Immobilizing Arsenic and Copper Ions in Manure Using a

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Immobilizing arsenic and copper ions in manure using a nanocomposite Dongfang Wang, Guilong Zhang, Linglin Zhou, Dongqing Cai, and Zhengyan Wu J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b02370 • Publication Date (Web): 12 Sep 2017 Downloaded from http://pubs.acs.org on September 18, 2017

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Journal of Agricultural and Food Chemistry

1

Immobilizing arsenic and copper ions in manure using a

2

nanocomposite

3

Dongfang Wang,†,§ Guilong Zhang,†,‡ Linglin Zhou,†,§ Dongqing Cai,†,‡,* Zhengyan

4

Wu†,‡,*

5

†

6

Hefei Institutes of Physical Science, Chinese Academy of Sciences, 350 Shushanhu

7

Road, Hefei, Anhui 230031, People’s Republic of China

8

§

9

230026, People’s Republic of China

Key Laboratory of High Magnetic Field and Ion Beam Physical Biology,

University of Science and Technology of China, No. 96 Jinzhai Road, Hefei, Anhui

10

‡

11

Anhui Province, Hefei Institutes of Physical Science, Chinese Academy of Sciences,

12

350 Shushanhu Road, Hefei, Anhui 230031, People’s Republic of China

13

*D.C. Email: [email protected].

14

*Z.W. Email: [email protected].

Key Laboratory of Environmental Toxicology and Pollution Control Technology of

15

1

ACS Paragon Plus Environment


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ABSTRACT: Livestock manures (Man) commonly contains a certain quantity of

17

heavy metal ions such as arsenic (As) and copper (Cu) ions, resulting in a high risk on

18

soil contamination. To solve this problem, heavy metal of manure was immobilized

19

into Sodium carbonate/Biosilica/Attapulgite composite (Na2CO3/BioSi/Attp) which

20

was developed using a nanocomposite consisting of anhydrous sodium carbonate

21

(Na2CO3), straw ash-based biochar and biosilica (BioSi), and attapulgite (Attp). When

22

Na2CO3/BioSi/Attp was mixed with Man/AsCu, the obtained nanocomposite

23

(Na2CO3/BioSi/Attp/Man/AsCu) with a porous nano-networks structure could

24

effectively control the release of As and Cu ions from manure through adsorption and

25

chemical

26

Na2CO3/BioSi/Attp/Man/AsCu could increase the pH value of acid soil, promote the

27

growth of rices, and significantly decrease the uptake of As and Cu ions by rices.

28

Therefore, this work provides a promising approach to immobilize heavy metal ions

29

in manure and thus lower the contamination risk to environment. Na2CO3, BioSi, and

30

Attp powders were mixed evenly with weight ratio of WNa2CO3:WBioSi:WAttp =3:1:2.

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KEYWORDS: manure, nanocomposite, immobilizing, arsenic, copper

reaction.

Meanwhile,

pot

experiment

32

2


indicated

that

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INTRODUCTION

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To increase feed intake and promote the growth of livestock, heavy metal ions such as

35

arsenic (As) and copper (Cu) ions and so on have been widely used as additives for

36

feed.1-5 However, a small portion of the intake heavy metal ions are absorbed by

37

livestock and most of the heavy metal ions are excreted in form of manure (Man).6,7

38

Therein, plenty of the manures are used as the raw materials to produce organic

39

fertilizer through composting.8,9 When applied in soil, the heavy metal containing

40

organic fertilizer can introduce some heavy metal ions to soil, resulting in soil

41

contamination in different degrees. Subsequently, the heavy metal ions tend to be

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absorbed by crops and then human beings, causing a series of diseases.10-12 Therefore,

43

it is rather important to immobilize the heavy metal ions in manure to lower the

44

harmful effects on environment and human beings.

45

Until now, several materials such as zeolite, lime, bentonite and so on have been

46

used to immobilize heavy metal ions in manure mainly through adsorption and

47

chemical reaction.13-17 Therein, the zeolite was commonly used to remove heavy

48

metal ions from manure through adsorption and separation effects during the

49

composting process, nevertheless this method was difficult to be applied because of

50

its disadvantages of labor-consuming, time-costing, and high cost.13,14 The lime was

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mainly used to decrease the solubility of some heavy metal ions through chemical

52

reaction, however this approach was only suitable for a few types of heavy metal ions,

53

which greatly hindered its application.15,16 Bentonite possessed a high adsorption

54

efficiency on hydrophilic compounds such as urea, cations such as Cu2+, Cd2+ and so

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on because of the negative zeta potential of bentonite, while a relatively low

56

adsorption efficiency on heavy metal anions.17,18 Therefore, it is necessary to fabricate

57

a new nanocomposite with high efficiency, low cost, and simple procedure to 3



58

efficiently immobilize heavy metal ions in manure.

