Accepted Manuscript

Synergistic deep removal of As(III) and Cd(II) by a calcined multifunctional MgZnFe-

CO3 layered double hydroxide: Photooxidation, precipitation and adsorption

Junqin Liu, Pingxiao Wu, Shuaishuai Li, Meiqing Chen, Wentin Cai, Dinghui Zou,
Nengwu Zhu, Zhi Dang
PII: S0045-6535(19)30441-2
DOI: https://doi.org/10.1016/j.chemosphere.2019.03.009
Reference: CHEM 23323

To appear in: ECSN

Received Date: 14 January 2019

Revised Date: 1 March 2019
Accepted Date: 3 March 2019

Please cite this article as: Liu, J., Wu, P., Li, S., Chen, M., Cai, W., Zou, D., Zhu, N., Dang, Z.,
Synergistic deep removal of As(III) and Cd(II) by a calcined multifunctional MgZnFe-CO3 layered
double hydroxide: Photooxidation, precipitation and adsorption, Chemosphere (2019), doi: https://
doi.org/10.1016/j.chemosphere.2019.03.009.

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

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

1 Synergistic deep removal of As(III) and Cd(II) by a calcined multifunctional

2 MgZnFe-CO3 layered double hydroxide: Photooxidation, precipitation and

3 adsorption

4 Junqin Liua,b, Pingxiao Wua,b,c,d,e*, Shuaishuai Lia,b, Meiqing Chena,b, Wentin Caia,

PT
5 Dinghui Zoua, Nengwu Zhua,b,e, Zhi Danga,b,c

RI
6 a school of Environment and Energy, South China University of Technology,

SC
7 Guangzhou 510006, P.R. China

8 b The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters,

9
U
Ministry of Education, Guangzhou 510006, P.R. China
AN
10 c Guangdong Provincial Engineering and Technology Research Center for
M

11 Environmental Risk Prevention and Emergency Disposal, South China University of

12 Technology, Guangzhou Higher Education Mega Centre, Guangzhou 510006, PR

D
TE

13 China

14 d Guangdong Engineering and Technology Research Center for Environmental

EP

15 Nanomaterials, Guangzhou 510006, China

C

16 e Guangdong Environmental Protection Key Laboratory of Solid Waste Treatment

AC

17 and Recycling, Guangzhou 510006, PR China

18 *Corresponding author

19 Tel.: +86-20-39380538;

20 Fax: +86-20-39383725.

21 E-mail: pppxwu@scut.edu.cn (P.X. Wu).

1
 ACCEPTED MANUSCRIPT

22 Abstract

23 A high removal rate (>99.7%) of combined arsenite (As(III)) and Cd (Cd(II)) in

24 low concentration (1000µg/L) from contaminated water was achieved by a calcined

25 MgZnFe-CO3 layered double hydroxide (CMZF) adsorbent. Batch control studies and

PT
26 a series of spectroscopy detection technologies were employed to investigate the

RI
27 removal mechanism and interactions between As(III) and Cd(II) on the interface of

SC
28 water/CMZF. Synergistic adsorption and photooxidation occurred based on the

29 systematical kinetic and isotherm studies. The enhanced removal of As(III) was

30
U
achieved by the photooxidation, formation of ternary As(III)-Cd(II) surface
AN
31 complexes and enhanced hydrogen bond. Meanwhile, oxidative formed negative
M

32 charged As(V) could reduce the electrostatic repulsion force between Cd(II) cations

33 and play a role as anion bridging, consequently resulted in a stronger attraction

D
TE

34 between CMZF and Cd(II). Combined with the verdicts of relevant characterizations

35 such as XRD, XPS and EPR, it was assumed that the deep co-removal mechanism
EP

36 could be attributed to the coupling of various processes including intercalation,

C

37 complexation, photooxidation of As(III) and precipitation of CdCO3. Moreover, the

AC

38 successful removal of As(III) and Cd(II) from real water matrix qualified the CMZF a

39 potentially attractive adsorbent for both As(III) and Cd(II) deep treatment in practical

40 engineering.

41 Keywords: MgZnFe-CO3 layered double hydroxide; simultaneous adsorption; deep

42 removal; As(III) molecule; As (V) anion; Cd(II) cation

2
 ACCEPTED MANUSCRIPT

43 1. Introduction

44 Arsenic (As) and cadmium (Cd) are both notorious in water resource which can

45 cause advese effects, even in a trace concentration (Esposito et al., 2018), to ecosphere

46 and human body (Lofrano et al., 2016; Yu et al., 2016). As is commonly exist as

PT
47 inorganic species of nonionized arsenite (As(III)) and oxyanions arsenate (As(V))

RI
48 based on the redox conditions (Vaiano et al., 2018; Zhang et al., 2018a), As(III) is

SC
49 much more hazardous than As(V) due to its more toxic, more mobile and less

50 adsorptive characteristics (Kim and Kim, 2014). While Cd is mainly exist as

51
U
hyper-toxic metal cation (Cd(II)) in various aquatic systems (Yoon et al., 2017).
AN
52 Elevated levels of As and Cd contaminated water derived from industrial activities
M

53 and natural water (Yan et al., 2015; Genc-Fuhrman et al., 2016; Wu et al., 2018) has

54 raised serious concerns as it posed threats to human health through the food chain
D
TE

55 accumulation and provision of drinking water (Chen et al., 2018; Li et al., 2018). Thus,

56 China has set limit for farming irrigation water that the concentration of As and Cd
EP

57 shall not exceed 0.05 and 0.01 mg/L. The World Health Organization (WHO) also has
C

58 set guidelines for drinking water that the maximum allowable concentration is 10µg/L
AC

59 and 3µg/L for As and Cd, respectively. (Wasana et al., 2017; Sun et al., 2018).

60 Heavy metals concentration in natural aqueous environment substantially

61 governed by mineral-surface interactions owning to the high affinity of minerals to

62 heavy metals (Zhang et al., 2018a). Thus metal oxides and metal hydroxides minerals

63 have been widely applied as adsorbents to remove As and Cd from the aqueous phase

3
 ACCEPTED MANUSCRIPT

64 in practical water treatment. So far, numerous techniques have been developed for the

65 removal of either As(III) or Cd(II) from water (Xie et al., 2016; López-Muñoz et al.,

66 2017; Huang et al., 2018). However, due to the different physicochemical properties

67 such as surface charge, ion form and redox activity between As(III) and Cd(II), it is

PT
68 more challenging to removal them simultaneously, especially in low concentration

RI
69 level (Li et al., 2018; Pawar et al., 2018). Furthermore, the interaction mechanism

SC
70 including the competition/synergy effect, complexation model as well as the affinity

71 of As(III) and Cd(II) on the mineral surface has been rarely investigated, which seems

72
U
the key for their synchronous removal when they coexist in the aqueous environment.
AN
73 Layered double hydroxides (LDHs) is a class of hydroxide minerals with the
M

74 brucite-like layer structure, which is also well-know as the anionic clay. The general

75 formula of LDHs can be presented as [M1-xIIMxIII(OH)2]x+[Ax/n]n- mH2O, where MII

D

and MIII denote mental ions located on the positively charged octahedral sheets, An- is
TE

76

77 exchangeable interlayer anion to neutralize the positive charge, X is range frome 0.17
EP

78 to 0.33 (Lu et al., 2016; Yan et al., 2018). Calcination treatment is commonly
C

79 performed as pre-treated method to enhance the adsorption performance of LDHs

AC

80 before application due to the elimination of interlayer substances (Lee et al., 2018; Yan

81 et al., 2018). In recent years, LDHs or calcined LDHs have been widely used as a

82 multifunctional material for environmental applications owing to their tunable metal

83 ions on brucite-like sheets and intercalated anions in hydrated interlayer regions

84 (Wang and O Hare, 2012; Fan et al., 2014). Fe based LDHs were used as adsorbent for

4
 ACCEPTED MANUSCRIPT

85 As treatment based on the high affinity of iron phase surface towards As (Türk et al.,

86 2009; Zhang et al., 2014). Zn based LDHs were performed as photocatalyst to degrade

87 pollutants based on its appropriate valance and conduction band location contributed

88 from the derived zinc oxide (Parida and Mohapatra, 2012; Bouaziz et al., 2018). In

PT
89 addition, the abundant functional hydroxyl groups (-OH) on the surface or various

RI
90 intercalated anions also qualified LDHs as a promising material for metal cations

SC
91 removal (González et al., 2015; Rahman et al., 2018). Thus there are reasons to believe

92 that LDHs particle will be a superior material for the treatment of combined As(III),

93
U
Cd(II) wastewater as well as an ideal medium to help dig out the underlying
AN
94 interaction mechanisms between As(III) and Cd(II). Unfortunately, to the best of our
M

95 knowledge, no research has been done in this aspect.

