applied, bidentate mononuclear and bidentate binuclear complexes forms.
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223 The monodentate complex formation is supposed to be faster than bidentate complex

224 formation(Raven et al., 1998).

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225 3.4. Effect of pH and ionic strength

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226 Experiments were done with varying the initial pH of the solution and hence the effect of
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227 pH on the arsenate removal was observed (Fig. 6c). It is found that the adsorption was

228 stable up to pH 6 but as the pH increased, the adsorption started to decrease. At higher pH,
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229 the net surface charge on magnetite remains negative and repel the approaching arsenate

230 anions. In the earlier literature, it was discussed that the surface charge of magnetite
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231 remains positive at a pH lower than 6 and negative at pH over than 6(Giraldo and
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232 Moreno-piraján, 2013; Legodi and de Waal, 2006). Finally, it can be concluded that the

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233 arsenate adsorption is highly pH-dependent and any change in solution pH can

234 significantly effects the net surface charge of adsorbent followed by change in adsorption

235 behavior. Apart from pH variation, different molar concentrations of NaCl were also

236 added in the system and no specific change in arsenate adsorption was observed in the

237 presence of other anions.

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238 Fig. 7 shows the PZC for the adsorbent. It indicates the pH value at which the net surface

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239 charge on the solid remains zero in an electrolyte solution. The pHPZC for magnetite

240 particles is found at 6 which is in consistence with earlier studies(Giménez et al., 2007;

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241 Ntavou et al., 2016).

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242 Fig. 7. Point of zero charge with pH drift method
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243 3.5. Regeneration
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244 The used magnetite particles were dried at ambient temperature for 48 h and then washed

245 with 0.1 N alkali solution. It was found that almost 100% arsenate leached from the
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246 magnetite and same particles were found effective for adsorption of arsenate for up to 5
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247 consecutive cycles.

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248 4. Conclusions

249 This study describes the synthesis of magnetite particles from the raw mill scale and their
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250 application for the adsorptive removal of arsenate from contaminated water. The
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251 magnetite particles were successfully synthesized with the chemical co-precipitation

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252 method and the characterization was done with XRD, SEM, EDS and FTIR. The particle

253 size for the synthesized adsorbent was examined about 10<d<50 µm. The adsorptive

254 behavior of synthesized magnetite was examined with a series of experiments with

255 varying initial arsenate concentration, pH and contact time. The arsenate adsorption was

256 also examined in the presence of other anions in the system. The synthesized magnetite

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257 particles were found successful to remove arsenate at the pH 6 with the maximum

258

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adsorption capacity of 7.69 mg arsenate on 1 g of magnetite. The PZC of magnetite was

259 found at pH 6. The used particles were successfully regenerated with alkali cleaning and

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260 found effective for arsenate removal up to 5 cycles of adsorption. Finally, raw mill scale

261 was found as a cheapest source for magnetite synthesis followed by adsorptive removal of

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262 arsenate from contaminate water.
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263 Acknowledgement
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264 This work was supported by “Development of Eco-Smart Waterworks System” Program

265 by the Ministry of Environment (MOE), Republic of Korea (Project #: 2016002110009).

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Figure Captions

Fig. 1. (a) Operational scheme of the magnetite synthesis from mill scale; (b) glass reactor for the

preparation of ferrous precursor

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Fig. 2. XRD pattern of raw mill scale (XRD pattern of synthesized magnetite and reference JCPDS 19-

0629 is presented in sub section)

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Fig. 3. SEM micrograph of mill scale and the synthesized magnetite particles

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Fig. 4. EDS spectra of the synthesized magnetite particles

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Fig. 5. FTIR spectra of the synthesized magnetite particles
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Fig. 6. (a) Adsorption isotherm of magnetite particles; (b) Kinetic of magnetite particles. Bars denote the

standard deviation; (c) Effect of pH and ionic strength on arsenate adsorption by magnetite particles. Bars
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denote the standard deviation.

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Fig. 7. Point of zero charge with pH drift method

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