59

Acid soil, a typical low-quality soil all over the world, has negative effects on the

60

growth of crops and can enhance the activity of heavy metal ions.19 Therefore,

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remediation of acid soil is rather important to decrease the harmful effects of heavy

62

metal ions. In our previous work, attapulgite (Mg,Al)4(Si)8(O,OH,H2O)26·nH2O)

63

(Attp), a kind of rod-shaped nanoclay, was combined with straw ash-based biochar

64

and biosilica (BioSi) and anhydrous sodium carbonate (Na2CO3) with a certain weight

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ratio (WNa2CO3:WBioSi:WAttp =3:1:2) to obtain an acid soil remediation agent.19-22 The

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acid soil remediation agent possessed a porous nano-networks structure and a high

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ability on controlling the migration of hexavalent chromium in soil.19 Herein, acid soil

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remediation agent, with advantages of low cost and simple preparation procedure, was

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attempted to be used as an immobilizing agent (Na2CO3/BioSi/Attp) for heavy metal

70

ions in manure, and the effect of Na2CO3/BioSi/Attp on the migration behavior of As

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and Cu ions was investigated. This work provides a promising approach to control the

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migration of heavy metal in manure and decrease the contamination risk to

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environment.

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MATERIALS AND METHODS

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Materials. ATP powder (100-200 mesh) was purchased from Mingmei Co., Ltd.

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(Anhui, China). BioSi (approximately 35% SiO2 and 60% carbon) with an average

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particle size of 10 µm was purchased from Kaidi Electric Power Co., Ltd. (Wuhan,

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China). manure powder (50-100 mesh, N-P2O5-K2O≥5%, organic matter≥45%) made

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from livestock manure without heavy metal ions was provided by Shanghai Original

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Biotechnology Co., Ltd. (Shanghai, China). Other chemicals of analytical reagent

81

grade were provided by Sinopharm Chemical Reagent Company (Shanghai, China).

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Deionized water was used in all the experiments except the pot experiments. Rice 4


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seeds were purchased from Happy Agriculture Co., Ltd. (Jiangsu, China). Soil used in

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the pot experiments was taken from Dongpu Island (Hefei, China).

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Na2CO3/BioSi/Attp Preparation. Na2CO3 (3 g), BioSi (1 g), and Attp (2 g)

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powders were mixed with 5 mL of deionized water evenly. After that, the mixture was

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dried at 50oC for 24 h and then ground to obtain Na2CO3/BioSi/Attp powders.

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Preparation of Na2CO3/BioSi/Attp/Man/AsCu. Ca3(AsO4)2 powder (40 mg)

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and CuSO4·5H2O powder (585 mg) were mixed evenly with 5 g of manure powder to

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obtain Man/AsCu. Then Na2CO3/BioSi/Attp with a given amount was mixed evenly

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with 5 g of Man/AsCu to obtain Na2CO3/BioSi/Attp/Man/AsCu. Finally,

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Na2CO3/BioSi/Attp/Man/AsCu powder was granulated by a BY400 pelletizer

93

(Taizhou Changjiang Medicine Machinary Limited Co., Jiangsu, China) to obtain

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Na2CO3/BioSi/Attp/Man/AsCu granules with diameter of 2-3 mm.

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Effect of Na2CO3/BioSi/Attp on the Release of As and Cu Ions. The

96

Na2CO3/BioSi/Attp/Man/AsCu

(the

optimal

one

was

optimal

97

Na2CO3/BioSi/Attp/Man/AsCu) granules with a given amount was put in 25 mL of

98

deionized water and the resulting system was shaken for 24 h, then the concentrations

99

of As and Cu ions in the supernatant were measured after centrifuging (4500 rpm) for

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5 minutes. Herein, the optimal Na2CO3/BioSi/Attp/Man/AsCu with a weight ratio of

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WNa2CO3/BioSi/Attp:WMan/AsCu =0.3 g:5 g was obtained and designated as optimal

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Na2CO3/BioSi/Attp/Man/AsCu. All experiments were performed in triplicate.