96 In this research a novel calcined MgZnFe-CO3 LDH (CMZF) was synthesized

D
TE

97 by a facile coprecipitation and calcination method. The prepared material exhibited an

98 outstanding removal efficiency for both As(III) and Cd(II) in low concentration level.
EP

99 A systematic study including kinetic studies, isotherm studies and relevant

C

100 characterizations, such as SEM, XRD, XPS and EPR techniques, were investigated.
AC

101 The objectives of this study is (1) to develop a high-efficient and low-cost adsorbent

102 for simultaneous depth treatment of As(III) and Cd(II) in contaminated water, (2) to

103 explore the interaction mechanisms between As(III) and Cd(II) pollutants in aqueous

104 environment, and (3) to explain the possible synergistic removal mechanisms of

105 As(III) and Cd(II) by CMZF adsorbent.

5
 ACCEPTED MANUSCRIPT

106

107 2. Materials and methods

108 2.1 Materials and chemicals

109 Chemical reagents including nitrate salts (Mg(NO3)2·6H2O, Zn(NO3)2·6H2O,

PT
110 Fe(NO3)3·9H2O, Cd(NO3)2·4H2O), nitric acid (HNO3), sodium hydroxide (NaOH)

RI
111 and Sodium carbonate (Na2CO3) were obtained from Guangzhou Chemical Reagent

SC
112 Factory (Guangzhou, P.R.C.). Sodium arsenite (NaAsO2) and disodium hydrogen

113 arsenate (Na2HAsO4·7H2O) were purchased from Sigma-Aldrich Chemical Company.

114
U
5,5-dimethyl-1-pyrrolidine N-oxide (DMPO) and 2,2,6,6-tetramethyl-4-piperidone
AN
115 (TEMP) were purchased from Aladdin Chemistry. The chemicals above are all
M

116 analytical reagent (AR) purity. The As(III), As(V) and Cd(II) stock solution were

117 obtained by adding adequate NaAsO2, Na2HAsO4 · 7H2O and Cd(NO3)2·4H2O to

D
TE

118 deionized water respectively.

119
EP

120 2.2 Preparation of MgZnFe layered double hydroxides particles

C

121 The MgZnFe layered double hydroxide (MZF LDH) and its calcined sample
AC

122 (CMZF) were obtained using co-precipitation and calcination method, the detail was

123 shown in Text S1. For comparison, MgFe layered double hydroxide (MF LDH) and

124 its calcined sample (CMF) were synthesized followed by similar methods except for

125 adding zinc nitrate. All of the materials were ground into powder for further use.

126

6
 ACCEPTED MANUSCRIPT

127 2.3 Characterization

128 The X-ray diffraction (XRD) patterns of the materials were recorded by a D8

129 Advance diffractometer with Cu Ka radiation (λ= 1.5406 Å) at 40 kV and 40 mA. The

130 morphology and distribution of major elements were detected on a field-emission

PT
131 scanning electron microscopy (SEM, Carl Zeiss, Germany) combined with

RI
132 energy-dispersive X-ray spectroscopy (EDS). High-resolution transmission electron

SC
133 microscopy (TEM) images were obtained by JEM-2100F field emission transmission

134 electron microscope with an accelerating voltage of 200 kV. Solid state UV-vis diffuse

135
U
reflectance spectra (UV-vis DRS) was recorded on a UV-2550 (Shimadzu, Japan)
AN
136 spectrometer equipped with an integrating sphere within 190-900 nm wavelength
M

137 range. The Brunauer-Emmett-Teller (BET) specific surface area were investigated

138 utilizing a Micrometric ASAP 2020 analyzer. Thermogravimetric analysis (TGA)

D
TE

139 were carried out on a Netzsch STA 409 PC/PG instrument under air atmosphere.

140 X-ray photoelectron-spectra (XPS) analysis was carried out on the X-ray
EP

141 photoelectron spectrometer (AES430S, ANELVA, Japan). The ROS were identified
C

142 on an Electron Paramagnetic Resonance (EPR) Spectrometer Bruker A300 seted up as

AC

143 center magnetic field of 3509.44 G, sweep width of 100 G, microwave frequency of

144 9.87GHz and power of 20.00 mW.

145

146 2.4 Experiment for As and Cd adsorption

147 The batch kinetic adsorption experiments were carried out to estimate the

7
 ACCEPTED MANUSCRIPT

148 adsorption characteristics of Cd and As on LDH adsorbent. In details, 0.01g

149 adsorbents were added into 20 ml single or mixed solution of Cd and As obtained by

150 diluting the stock solution to desired concentration, then shaken in a

151 temperature-controlled rotary at 30±1 ℃ and pH of 6 under dark or irradiation

PT
152 conditions. The simulated visible light source was provided by a 300 W xenon lamp.

RI
153 After reaction has reached desired time, the suspension was filtered through a 0.45µm

SC
154 filter membrane and the residual solution was collected for analysis. For isotherm

155 studies, 20 mL solution contain As(III)/As(V) or Cd(II) with the concentration

156
U
varying from 1 to 100 and 1-260 mg/L, respectively, was adjusted on pH to 6.0 and
AN
157 then added with 10 mg of materials for 12 h oscillation to fit the Langmuir or
M

158 Freundlich model (Rehman et al., 2018), the model equations can be found in

159 supplement materials. The effect of pH on removal of As(III) and Cd(II) was studied
D
TE

160 in a pH range of 3-10.0 adjusted by 0.1M NaOH or HNO3. The real water adsorption

161 was carried out using the spiked river water (added concentration of 429 µg/L As(III)
EP

162 and 363 µg/L Cd (II), Pearl River, Guangdong Province, China. Detailed
C

163 water-quality index can be found in supplement materials, Table S4). The
AC

164 concentrations of Cd(II) and total As in the obtained solutions were analyzed by

165 ICP-MS (Agilent, 7700, USA). The concentration of As(V) was analyzed by

166 spectrophotometric method based on the molybdenum blue at λ= 880nm (Vaiano et

167 al., 2014). All the experiments were conducted in triplicate and the average data were

168 presented with their standard deviations.

8
 ACCEPTED MANUSCRIPT

169

170 3.Results and discussion

171 3.1 Characterization of as-prepared samples

172 3.1.1 XRD analysis

PT
173 The XRD patterns of MZF LDH and its calcined sample CMZF were depicted in

RI
174 Fig. S1a. All the characteristic peaks including (003), (006), (009), (015), (018), (110)

SC
175 and (113) could be found clearly in MZF LDH, meaning the well crystallographic

176 LDHs were synthesized. After calcination, the wide and weak spinel characteristic

177
U
peaks of MgFe2O4 (JCPDS No. 88-1943) or ZnFe2O4 (JCPDS no. 82-1042) (Wang et
AN
178 al., 2017) were observed. The d spaces decreased from 0.78 to 0.25 nm after
M

179 calcination, indicating a partial interlayer molecules and ions were removed during

180 thermal treatment, which could improve the adsorption capacity by ion intercalation
D
TE

181 during the layer reconstruction process (Kang et al., 2013).

