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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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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
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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
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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
42
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
51
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
55
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
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a new nanocomposite with high efficiency, low cost, and simple procedure to 3
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efficiently immobilize heavy metal ions in manure.
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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,
61
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
65
ratio (WNa2CO3:WBioSi:WAttp =3:1:2) to obtain an acid soil remediation agent.19-22 The
66
acid soil remediation agent possessed a porous nano-networks structure and a high
67
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
69
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
71
and Cu ions was investigated. This work provides a promising approach to control the
72
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
77
particle size of 10 µm was purchased from Kaidi Electric Power Co., Ltd. (Wuhan,
78
China). manure powder (50-100 mesh, N-P2O5-K2O≥5%, organic matter≥45%) made
79
from livestock manure without heavy metal ions was provided by Shanghai Original
80
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)
86
powders were mixed with 5 mL of deionized water evenly. After that, the mixture was
87
dried at 50oC for 24 h and then ground to obtain Na2CO3/BioSi/Attp powders.
88
Preparation of Na2CO3/BioSi/Attp/Man/AsCu. Ca3(AsO4)2 powder (40 mg)
89
and CuSO4·5H2O powder (585 mg) were mixed evenly with 5 g of manure powder to
90
obtain Man/AsCu. Then Na2CO3/BioSi/Attp with a given amount was mixed evenly
91
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
94
Na2CO3/BioSi/Attp/Man/AsCu granules with diameter of 2-3 mm.
95
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
100
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
104
shape, height of 6.5 cm, width of 7.8 cm (bottom) and 11.3 cm (top), and length of
105
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
112
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
114
one by one, and the resulting system was shaken for 24 h. After centrifuging (4500
115
rpm) for 5 minutes, the concentration of Na+ in the supernatant was measured to
116
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
120
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
123
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.
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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
138
of As, Cu and Na ions were measured by an inductively coupled plasma-optical
139
emission spectrometer ((ICP-AES) (ICAP7200, Thermo Fisher Scientific, USA)).
140
Statistical Analyses. The data are presented as the mean ± standard error of the
141
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
143
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).
197
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
201
those in the stems and leaves, indicating that As and Cu elements tended to
202
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
204
Cu
205
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,
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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
210
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.
212
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
215
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
219
increase of distance away from Na2CO3/BioSi/Attp, the concentration of -CO32- in soil
220
decreases, resulting in the decreased pH of soil. This result indicated that, under the
221
condition
222
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
229
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
240
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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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
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technology
to
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inorganic
nanorods
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Figure captions:
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Figure 1. Influence of Na2CO3/BioSi/Attp amount on the release of (A) As and (B) Cu
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ions from Na2CO3/BioSi/Attp/Man/AsCu (Man/AsCu=5 g) granules in aqueous
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solution; (C) Effect of Na2CO3/BioSi/Attp amount on the pH of aqueous solution.
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Error bars indicate standard deviation (n=3). Statistical analysis of the data was
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performed using one-way ANOVA with significant differences as (***) p< 0.001, (**)
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p< 0.01, and (*) p< 0.05.
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Figure 2. (A) and (B) Digital photographs of rices; (C) pH of soil treated with
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different samples; (D-F) yellow leaf ratio, height, and root length of rices treated with
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different samples; total amounts of (G) As and (H) Cu elements in stems and leaves;
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total amounts of (I) As and (J) Cu elements in rice roots. (a) Acid soil, (b) acid soil +
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Man/AsCu
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(WNa2CO3/BioSi/Attp:WMan/AsCu=0.4
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Na2CO3/BioSi/Attp/Man/AsCu (WNa2CO3/BioSi/Attp:WMan/AsCu=0.6 g:10 g), and (e) acid
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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
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optimal Na2CO3/BioSi/Attp/Man/AsCu on acid sand in (A) lateral and (C) vertical
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directions; effect of optimal Na2CO3/BioSi/Attp/Man/AsCu on the pH of acid sand in
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(B) lateral and (D) vertical directions. Error bars indicate standard deviation (n=3).
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Figure 4. SEM images of (A) Attp, (B) and (b) Attp/Na2CO3 (WAttp:WNa2CO3=2:3), (C)
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Attp/BioSi (WAttp:WBioSi=2:1), (D) Na2CO3/BioSi/Attp, (E) Man/AsCu, and (F)
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optimal Na2CO3/BioSi/Attp/Man/AsCu. (I-IV) Arrows note Attp, Na2CO3, BioSi, and
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Man.
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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)
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(B), and optimal Na2CO3/BioSi/Attp/Man/AsCu (C); XRD patterns (D) and FTIR
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spectra (E) with different samples: (a) Na2CO3/BioSi/Attp, (b) Man/AsCu, (c) optimal
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Na2CO3/BioSi/Attp/Man/AsCu.
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Figure
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Na2CO3/BioSi/Attp/Man/AsCu and the practical application in a field.
6.
Schematic
illustrations
of
the
fabrication
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of
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