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Pot Experiments. 340 g of acid soil (pH=4.75) was put in a pot (trapezoidal

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shape, height of 6.5 cm, width of 7.8 cm (bottom) and 11.3 cm (top), and length of

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13.4 cm (bottom) and 17.2 cm (top)) and then Na2CO3/BioSi/Attp/Man/AsCu

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granules with different weight ratios (WNa2CO3/BioSi/Attp:WMan/AsCu =0 g:10 g, 0.4 g:10 g,

107

0.6 g:10 g, and 0.8 g:10 g) were spread on the surface of the acid soil. After that, 60 g 5



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of acid soil was placed on the top of Na2CO3/BioSi/Attp/Man/AsCu and then forty

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rice seeds were planted in the acid soil (top layer). Finally, the system was placed in a

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greenhouse at 20oC, and 50 mL of water was sprayed evenly to the system every day.

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All experiments were performed in triplicate. Besides, seven such pots were prepared

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to investigate the release of Na+ from Na2CO3/BioSi/Attp in soil. From the 1st to 7th

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day, 5 g of acid sand on the top of a pot was transferred to 25 mL of deionized water

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one by one, and the resulting system was shaken for 24 h. After centrifuging (4500

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rpm) for 5 minutes, the concentration of Na+ in the supernatant was measured to

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obtain the release amount of Na+ from Na2CO3/BioSi/Attp in soil.

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Effect of Optimal Na2CO3/BioSi/Attp/Man/AsCu on the pH of Acid Sand.

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HCl (80 mL, 0.03 mol/L) was added to 200 g of dry sand (50-100 mesh), and the

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resulting sand was dried at 50oC overnight to obtain acid sand. Then a certain amount

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of acid sand was put in polyvinyl chloride tubes in lateral and vertical directions

121

respectively, and optimal Na2CO3/BioSi/Attp/Man/AsCu granules with a given

122

amount was placed as a layer on the left (lateral column) or top (vertical column) of

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the sand column. Then a filter paper was placed on the left (lateral column) or top

124

(vertical column) of the sand column. A certain amount of deionized water was added

125

to the left (lateral column) or top (vertical column) of the filter paper. After 24 h, 5 g

126

of

127

Na2CO3/BioSi/Attp/Man/AsCu layer was transferred to 25 mL of deionized water

128

respectively, and the resulting system was shaken for 24 h. After centrifuging (4500

129

rpm) for 5 minutes, the pH of the supernatant was measured to obtain the effect of

130

optimal Na2CO3/BioSi/Attp/Man/AsCu on the pH of acid sand. All experiments were

131

performed in triplicate.

132

acid

sand

in

different

distance

(every

3

cm)

from

the

optimal

Characterizations. The morphology was measured using a scanning electron 6


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microscope (SEM) (Sirion 200, FEI Co., USA). The structure and compositions

134

analyses were conducted on a TTR-III X-ray diffractometer (XRD) (Rigaku Co.,

135

Japan) and a Fourier transform infrared (FTIR) spectrometer (iS10, Nicolet Co., USA).

136

The thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) were

137

carried out by a thermogravimetric analyzer (Q5000IR, TA Co., USA). The contents

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of As, Cu and Na ions were measured by an inductively coupled plasma-optical

139

emission spectrometer ((ICP-AES) (ICAP7200, Thermo Fisher Scientific, USA)).

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Statistical Analyses. The data are presented as the mean ± standard error of the

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mean. Yellow leaf ratio, height, and root length of rices, the concentrations of As, Cu

142

and Na, and pH value were analyzed under different treatments. Statistical analyses of

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the As and Cu release in aqueous solution, and pH value of aqueous solution were

144

performed using one-way ANOVA with signiﬁcant differences at p 0.3 g) with the increase of Na2CO3/BioSi/Attp amount

194

(Figure 2G and I). As for Cu, Na2CO3/BioSi/Attp/Man/AsCu could efficiently

195

decrease the amounts of Cu element in these three parts of rices, and the amounts

196

decreased with the increase of Na2CO3/BioSi/Attp amount (Figure 2H and J).