182
EP

183 3.1.2 Optical adsorption properties

C

184 UV-vis DRS spectra and calculated band gap were recorded in Fig. S1b and c.
AC

185 From S1b, the light adsorption of samples within visible-light range has been

186 improved significantly after calcination. That is possibly due to the topotactic

187 transformation of LDH during thermal treatment leading to a surface defects, resulting

188 in a red-shift of optical absorption (Lin et al., 2017). As a result, the band gap (Fig.

189 S1c) of CMZF became narrower compared with LDH. Noticeably, the band gap

9
 ACCEPTED MANUSCRIPT

190 distance were only 2.05 and 2.1 eV for CMZF and MZF LDH, respectively, meaning

191 the efficient utilization of photons which could results in more electron-hole pairs on

192 LDHs under illumination therefore leading to high photocatalytic activities (Zhang et

193 al., 2018).

PT
194

RI
195 3.1.3 Surface morphological and pore structure analysis

SC
196 Fig. 1 presented the SEM, TEM and corresponding mapping images of the MZF

197 LDH and CMZF. The thin plate-like structure of MZF LDH and CMZF can be

198
U
observed clearly with the diameter around 200 nm., which is the typical morphology
AN
199 for the LDHs based materials. While the TEM image of CMZF exhibited obvious
M

200 pore structure compared with MZF LDH, indicating the emerging of abundant

201 meso-pore after thermal treatment (details see Fig. S2). It is therefore leading to the
D
TE

202 total pore volume and BET surface area of CMZF increased significantly (Table S1),

203 which play important roles for increasing the adsorption capacity. The different
EP

204 electron diffractions (embedded graph) further proved the topotactic transformation
C

205 during thermal treatment, which was in agreement with the XRD result. The EDS and
AC

206 mapping imagines of CMZF were presented in Fig. 1f. Mg, Zn and Fe are

207 homodisperse throughout the entire material, indicating the regularly Structured

208 arrangement of Mg, Zn and Fe in the layer sheets with the ratio of around 3:1:2. The

209 molecular-scale structure could be found in Fig. S3.

210

10
 ACCEPTED MANUSCRIPT

211 3.2 Batch adsorption experiments

212 3.2.1 Effect of metal composition.

213 The removal efficiency of Cd(II) and As(III) by MZF LDH, MF LDH and their

214 calcined samples was given in Fig. S5. Compared with MF LDH, MZF LDH showed

PT
215 a higher As(III) removal but a lower Cd(II) removal efficiency. However the

RI
216 difference of surface area pore volume and average pore diameter (Table S1) between

SC
217 MF and MZF LDH is negligible, thus it was deduced that the element composition

218 rather than the structure played a key role for As(III) or Cd(II) selective adsorption.

219
U
Zn and Fe mainly responsible for As(III) adsorption, while Mg mainly responsible for
AN
220 Cd(II) adsorption, which agree with the later XPS and SEM mapping results.
M

221

222 3.2.2 Effect of pH and irradiation

D
TE

223 The effect of pH and irradiation have been researched as shown in Fig. 2. In the

224 dark condition, As(III) mainly present as neutral H3AsO3 in a wide pH range from 1 to
EP

225 9 (Zhu et al., 2018), thus the changing of surface charge of CMZF showed little effect
C

226 to the As(III) removal. Cd(II) mainly present as cation ion, the lower zeta potential of
AC

227 CMZF could enhance the attraction between the surface hydroxyl groups and Cd(II)

228 at a higher pH. While under illumination, As(III) removal efficiency was improved to

229 a great extent whatever the pH was, proving that the CMZF had a great photocatalysis

230 property for improving As(III) removal. In the binary system of As(III) and Cd(II), no

231 obvious decrease was found in both As(III) and Cd(II) removal within all the pH

11
 ACCEPTED MANUSCRIPT

232 range, but a little improve was observed at basic condition. Both the As and Cd

233 residual concentration met the WHO drink water standard (10µg and 3µg/L

234 respectively) when the pH was above 6. Additionally, the dissolved Fe level were

235 depicted in Fig. S6. Negligible leached Fe ion was detected (<4µg/L) within all pH

PT
236 range above 4. All of these results indicate the great potential and safety of CMZF in

RI
237 the actual application.

SC
238 Zeta potentials of CMZF before and after reaction with As(III) and Cd(II) were

239 exhibited in Fig. S7, the isoelectric points of CMZF decreased from 3.4 to 3.2 (in

240
U
dark)/2.9 (in light) after adsorption of As(III) and increased to 3.6 after Cd(II)
AN
241 adsorption. The isoelectric points could been shifted by the formation of
M

242 inter-sphere complexes based on the covalent or ionic bond (Goldberg and Johnston,

243 2001). Thus both the As(III) and Cd(II) adsorption process on the interface of CMZF
D
TE

244 adsorbent could be concluded as not only an electrostatic adsorption, but also

245 characteristic adsorption.

EP

246
C

247 3.2.3 Kinetic studies

AC

248 The removal efficiency is crucial for practical application engineering, kinetic

249 studies in the single or binary As(III) and Cd(II) system were conducted and the

250 results were displayed in Fig. 3. As shown in Fig. 3a, the CMZF exhibited a higher

251 adsorption efficiency toward As(V) compared with As(III). It could be ascribed to the

252 bigger As(V) group possess a stronger steric effect which qualified it more easily be

12
 ACCEPTED MANUSCRIPT

253 caught by surface defects of CMZF to form complexes (Mueller et al., 2010; Liu et al.,

254 2018). Besides, the extra O atom in the As(V) groups might also contributed

255 additional site for hydrogen bond. Fig. 3b displayed the light adsorption experiment,

256 the total As concentration decreased much faster and lower in the presence of light,

PT
257 meaning the photo-oxidation played a crucial role enhancing As(III) uptake. The

RI
258 generated As(V) concentration (see embedded graph of Fig. 3b) could further prove

SC
259 this conclusion for it raised a little at fist 20 min due to higher oxidation rate of As(III)

260 to As(V) than adsorption, then dropped to an extremely low level by the combined

261
U
process of photocatalysis and adsorption. Kinetic curves in the binary As(III) and
AN
262 Cd(II) systems were also recorded in Fig. 3c and d. From Fig. 3c, though As(III)
M

263 removal was enhanced in the dark by Cd(II), it still remain 37.2µg/L after 180min

264 adsorption, much higher than the drink water standard (10 µg/L). While only 3.4 µg/L
D
TE

265 As with a unconspicuous adsorption decrease was found under illumination in the

266 binary system. Considering As(III) were presented as As(V) under the irradiation
EP

267 condition, thus we proposed that Cd(II) can improve As(III) adsorption but decrease
C

268 the adsorption of As(V), which displayed a accordance with the later studies in binary
AC

269 Cd(II) system. As shown in Fig. 3d, the removal of Cd(II) by CMZF was a fast

270 process with establishing a balance within 10 min and fell into a ultra low

271 concentration of 2.4 µg/L Cd(II) after 180min, indicating a strong interaction between

272 Cd(II) and CMZF (Chen et al., 2017). The additional As(III) improved Cd(II)

273 adsorption in the light while depressed Cd(II) in darkness, further proved that Cd(II)

13
 ACCEPTED MANUSCRIPT

274 could compete the adsorption site on CMZF with As(V). In this study, the equilibrium

275 pH was 8.5, thus the surface charge of CMZF (pHphz=3.4) was more favorable for

276 Cd(II) adsorption in neutral condition. On the other hand, the photo-generated

277 negative charged As(V) could meanwhile provide shielding effect (Zhu et al., 2015) to

PT
278 compensate the positive repulsion between different Cd(II) leading to more accessible

RI
279 adsorption sites for Cd(II), Cd(II) adsorption was therefore improved with As(III) in

SC
280 the light. While As(III) was mainly present as neutral H3AsO3 in a wide pH range

281 from 1-9 (pKa=9.2) without lighting. The competition of Cd(II) to As(III) was

282
U
negligible compared with that of As(V). In contrary, Cd(II) can enhance As(III)
AN
283 uptake through the formation of ternary surface complexation or coordination
M

284 complexes (Ren et al., 2016). Noticeably, the residual concentration of As(III) and

285 Cd(II) was below 10µg/L and 3 µg/L respectively in their both single or mixed
D
TE

286 systems, well met the drinking water provision.

287
EP

288 3.2.4 Isotherm studies

C

289 As depicted in Fig. 4, isotherm studies in single or mixed systems have been
AC

290 investigated to better understand the coordination between As(III) and Cd(II). The

291 mass ratio of As to Cd was selected as 2:1 and 1:10 for As and Cd isotherms in the

292 mixed system respectively. The single As(III) and As(V) isotherms fitted both

293 Langmuir and Freundlich model well. That means As(III) and As(V) could form

294 multilayers on the adsorbent (Fig. S8a), which might attribute to the hydrogen bond

14
 ACCEPTED MANUSCRIPT

295 between O atom and hydroxyl group from different As groups. While the isotherms of

296 single Cd(II) fitted Langmuir model well with an incredible high adsorption constant

297 (K=1.37L/mg), suggesting the strong interaction involved in Cd(II) and CMZF

298 adsorbent. After the appearance of Cd(II), As(III) turn into Freundlich model and

PT
299 As(V) transferred to Langmuir model respectively. That indicating the ternary surface

RI
300 complexation or coordination happened between neutral As(III) and Cd(II). Besides,

SC
301 due to Cd possesses a lower absolute electronegativity (1.69) than H (2.2) and As

302 (2.18) dose, the electron cloud density of adjoining O will be raised after

303
U
complexation with Cd thus leading to an enhanced hydrogen bond effect. While
AN
304 owing to As(V) group has a higher electronegativity and negative charge compared
M

305 with As(III) groups, it is more difficult to approach the negative charged surface of

306 CMZF when Cd(II) appeared (Fig. S8b). In contrast, the coordinated deprotonated
D
TE

307 As(V) could play a role as anion bridging to attract positive charged Cd(II) (Zhu et al.,

308 2016). Moreover, the dissociative As(V) could provide shielding effect to Cd(II), thus
EP

309 the Cd(II) isotherm was changed into Freundlich model illustrated in Fig. 4d. These
C

310 analyses agree with that proposed in kinetic studies, As(III) can occupy the adsorption
AC

311 site for Cd(II). While As(V) was weaker at the sites competition, which prefer to build

312 hydrogen bound rather than a direct sites adsorption thus improved the removal of

313 Cd(II) and As(III). In short, the competitiveness ranking of these three pollutants was

314 As(III) > Cd(II) >As(V). All the parameters of isotherms were given in Table S2 and

315 the Schematic diagrams were proposed in Fig. S8. Additionally, the maximum As and

15
 ACCEPTED MANUSCRIPT

316 Cd adsorption capacities of CMZF and previously reported adsorbents were compared

317 in Table S3. CMZF outperformed most of other adsorbents, indicating the CMZF

318 particle is a rather competitive alternative for As and Cd removal in actual water

319 treatment.

PT
320

RI
321 3.2.5 Effect of ionic strength

SC
322 The effect of ionic strength on the removal of As(III) and Cd(II) by the CMZF

323 was depicted in Fig. S9. No significant decrease even a slight enhancement of As(III)

324
U
and Cd(II) removal was observed as the ionic strength increased from 0.1 mM to
AN
325 10mM, indicating the good selectivity adsorption for As(III) and Cd(II) of CMZF.
M

326 Particularly, adsorption of ions via outer-sphere complexation is strongly effected by

327 ionic strength based on electrostatic force, as their adsorption is inhibited by

D

competition of weakly adsorbing ions (such as Na+, NO3-). On the contrary,

TE

328

329 adsorption by inner-sphere coordination (ligand exchange) shows little sensitivity to

EP

330 ionic strength with a stronger chemical bond (McBride, 1997). It further suggested
C

331 that both As(III) and Cd(II) were coordinated by CMZF to form stubborn inner-sphere
AC

332 complexes.

333

334 3.2.6 Real water adsorption test.

335 Water matrix in reality is far more complex than deionized water as various

336 types of inorganic and organic matters will be generally contained in it. Test of

16
 ACCEPTED MANUSCRIPT

337 application of CMZF for practical As(III) and Cd(II) contaminated water treatment

338 was implemented using the spiked river water (Pearl River, Guangdong Province,

339 China, spiked concentration of 429 µg/L As(III) and 363 µg/L Cd (II) with 0.25 g/L

340 CMZF) and the result was displaced in Fig. S10. Apparently, CMZF effectively

PT
341 removed both As(III) and Cd(II) under natural light or simulated visible light. All the

RI
342 residual concentration of As(III) and Cd(II) were reduced to value lower than 10µg/L

SC
343 and 3µg/L, respectively, after 6 h adsorption. That indicating the great potential of the

344 CMZF adsorbent on practical application for As(III) and Cd(II) deep removal.

345
U
AN
346 3.3 Removal mechanism analysis
M

347 3.3.1 Surface characterization using XPS

348 X-ray photoelectron spectroscopy (XPS) is a powerful tool for identify the
D
TE

349 chemical state changes of elements in the upper atomic layers of solid surfaces. The

350 surface state of compositions of the CMZF before and after As(III) and Cd(II)
EP

351 adsorption were characterized by XPS and the high-resolution scan of As3d,, C1s,
C

352 Fe2p and O1s core-level photoelectron spectra were presented in Fig. 5.
AC

353 As depicted in Fig. 5a, the binding energy peaks of As 3d after treatment of

354 As(III) solution in the dark and light conditions located at 44.3 and 45.4 eV, which

355 can be assigned to As(III) and As(V) respectively (Sun et al., 2017). These results

356 indicate that As adsorbed on to the CMZF was mainly As(III) in the dark and As(V)

357 in the light, proving that the As(III) existed on the surface of CMZF could be

17
 ACCEPTED MANUSCRIPT

358 efficiently oxidized to less toxic As(V) during the photooxidation process.

359 The high-resolution scan of C 1s were shown in Fig. 5b, the peaks located at

360 288.5eV were attribute to the C=O (Singh et al., 2014) in CO32- at the surface or

361 interlayer of CMZF. After adsorption of Cd(II), a new peak appeared at 291 eV which

PT
362 was attributed to the n-π* transition of C=O bound (M. and T. C., 2017). suggesting

RI
363 that Cd(II) bounded onto the interlayer CO32- group and thus the electron density

SC
364 towards the C=O is decreased (Irani et al., 2015). While after simultaneous treatment

365 of Cd(II) and As(III), an obviously decrease of the n-π* transition C=O bound was

366
U
observed, implying As(III) was more competitive to be exchanged into the CMZF
AN
367 interlayer.
M

368 Fig. 5c illustrated The high-resolution scan of Fe 2p, the binding energy value of

369 Fe2p 3/2 (711.4 eV) and Fe2p 1/2 (724.8 eV) indicated the Fe oxidation state in the
D
TE

370 adsorbent was +3 (Yang et al., 2018). After the adsorption of As(III) or simultaneous

371 adsorption of As(III) and Cd(II), a significant decrease of the Fe 2p 3/2 spectra
EP

372 intensity was observed, suggesting the strong interactions between As and Fe phase
C

373 (Zhang et al., 2005). While after reaction with single Cd(II), the Fe 2p 3/2 spectra
AC

374 intensity changed slightly. That means Fe species in the CMZF adsorbent mainly

375 perform as an adsorbent for As. Compared with Fe 2p, other metal spectra like Zn 2p

376 and Mg 1s changed inconspicuously.