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Noteworthily, the As and Cu amounts in rices displayed the similar trends to their

198

release behaviors in aqueous solution respectively (Figure 1A and B), indicating that

199

the release of As and Cu ions had a significant influence on their uptake by rices.

200

Interestingly, the As and Cu amounts in rice roots were greatly higher compared with

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those in the stems and leaves, indicating that As and Cu elements tended to

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accumulate in rice roots other than stems and leaves. The pot experiment

203

demonstrated that Na2CO3/BioSi/Attp could effectively decrease the uptake of As and

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Cu

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Na2CO3/BioSi/Attp/Man/AsCu was also obtained at WNa2CO3/BioSi/Attp:WMan/AsCu of 0.3

206

g:5 g. Besides, the release of Na+ from Na2CO3/BioSi/Attp in soil with time was

207

investigated. As shown in Figure S1, the release amount of Na+ in soil was

ions

by

rices

through

immobilization

effect,

9


and

the

optimal


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approximately 3.4 ppm, which was similar to that of soil background (3.13 ppm), and

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the release amount of Na+ increased rather slowly with time, proving the relatively

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high stability of Na+ in Na2CO3/BioSi/Attp.

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Effect of Optimal Na2CO3/BioSi/Attp/Man/AsCu on the pH of Acid Sand.

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Additionally, the effect of optimal Na2CO3/BioSi/Attp/Man/AsCu on pH of acid sand,

213

as simulated acid soil, in both lateral (Figure 3A and B) and vertical (Figure 3C and D)

214

directions was investigated. It was found that the pH of acid sand decreased gradually

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from approximately 8.0 and 8.7 (in distance of 0 cm) to 5.9 and 5.8 (in distance of 12

216

cm) with the increasing distances from the optimal Na2CO3/BioSi/Attp/Man/AsCu

217

layer in lateral and vertical directions respectively. Na2CO3/BioSi/Attp contains

218

Na2CO3 and thus displays an alkaline property because of the reaction (2). With the

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increase of distance away from Na2CO3/BioSi/Attp, the concentration of -CO32- in soil

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decreases, resulting in the decreased pH of soil. This result indicated that, under the

221

condition

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Na2CO3/BioSi/Attp/Man/AsCu on acid sand pH in lateral (both leftwards and

223

rightwards) and vertical (downwards) directions were both approximately 12 cm.

in

work,

the

effective

distances

-CO32-+H2O=-HCO3-+-OH

224 225

this

Mechanism

of

Optimal

of

optimal

(2)

Na2CO3/BioSi/Attp/Man/AsCu

on

the

226

Immobilization of As and Cu Ions. In order to reveal the mechanism of optimal

227

Na2CO3/BioSi/Attp/Man/AsCu on the immobilization of As and Cu ions, the

228

morphology of optimal Na2CO3/BioSi/Attp/Man/AsCu system was observed. As

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shown in Figure 4A, Attp with elementary unit of nano rod can easily aggregate to

230

form plenty of bunches attributed to the nano scale effect. These Attp rods connected

231

and crosslinked with each other to obtain plenty of micro-nano pores, favoring the

232

adsorption of Na2CO3 (noted by arrow II). At the same time, the adsorbed Na2CO3 10


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could probably endow Attp a higher zeta potential (absolute value) and thus a better

234

dispersion. As a result, the isolated irregular Attp rods (noted by arrow I) could

235

crosslink with each other to form micro/nano network-structured Attp/Na2CO3 (Figure

236

4B and b). When combined with BioSi having micro pores, the Attp and Attp/Na2CO3

237

could be immobilized in the micro pores of BioSi to form Attp/BioSi (Figure 4C) and

238

Na2CO3/BioSi/Attp (Figure 4D). When added to Man/AsCu, the network-structured

239

Na2CO3/BioSi/Attp could load Man/AsCu (Figure 4E) in the micro/nano pores of

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Na2CO3/BioSi/Attp to form optimal Na2CO3/BioSi/Attp/Man/AsCu (Figure 4F),

241

which was favorable to adsorb As and Cu ions in the networks through chemical

242

reaction (1) and electrostatic attraction and control their release.