377 At the last as depicted in Fig. 5d, the high resolution scans of O1s spectra could

378 be deconvoluted into three overlapped peaks at around 529.6, 530.4 and 531.7 eV

18
 ACCEPTED MANUSCRIPT

379 corresponding to oxide oxygen (M-O), hydroxyl groups (-OH) and adsorbed water

380 (H2O) respectively (Li et al., 2010). After adsorption, the total O1s, M-O and H2O

381 spectra intensity increased obviously, while a significant intensity decrease was

382 observed in -OH. Besides, the peak area ratio of -OH group decreased obviously from

PT
383 38.5% to 27.9% (As (III)), 21.6% (Cd(II)) and 24.6% (As(III) and Cd(II))

RI
384 respectively, By contrast, the peak area ratio of M-O increased signally from 25.3% to

SC
385 37%, 35.5% and 38.9 respectively. All the results implying several -OH has been

386 replaced by As or Cd during the adsorption process and inner-sphere surface

387 complexes were subsequently formed.

U
AN
388
M

389 3.3.2 Identification of oxidant for As(III)

390 It is well known that the process of photocatalytic oxidation for As(III) involves
D

diverse active species, such as photo-generated holes (h+), hydroxyl radicals ( OH)
TE

391

392 and singlet oxygen (1O2). Electron paramagnetic resonance (EPR) was employed for
EP

393 radical detection and the results was depicted in Fig. S11. The 3-line TEMP-1O2
C

394 adducts EPR spectra with equal intensities (special hyperfine coupling constants of
AC

395 αN=16.9G (Li et al., 2017)) in the CMZF/light system was captured after 5min

396 irradiation, revealing that 1O2 was produced as the ROS during photocatalysis process.

397 Additionally, both energy transfer and radical reaction of superoxide anion ( O2- )

398 could produce 1O2 (Zhang et al., 2018b; Bai et al., 2019), thus O2- should be

399 involved in the CMZF/Light system (Eq. (5)). Unfortunately, other primary oxidizing

19
 ACCEPTED MANUSCRIPT

400 radicals was not detected during EPR analyses, which could be the reason of low

401 intensity. Therefore, it is concluded that the main oxidant in the CMZF/light system

402 were the h+ and 1O2, which resulted in the effective oxidization reaction of As(III) to

403 As(V) described in the Eqs. (4) and (7).

PT
404 CMZF + hv → e- + h+ (3)

RI
405 h+ + As (III) → As (IV)→ As (V) (4)

e- + O2 → O2-

SC
406 (5)

407 O2- + h+ → 1O2 (6)

U
1
408 O2 + As (III) → As (IV)→ As (V) (7)
AN
409
M

410 3.3.3 Surface characterization using XRD and mapping images.

411 XRD data and Element mapping images of CMZF after adsorption were also
D
TE

412 obtained to better understanding the removal mechanism. As depicted in Fig. 6a, after

413 adsorption of As(III), three main characteristic XRD peaks assigned to (003), (006),
EP

414 (009) of layered double hydroxides was found with layer distance of 0.79nm,
C

415 indicating the reconstruction of the interlayer area. Neutral or negative charged groups
AC

416 like H3AsO3, H2O, H2AsO4- and CO32- will be adsorbed and exchanged into the

417 interlayer by positive charged metal octahedral sheets. The SEM images of CMZF

418 after As(III) treatment became more rough on the surface compared with that before

419 adsorption in a sheet structure morphology. The mapping imagines of All metals As

420 and C were homodisperse on the whole area, suggesting As uniformly coordinated

20
 ACCEPTED MANUSCRIPT

421 with -OH groups.

422 After treatment of Cd(II) (Fig. 6b), the XRD data showed a series of

423 characteristic peaks of CdCO3, which was in agreement with the XPS analysis of C1s

424 (Fig. 5b). From SEM image we can see the square bulks appeared and destroyed the

PT
425 sheet morphology of CMZF. Mapping images showed an intensive electron density of

RI
426 Cd and C on the bulk area, further proved the formation of CdCO3 crystal. The

SC
427 electron density of Mg in the bulk area was higher than that of Zn or Fe, indicating

428 CdCO3 mainly combine with Mg phase which agree with the former results (Section

429 3.2.1). The intensive and sharp peaks

U of CdCO3 crystal (Ksp=1X10-12,
AN
430 C(Cd)=0.1µmol/L) indicating the strong concentration process of Cd(II) give rise to
M

431 the outstanding removal efficiency at low concentration.

432 Fig. 6c presented the XRD and mapping images after adsorption of Cd(II) and
D
TE

433 As(III). The XRD data shown only the (012) characteristic peak of CdCO3. And the

434 SEM image shown a homogeneous sheet layer rather than the bulked CdCO3. It could
EP

435 be explained as follow (i) first, in the binary system, As(III) was easier to be
C

436 exchanged into the interlayer owning to the positive charged octahedral sheets of
AC

437 CMZF, and (ii) As(III) will occupy the interlayer area therefore prevent the

438 agglomeration of CdCO3 into well crystallographic bulk at some extent, thus (iii) the

439 isolated CdCO3 only preferentially orientated to the (012) crystal face and growth to

440 the nanocrystals CdCO3 in the surface or interlayer area of CMZF without destroy the

441 sheet structure. The mapping images of all metals, Cd and As are uniform

21
 ACCEPTED MANUSCRIPT

442 homodisperse on the surface of CMZF, suggesting the symmetrically multilayer

443 complexes are formed on the -OH sites.

444 From all the mechanism analysis, the removal mechanisms and interactions of

445 As(III) and Cd(II) were a series process coupled by (i) photooxidation, (ii)

PT
446 precipitation and (iii) adsorption. Particularly, for photooxidation process, As(III) will

RI
447 first be adsorbed onto the surface of CMZF, then acquired two electrons by generated

holes (h+) or ROS (1O2, O2-) under irradiation and to be oxidated into less toxic

SC
448

449 As(V), the oxidative formed As(V) will keep stay on the CMZF surface or go into the

450
U
bulk solution based on the concentration difference on the solid-liquid interface. For
AN
451 precipitation process, Cd(II) will be attracted by the negative charged CO32- anions on
M

452 the surface or in the interlayer of CMZF, then rapidly be precipitated to the CdCO3

453 crystal. The dissociative As(III) or As(V) could regulate the agglomerated bulk
D
TE

454 CdCO3 into the nano CdCO3 and fixed it in the interlayer of CMZF. And for the

455 adsorption process, As(III) or oxidative formed As(V) and residual Cd(II) will be
EP

456 specifically adsorbed by the CMZF adsorbent and coordinated by the -OH groups to
C

457 form inner-sphere complexes in a combined multilayer, where the negative charged
AC

458 As(V) will provide shielding effect to balance the electrical force among Cd(II), and

459 the coordinated deprotonated As(V) will also play a role as anion bridging to enhance

460 the attraction to Cd(II). In return, Cd(II) could enhance the As(III) adsorption by

461 formation of the ternary surface complexation or coordination and enhanced hydrogen

462 bond. All these mechanisms and synergistic effects qualified the ability of CMZF to

22
 ACCEPTED MANUSCRIPT

463 deep remove As and Cd in trace concentration level. The summary schematic diagram

464 of removal mechanism was illustrated in Fig. 7.

465

466 4. Conclusion

PT
467 A novel nanostructured CMZF adsorbent was synthesized for effective arsenite

RI
468 and cadmium deep removal. The developed material showed a significant uptake rate

SC
469 for both As(III) and Cd(II) (>99.7%) in low concentration level. The coupled process of

470 photooxidation and adsorption account for the strong removal of As(III), the fast

471
U
precipitation of CdCO3 and adsorption process is the reason for successful deep
AN
472 removal of Cd(II). The results of the kinetic and isotherm experiment indicated that the
M

473 light illumination could oxidize As(III) specie to As(V) and enhance the removal of

474 both As(III) and Cd(II) on the water/CMZF interface, where the oxidative formed As(V)
D
TE

475 could further enhance Cd(II) adsorption by anion bridging and shielding effect. In

476 return, Cd(II) strengthened the As(III) adsorption by formation of the ternary surface
EP

477 complexation or coordination and enhanced hydrogen bond. The effect of ionic
C

478 strength and Zeta potential measurements results confirmed that both As(III) and Cd(II)
AC

479 were coordinated by CMZF via forming inner-sphere complexes. This work has

480 provided a promising material for the efficient simultaneous deep elimination of

481 environmental neutral and charged inorganic pollutants in practical water treatment

482 application.

483 .

23
 ACCEPTED MANUSCRIPT

484 Acknowledgments

485 The authors appreciate financial support from the National Key Research and

486 Development Program of China (2017YFD0801000), the National Natural Science

487 Foundation of China (Grant Nos. 41673092, 41472038), the Science and Technology

PT
488 Plan of Guangdong Province, China (No. 2014A020216002, 2016B020242004),

RI
489 Guangdong special support program for millions of leading engineering talents (No.

SC
490 201626011) and the Science and Technology Program of Guangzhou, China (No.

491 201604020064).

492
U
AN
493

494 References:
M

495 Bai, Y., Shi, X., Wang, P., Wnag, L., Zhang, K., Zhou, Y., Xie, H., Wang, J., Ye, L., 2019. BiOBrxI1−
496 x/BiOBr heterostructure engineering for efficient molecular oxygen activation. CHEM ENG J 356,
D

497 34-42.
498 Bouaziz, Z., Soussan, L., Janot, J., Jaber, M., Amara, A.B.H., Balme, S., 2018. Dual role of layered
TE

499 double hydroxide nanocomposites on antibacterial activity and degradation of tetracycline and
500 oxytetracyline. CHEMOSPHERE 206, 175-183.
501 Chen, L., Zhou, S., Shi, Y., Wang, C., Li, B., Li, Y., Wu, S., 2018. Heavy metals in food crops, soil,
EP

502 andwater in the Lihe River Watershed of the Taihu Region and their potential health risks when ingested.
503 SCI TOTAL ENVIRON 615, 141-149.
504 Chen, M., Wu, P., Yu, L., Liu, S., Ruan, B., Hu, H., Zhu, N., Lin, Z., 2017. FeOOH-loaded MnO 2
C

505 nano-composite: An efficient emergency material for thallium pollution incident. J ENVIRON
506
AC

MANAGE 192, 31-38.

507 Esposito, G., Meloni, D., Abete, M.C., Colombero, G., Mantia, M., Pastorino, P., Prearo, M., Pais, A.,
508 Antuofermo, E., Squadrone, S., 2018. The bivalve Ruditapes decussatus: A biomonitor of trace elements
509 pollution in Sardinian coastal lagoons (Italy). ENVIRON POLLUT 242, 1720-1728.
510 Fan, G., Li, F., Evans, D.G., Duan, X., 2014. Catalytic applications of layered double hydroxides: recent
511 advances and perspectives. CHEM SOC REV 43, 74-766.
512 Genc-Fuhrman, H., Mikkelsen, P.S., Ledin, A., 2016. Simultaneous removal of As, Cd, Cr, Cu, Ni and Zn
513 from stormwater using high-efficiency industrial sorbents: Effect of pH, contact time and humic acid.
514 SCI TOTAL ENVIRON 566, 76-85.
515 Goldberg, S., Johnston, C.T., 2001. Mechanisms of arsenic adsorption on amorphous oxides evaluated

24
 ACCEPTED MANUSCRIPT
516 using macroscopic measurements, vibrational spectroscopy, and surface complexation modeling. J
517 COLLOID INTERF SCI 234, 204-216.
518 González, M.A., Pavlovic, I., Barriga, C., 2015. Cu(II), Pb(II) and Cd(II) sorption on different layered
519 double hydroxides. A kinetic and thermodynamic study and competing factors. CHEM ENG J 269,
520 221-228.
521 Huang, J., Li, H., Zeng, G., Shi, L., Gu, Y., Shi, Y., Tang, B., Li, X., 2018. Removal of Cd(II) by
522 MEUF-FF with anionic-nonionic mixture at low concentration. SEP PURIF TECHNOL 207, 199-205.
523 Irani, M., Ismail, H., Ahmad, Z., Fan, M., 2015. Synthesis of linear low-density polyethylene-g-poly

PT
524 (acrylic acid)-co-starch/organo-montmorillonite hydrogel composite as an adsorbent for removal of
525 Pb(II) from aqueous solutions. J ENVIRON SCI-CHINA 27, 9-20.

RI
526 Kang, D., Yu, X., Tong, S., Ge, M., Zuo, J., Cao, C., Song, W., 2013. Performance and mechanism of
527 Mg/Fe layered double hydroxides for fluoride and arsenate removal from aqueous solution. CHEM ENG
528 J 228, 731-740.

SC
529 Kim, J., Kim, J., 2014. Arsenite Oxidation-Enhanced Photocatalytic Degradation of Phenolic Pollutants
530 on Platinized TiO2. ENVIRON SCI TECHNOL 48, 13384-13391.
531 Lee, S., Tanaka, M., Takahashi, Y., Kim, K., 2018. Enhanced adsorption of arsenate and antimonate by

U
532 calcined Mg/Al layered double hydroxide: Investigation of comparative adsorption Check for
533 mechanism by surface characterization. CHEMOSPHERE 211, 903-911.
AN
534 Li, D., Duan, X., Sun, H., Kang, J., Zhang, H., Tade, M.O., Wang, S., 2017. Facile synthesis of
535 nitrogen-doped graphene via low-temperature pyrolysis: The effects of precursors and annealing
536 ambience on metal-free catalytic oxidation. CARBON 115, 649-658.
M

537 Li, X., Li, Z., Lin, C., Bi, X., Liu, J., Feng, X., Zhang, H., Chen, J., Wu, T., 2018. Health risks of heavy
538 metal exposure through vegetable consumption near a large-scale Pb/Zn smelter in central China.
D

539 ECOTOX ENVIRON SAFE 161, 99-110.

540 Li, Z., Deng, S., Yu, G., Huang, J., Lim, V.C., 2010. As(V) and As(III) removal from water by a Ce-Ti
TE

541 oxide adsorbent: Behavior and mechanism. CHEM ENG J 161, 106-113.
542 Li, Z., Wang, L., Meng, J., Liu, X., Xu, J., Wang, F., Brookes, P., 2018. Zeolite-supported nanoscale
543 zero-valent iron: New findings on simultaneous adsorption of Cd(II), Pb(II), and As(III) in aqueous
EP

544 solution and soil. J HAZARD MATER 344, 1-11.

545 Lin, L., Liu, J., Lv, J., Shen, S., Wu, X., Wu, D., Qu, Y., Zheng, W., Lai, F., 2017. Correlation between
546 native defects and morphological, structural and optical properties of ZnO nanostructures. J ALLOY
C

547 COMPD 695, 1523-1527.

548
AC

Liu, X., Liu, W., Rong, W., Li, J., Lin, Z., 2018. Surface defects enhance the adsorption affinityband
549 selectivity of Mg(OH)2 towards As(V) and Cr(VI) oxyanions: a combined theoretical and experimental
550 study. Environmental Science Nano 5, 2570-2578.
551 Lofrano, G., Carotenuto, M., Libralato, G., Domingos, R.F., Markus, A., Dini, L., Gautam, R.K.,
552 Baldantoni, D., Rossi, M., Sharma, S.K., Chattopadhyaya, M.C., Giugni, M., Meric, S., 2016. Polymer
553 functionalized nanocomposites for metals removal from water and wastewater: An overview. WATER
554 RES 92, 22-37.
555 López-Muñoz, M.J., Arencibia, A., Segura, Y., Raez, J.M., 2017. Removal of As(III) from aqueous
556 solutions through simultaneous photocatalytic oxidation and adsorption by TiO 2 and zero-valent iron.
557 CATAL TODAY 280, 149-154.