243

Additionally, TG analysis was conducted to evaluate the actual weight ratio and

244

thermal

stability

of

245

Na2CO3/BioSi/Attp/Man/AsCu. As shown in Figure 5A, the characteristic DTA peak

246

(89°C) of Na2CO3/BioSi/Attp mainly corresponded to the loss of water. As shown in

247

Figure 5B, the characteristic DTA peak (288°C) was probably attributed to the loss of

248

water and organic matter in Man/AsCu, and the peak (461°C) was corresponding to

249

the degradation of organic matter. Figure 5C illustrated that the peak (89°C) of

250

Na2CO3/BioSi/Attp and the peaks (288 and 461°C) of Man/AsCu could be found in

251

the DTA spectrum of optimal Na2CO3/BioSi/Attp/Man/AsCu, suggesting the

252

successful incorporation of Na2CO3/BioSi/Attp and Man/AsCu. Meanwhile, the

253

weight loss of optimal Na2CO3/BioSi/Attp/Man/AsCu was between those of

254

Na2CO3/BioSi/Attp

255

Na2CO3/BioSi/Attp and Man/AsCu.

and

Na2CO3/BioSi/Attp,

Man/AsCu,

further

Man/AsCu,

proving

the

and

optimal

incorporation

of

256

Besides, XRD measurement was carried out to analyze the crystal structure of

257

Na2CO3/BioSi/Attp, Man/AsCu, and optimal Na2CO3/BioSi/Attp/Man/AsCu. As 11



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shown in Figure 5D, optimal Na2CO3/BioSi/Attp/Man/AsCu and Man/AsCu

259

possessed similar XRD patterns approximately, attributing to the high content of

260

Man/AsCu in optimal Na2CO3/BioSi/Attp/Man/AsCu. Meanwhile, new characteristic

261

peaks

262

Na2CO3/BioSi/Attp/Man/AsCu, proving the successful combination of Man/AsCu

263

with

264

Na2CO3/BioSi/Attp with Man/AsCu, FTIR measurements were carried out. As shown

265

in Figure 5E, when Na2CO3/BioSi/Attp was added to Man/AsCu, the characteristic

266

peaks (3412 and 1423 cm-1) of Man/AsCu red-shifted to 3370 and 1420 cm-1, and the

267

peaks (1632 and 778 cm-1) blue-shifted to 1651 and 797 cm-1, which was probably

268

because of the existence of hydrogen bonds and electrostatic interactions between

269

Na2CO3/BioSi/Attp and Man/AsCu.

of

Na2CO3

were

Na2CO3/BioSi/Attp.19

found

To

further

in

the

spectrum

investigate

the

of

optimal

interaction

of

270

The practical application of this technology was shown in Figure 6. The optimal

271

Na2CO3/BioSi/Attp/Man/AsCu granules were spread evenly onto the surface of acid

272

soil field. Afterward, the soil was ploughed by a tractor-pulled plow to make the

273

optimal Na2CO3/BioSi/Attp/Man/AsCu locate in the soil about 20 cm deep from the

274

soil surface. As a result, the optimal Na2CO3/BioSi/Attp/Man/AsCu could promote

275

the growth of rices in acid soil and decrease the accumulation amounts of As and Cu

276

in rices. This technology could effectively decrease the pollution of Man/AsCu and

277

remediate acid soil, and has a promising application prospect.

278

In summary, this work describes a facile approach of immobilizing As and Cu

279

ions in Man/AsCu using a nanocomposite named Na2CO3/BioSi/Attp. When added to

280

Man/AsCu, Na2CO3/BioSi/Attp with a porous nano-networks structure could

281

efficiently control the release of As and Cu ions from Man/AsCu through chemical

282

reaction and adsorption. Besides, Na2CO3/BioSi/Attp could efficiently increase the pH 12


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283

value of acid soil and decrease the solubility of As ions. Na2CO3/BioSi/Attp could

284

promote the growth of rices and significantly decrease the uptake of As and Cu ions

285

by rices. Therefore, this technology could effectively reduce the negative effect of

286

Man/AsCu on environment and crops and might have a huge application prospect.

287

ASSOCIATED CONTENT

288

Supporting Information

289

The Supporting Information is available free of charge on the ACS Publications

290

website. Figure S1, amount of Na+ in soil at different time. Table S1, list of

291

vocabularies and abbreviations.

292

AUTHOR INFORMATION

293

*Corresponding Authors.

294

Tel.: +86-551-65595012; Fax: +86-551-65595012.