25
 ACCEPTED MANUSCRIPT
558 Lu, H., Zhu, Z., Zhang, H., Zhu, J., Qiu, Y., Zhu, L., Küppers, S., 2016. Fenton-Like Catalysis and
559 Oxidation/Adsorption Performances of Acetaminophen and Arsenic Pollutants in Water on a Multimetal
560 Cu Zn Fe-LDH. ACS APPL MATER INTER 8, 25343-25352.
561 M., S., T. C., S.G., 2017. Enhanced nonlinear optical absorption and optical limiting properties of
562 superparamagnetic spinel zinc ferrite decorated reduced graphene oxide nanostructures. APPL SURF
563 SCI 392, 904-911.
564 McBride, M.B., 1997. A critique of diffuse double layer models applied to colloid and surface chemistry.
565 CLAY CLAY MINER 45, 598-608.

PT
566 Mueller, K., Ciminelli, V.S.T., Dantas, M.S.S., Willscher, S., 2010. A comparative study of As(III) and
567 As(V) in aqueous solutions and adsorbed on iron oxy-hydroxides by Raman spectroscopy. WATER RES

RI
568 44, 5660-5672.
569 Parida, K.M., Mohapatra, L., 2012. Carbonate intercalated Zn/Fe layered double hydroxide: A novel
570 photocatalyst for the enhanced photo degradation of azo dyes. CHEM ENG J 179, 131-139.

SC
571 Pawar, R.R., Lalhmunsiama, Kim, M., Kim, J., Hong, S., Sawant, S.Y., Lee, S.M., 2018. Efficient
572 removal of hazardous lead, cadmium, and arsenic from aqueous environment by iron oxide modified
573 clay-activated carbon composite beads. APPL CLAY SCI 162, 339-350.

U
574 Rahman, M.T., Kameda, T., Kumagai, S., Yoshioka, T., 2018. A novel method to delaminate
575 nitrate-intercalated Mg-Al layered double hydroxides in water and application in heavy metals removal
AN
576 from waste water. CHEMOSPHERE 203, 281-290.
577 Rehman, S., Adil, A., Shaikh, A.J., Shah, J.A., Arshad, M., Ali, M.A., Bilal, M., 2018. Role of sorption
578 energy and chemisorption in batch methylene blue and Cu2+ adsorption by novel thuja cone carbon in
M

579 binary component system: linear and nonlinear modeling. ENVIRON SCI POLLUT R 25, 31579-31592.
580 Ren, X., Wu, Q., Xu, H., Shao, D., Tan, X., Shi, W., Chen, C., Li, J., Chai, Z., Hayat, T., Wang, X., 2016.
D

581 New Insight into GO, Cadmium(II), Phosphate Interaction and Its Role in GO Colloidal Behavior.
582 ENVIRON SCI TECHNOL 50, 9361-9369.
TE

583 Singh, B., Fang, Y., Cowie, B.C.C., Thomsen, L., 2014. NEXAFS and XPS characterisation of carbon
584 functional groups of fresh and aged biochars. ORG GEOCHEM 77, 1-10.
585 Sun, T., Zhao, Z., Liang, Z., Liu, J., Shi, W., Cui, F., 2017. Efficient removal of arsenite through
EP

586 photocatalytic oxidation and adsorption by ZrO 2 -Fe 3 O 4 magnetic nanoparticles. APPL SURF SCI
587 416, 656-665.
588 Sun, T., Zhao, Z., Liang, Z., Liu, J., Shi, W., Cui, F., 2018. Efficient degradation of p-arsanilic acid with
C

589 arsenic adsorption by magnetic CuO-Fe3O4 nanoparticles under visible light irradiation. CHEM ENG J
590
AC

334, 1527-1536.
591 Türk, T., Alp, İ., Deveci, H., 2009. Adsorption of As(V) from water using Mg Fe-based hydrotalcite
592 (FeHT). J HAZARD MATER 171, 665-670.
593 Vaiano, V., Iervolino, G., Rizzo, L., 2018. Cu-doped ZnO as efficient photocatalyst for the oxidation of
594 arsenite to arsenate under visible light. Applied Catalysis B: Environmental 238, 471-479.
595 Vaiano, V., Iervolino, G., Sannino, D., Rizzo, L., Sarno, G., Farina, A., 2014. Enhanced photocatalytic
596 oxidation of arsenite to arsenate in water solutions by a new catalyst based on MoOx supported on TiO2.
597 Applied Catalysis B: Environmental 160-161, 247-253.
598 Wang, D., Wu, J., Bai, D., Wang, R., Yao, F., Xu, S., 2017. Mesoporous spinel ferrite composite derived
599 from a ternary MgZnFe-layered double hydroxide precursor for lithium storage. J ALLOY COMPD 726,

26
 ACCEPTED MANUSCRIPT
600 306-314.
601 Wang, Q., O Hare, D., 2012. Recent Advances in the Synthesis and Application of Layered Double
602 Hydroxide (LDH) Nanosheets. CHEM REV 112, 4124-4155.
603 Wasana, H.M.S., Perera, G.D.R.K., Gunawardena, P.D.S., Fernando, P.S., Bandara, J., 2017. WHO water
604 quality standards Vs Synergic effect(s) of fluoride, heavy metals and hardness in drinking water on
605 kidney tissues. SCI REP-UK 7.
606 Wu, J., Huang, D., Liu, X., Meng, J., Tang, C., Xu, J., 2018. Remediation of As(III) and Cd(II)
607 co-contamination and its mechanism in aqueous systems by a novel calcium-based magnetic biochar. J

PT
608 HAZARD MATER 348, 10-19.
609 Xie, L., Liu, P., Zheng, Z., Weng, S., Huang, J., 2016. Morphology engineering of V 2 O 5 /TiO 2

RI
610 nanocomposites with enhanced visible light-driven photofunctions for arsenic removal. Applied
611 Catalysis B: Environmental 184, 347-354.
612 Yan, H., Chen, Q., Liu, J., Feng, Y., Shih, K., 2018. Phosphorus recovery through adsorption by layered

SC
613 double hydroxide nano-composites and transfer into a struvite-like fertilizer. WATER RES 145, 721-730.
614 Yan, L., Huang, Y., Cui, J., Jing, C., 2015. Simultaneous As(III) and Cd removal from copper smelting
615 wastewater using granular TiO2 columns. WATER RES 68, 572-579.

U
616 Yang, S., Wu, P., Ye, Q., Li, W., Chen, M., Zhu, N., 2018. Efficient catalytic degradation of bisphenol A
617 by novel Fe0- vermiculite composite in photo-Fenton system: Mechanism and effect of iron oxide shell.
AN
618 CHEMOSPHERE 208, 335-342.
619 Yoon, K., Cho, D., Tsang, D.C.W., Bolan, N., Rinklebe, J., Song, H., 2017. Fabrication of engineered
620 biochar from paper mill sludge and its application into removal of arsenic and cadmium in acidic water.
M

621 BIORESOURCE TECHNOL 246, 69-75.

622 Yu, H., Ding, X., Li, F., Wang, X., Zhang, S., Yi, J., Liu, C., Xu, X., Wang, Q., 2016. The availabilities of
D

623 arsenic and cadmium in rice paddy fields from a mining area: The role of soil extractable and plant
624 silicon. ENVIRON POLLUT 215, 258-265.
TE

625 Zhang, G., Liu, F., Liu, H., Qu, J., Liu, R., 2014. Respective Role of Fe and Mn Oxide Contents for
626 Arsenic Sorption in Iron and Manganese Binary Oxide: An X-ray Absorption Spectroscopy Investigation.
627 ENVIRON SCI TECHNOL 48, 10316-10322.
EP

628 Zhang, W., Zhang, G., Liu, C., Li, J., Zheng, T., Ma, J., Wang, L., Jiang, J., Zhai, X., 2018a. Enhanced
629 removal of arsenite and arsenate by a multifunctional Fe-Ti-Mn composite oxide: Photooxidation,
630 oxidation and adsorption. WATER RES 147, 264-275.
C

631 Zhang, W., Zhang, G., Liu, C., Li, J., Zheng, T., Ma, J., Wang, L., Jiang, J., Zhai, X., 2018b. Enhanced
632
AC

removal of arsenite and arsenate by a multifunctional Fe-Ti-Mn composite oxide: Photooxidation,

633 oxidation and adsorption. WATER RES 147, 264-275.
634 Zhang, Y., Yang, M., Dou, X.M., He, H., Wang, D.S., 2005. Arsenate adsorption on an Fe-Ce bimetal
635 oxide adsorbent: Role of surface properties. ENVIRON SCI TECHNOL 39, 7246-7253.
636 Zhang, Y., Zhou, J., Feng, Q., Chen, X., Hu, Z., 2018. Visible light photocatalytic degradation of MB
637 using UiO-66/g-C3N4 heterojunction nanocatalyst. CHEMOSPHERE 212, 523-532.
638 Zhu, C., Liu, F., Xu, C., Gao, J., Chen, D., Li, A., 2015. Enhanced removal of Cu(II) and Ni(II) from
639 saline solution by novel dual-primary-amine chelating resin based on anion-synergism. J HAZARD
640 MATER 287, 234-242.
641 Zhu, C., Liu, F., Zhang, Y., Wei, M., Zhang, X., Ling, C., Li, A., 2016. Nitrogen-doped chitosan-Fe(III)

27
 ACCEPTED MANUSCRIPT
642 composite as a dual-functional material for synergistically enhanced co-removal of Cu(II) and Cr(VI)
643 based on adsorption and redox. CHEM ENG J 306, 579-587.
644 Zhu, J., Zhu, Z., Zhang, H., Lu, H., Zhang, W., Qiu, Y., Zhu, L., Küppers, S., 2018. Calcined layered
645 double hydroxides/reduced graphene oxide composites with improved photocatalytic degradation of
646 paracetamol and efficient oxidation-adsorption of As(III). Applied Catalysis B: Environmental 225,
647 550-562.
648
649

PT
RI
U SC
AN
M
D
TE
C EP
AC

28
 ACCEPTED MANUSCRIPT

Figures

Fig. 1 SEM images of (a) MZF LDH, (b) CMZF; TEM images (c) MZF LDH (d) CMZF and

Element mapping images (e, f) of MZF LDH

Fig. 2 Effects of pH and irradiation on CMZF adsorbent (Conditions: As(III) 1mg/L, Cd(II) 1mg/L,

PT
CMZF 0.5 g/L and Temperature 30±1 ℃).

RI
Fig. 3 Effect of reaction time and kinetic study of As and Cd on CMZF adsorbent (Conditions:

As(III) 1mg/L, As( )1mg/L Cd(II) 1mg/L, CMZF 0.5 g/L CMZF, Temperature 30±1 ℃and pH

SC
= 6).

U
Fig. 4 Effect of initial concentration and isotherm study of As and Cd on CMZF adsorbent
AN
(Conditions: As(III) and As( ) 1-100mg/L, Cd(II) 1-260mg/L, CMZF 0.5 g/L, reaction time 12h,

Temperature 30±1 ℃ and pH = 6).

M

Fig. 5 XPS spectra of (a) As 3d, (b) C 1s, (c) Fe 2p and (d) O 1s on the CMZF adsorbent surface
D

before and after adsorption.

TE

Fig. 6 XRD and Element mapping images of CMZF after the adsorption of (a)As, (b) Cd and (c)

As and Cd.
EP

Fig. 7 Schematic diagram of the arsenic and cadmium removal mechanism by CMZF adsorbent.
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
Fig. 1 SEM images of (a) MZF LDH, (b) CMZF; TEM images (c) MZF LDH (d) CMZF and
AN
Element mapping images (e, f) of MZF LDH.
M
D
TE
C EP
AC

Fig. 2 Effects of pH and irradiation on CMZF adsorbent (Conditions: As(III) 1mg/L, Cd(II) 1mg/L,

CMZF 0.5 g/L, reaction time 6h and Temperature 30±1 ℃).

 ACCEPTED MANUSCRIPT

50

a 1000
b 1000 45

40
in th e light
in th e dark
1000

A s(? ) concentra tion (ug/L)

35

As(III) in the dark 30

25
As(V) in the dark

As(? ) concentration (ug/L)

20

As concentration (ug/L)
As Concentration (ug/L)

15

10

100 100 5
100
0
0 20 40 60 80 10 0 1 20
Ti me (m in)

As(III) in the dark

PT
As(III) in the light
10 10 As(V) in the dark 10
As(V) in the light

RI
1 1 1
0 30 60 90 120 150 180 0 30 60 90 120 150 180

Time (min) Time (min)

c 1000
As(III) single in the dark
As(III) single in the light
d 1000
Cd(II) single

SC
Cd(II) with As(III) in the dark
As(III) with Cd(II) in the light
Cd(II) with As(III) in the light
As(III) with Cd(II) in the dark
As Concentration (ug/L)

Cd Concentration (ug/L)

100 100

U
10 10
AN
1 1
0 20 40 60 80 100 120 140 160 180 0 30 60 90 120 150 180
Time (min) Time (min)
M

Fig. 3 Effect of reaction time and kinetic study of As and Cd on CMZF adsorbent (Conditions:
D

As(III) 1mg/L, As( )1mg/L, Cd(II) 1mg/L, CMZF 0.5 g/L, Temperature 30±1 ℃and pH = 6).
TE
C EP
AC
 ACCEPTED MANUSCRIPT

100

a As(III)
b 80 As(V)

80

60

60
Qe (mg/g)

Qe (mg/g)
40
40

As(III) single As(V) single

As(III) with Cd(II) 20 As(V) with Cd(II)
20 Langmuir Langmuir
Freundlich Freundlich

PT
0 0
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80
Ce (mg/g) Ce (mg/g)
250

RI
250

c 200
d
200

SC
150
150
Qe (mg/g)

Qe (mg/g)
100 100 Cd(II) single
Cd(II) single
Cd(II) with As(III) Cd(II) with As(V)
Langmuir Langmuir

U
50 50
Freundlich Freundlich

0 0
AN
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160
Ce (mg/g) Ce (mg/g)

Fig. 4 Effect of initial concentration and isotherm study of As and Cd on CMZF adsorbent
M

(Conditions: As(III) and As( ) 1-100mg/L, Cd(II) 1-260mg/L, CMZF 0.5 g/L, reaction time 12h,
D

Temperature 30±1 ℃ and pH = 6).

TE
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
Fig. 5 XPS spectra of (a) O 1s, (b) C 1s, (c) Fe 2p and (d) As 3d on the CMZF adsorbent surface
M

before and after adsorption.

D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D

Fig. 6 XRD and Element mapping images of CMZF after the adsorption of (a)As, (b) Cd, (c) As
TE

and Cd.
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
Fig. 7 Schematic diagram of the arsenite and cadmium removal mechanism by CMZF adsorbent.
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Highlights

Multiple functions of photooxidation, precipitation and adsorption were

integrated into CMZF nanoparticle.

CMZF exhibits excellent synchronous removal ability towards trace

PT
concentration As(III) and Cd(II).

RI

The synergistic interaction among As(III) molecule, As (V) anion and Cd(II)

cation in removal process was proposed.

SC

As(III) and Cd(II) in actual water were removed simultaneously and efficiently to

U
satisfy drinking water provision.
AN
M
D
TE
C EP
AC