295

E-mail addresses: [email protected] (D.C.), [email protected] (Z.W.).

296

Funding

297

The authors acknowledge financial support from the National Natural Science

298

Foundation of China (No. 21407151), the Youth Innovation Promotion Association of

299

Chinese Academy of Sciences (No. 2015385), the Key Program of Chinese Academy

300

of Sciences (No. KSZD-EW-Z-022-05), the Science and Technology Service

301

Programs of Chinese Academy of Sciences (Nos. KFJ-STS-ZDTP-002 and

302

KFJ-SW-STS-143), and the Grant of the President Foundation of Hefei Institutes of

303

Physical Science of Chinese Academy of Sciences (No. YZJJ201502).

304

Notes

305

The authors declare no competing financial interest.

306

13



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technology

to

transform

inorganic

nanorods

382 16


into

nano-networks.

Page 17 of 25


383

Figure captions:

384

Figure 1. Influence of Na2CO3/BioSi/Attp amount on the release of (A) As and (B) Cu

385

ions from Na2CO3/BioSi/Attp/Man/AsCu (Man/AsCu=5 g) granules in aqueous

386

solution; (C) Effect of Na2CO3/BioSi/Attp amount on the pH of aqueous solution.

387

Error bars indicate standard deviation (n=3). Statistical analysis of the data was

388

performed using one-way ANOVA with significant differences as (***) p< 0.001, (**)

389

p< 0.01, and (*) p< 0.05.

390

Figure 2. (A) and (B) Digital photographs of rices; (C) pH of soil treated with

391

different samples; (D-F) yellow leaf ratio, height, and root length of rices treated with

392

different samples; total amounts of (G) As and (H) Cu elements in stems and leaves;

393

total amounts of (I) As and (J) Cu elements in rice roots. (a) Acid soil, (b) acid soil +

394

Man/AsCu

395

(WNa2CO3/BioSi/Attp:WMan/AsCu=0.4

396

Na2CO3/BioSi/Attp/Man/AsCu (WNa2CO3/BioSi/Attp:WMan/AsCu=0.6 g:10 g), and (e) acid

397

soil + Na2CO3/BioSi/Attp/Man/AsCu (WNa2CO3/BioSi/Attp:WMan/AsCu=0.8 g:10 g). Error

398

bars indicate standard deviation (n=3).

399

Figure 3. Schematic diagrams of the systems to investigate the remediation effects of

400

optimal Na2CO3/BioSi/Attp/Man/AsCu on acid sand in (A) lateral and (C) vertical

401

directions; effect of optimal Na2CO3/BioSi/Attp/Man/AsCu on the pH of acid sand in

402

(B) lateral and (D) vertical directions. Error bars indicate standard deviation (n=3).

403

Figure 4. SEM images of (A) Attp, (B) and (b) Attp/Na2CO3 (WAttp:WNa2CO3=2:3), (C)

404

Attp/BioSi (WAttp:WBioSi=2:1), (D) Na2CO3/BioSi/Attp, (E) Man/AsCu, and (F)

405

optimal Na2CO3/BioSi/Attp/Man/AsCu. (I-IV) Arrows note Attp, Na2CO3, BioSi, and

406

Man.

407

Figure 5. TGA (black) and DTA (blue) curves of Na2CO3/BioSi/Attp (A), Man/AsCu

(10

g),

(c)

acid

soil

g:10

+ g),

Na2CO3/BioSi/Attp/Man/AsCu (d)

17


acid

soil

+


Page 18 of 25

408

(B), and optimal Na2CO3/BioSi/Attp/Man/AsCu (C); XRD patterns (D) and FTIR

409

spectra (E) with different samples: (a) Na2CO3/BioSi/Attp, (b) Man/AsCu, (c) optimal

410

Na2CO3/BioSi/Attp/Man/AsCu.

411

Figure

412

Na2CO3/BioSi/Attp/Man/AsCu and the practical application in a field.

6.

Schematic

illustrations

of

the

fabrication

18


process

of

Page 19 of 25


Figures

Figure 1

19



Figure 2

20


Page 20 of 25

Page 21 of 25


Figure 3

21



Figure 4

22


Page 22 of 25

Page 23 of 25


Figure 5

23



Figure 6

24


Page 24 of 25

Page 25 of 25


TOC Graphic

25


Immobilizing Arsenic and Copper Ions in Manure Using a

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