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The influence of corncob-based biochar on remediation of arsenic

and cadmium in yellow soil and cinnamon soil

Mingke Luo, Hai Lin, Yinhai He, Ye Zhang

PII: S0048-9697(20)30524-6
DOI: https://doi.org/10.1016/j.scitotenv.2020.137014
Reference: STOTEN 137014

To appear in: Science of the Total Environment

Received date: 31 October 2019

Revised date: 17 January 2020
Accepted date: 29 January 2020

Please cite this article as: M. Luo, H. Lin, Y. He, et al., The influence of corncob-based
biochar on remediation of arsenic and cadmium in yellow soil and cinnamon soil, Science
of the Total Environment (2020), https://doi.org/10.1016/j.scitotenv.2020.137014

This is a PDF file of an article that has undergone enhancements after acceptance, such
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© 2020 Published by Elsevier.

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The influence of corncob-based biochar on remediation of arsenic and cadmium

in yellow soil and cinnamon soil

Mingke Luo a,b, Hai Lin a,b,*, Yinhai He a,b, Ye Zhang a,b

a
School of Energy and Environmental Engineering, University of Science and

Technology Beijing, Beijing 100083, China

b
Beijing Key Laboratory on Resource-oriented Treatment of industrial Pollutants,

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Beijing 100083, China

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ABSTRACT

Biochar plays a significant role in soil remediation. However, the simultaneous

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immobilization mechanism and relationship of biochar to cations and anions have
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never been clear. We designed a batch incubation experiment to investigate the impact
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of corncob-based biochars to cadmium (Cd) and arsenic (As) contaminations in

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yellow soil and cinnamon soil, and analyze the relationships among biochars

physicochemical characteristics (surface area: SA, total pore volume: TV, average
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pore size: AV and the C/O rate), soil properties, metals immobilization and microbial
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diversity indices. Results showed that the modified biochars (inorganic-modified

biochar: BCTD) had a good effect on heavy metals immobilization and transformed

acid extractable and reducible fraction into the residual fraction. Total nitrogen,

organic matter and available potassium increased in both soils after biochar

application. The principal component analysis presented that the smaller C/O rate was

favorable to As stabilization; the SA and TV of biochar were negatively correlated

with the leaching concentration of Cd. The larger surface area, higher porosity and

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organic matters of biochar were more beneficial to soil microbial diversity. This work

not only can demonstrate remediation mechanisms of heavy metals contaminated soil

by biochars, but also gain an application of biochars technology in the recycling and

reutilize of agricultural waste, and provide a clear strategy for heavy metals

contaminated soil, especially As and Cd.

Keywords: Biochar; Cd; As; Soil remediation; Response relationship analysis

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1.Introduction

With rapid industrialization and urbanization, soil pollution is becoming a severe

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problem in China. Heavy metals (HMs) in soil are poor mobility, non-biodegradable,
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and high toxicity, causing human health hazards and immense ecological damages by
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food chain accumulation. Of those heavy metals present, soil cadmium (Cd) and
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arsenic (As) are exceeding ratios of 7.0% and 2.7%, respectively[1]. Long-time
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exposure to Cd can affect the humans’ cardiovascular function, and damage plant

active oxygen metabolism which induce physiological disorder of plant. It is known

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to all that As is one of the most harmful agricultural pollutants and damaging human
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health. Chinese policy “Action plan on prevention and control of soil pollution”

exhibit a great determination to harness the soil contamination[2]. Currently, many

approaches for soil remediation have been utilized, including mechanical methods

(e.g., burying, evaporation, washing and so on), chemical remediation (e.g.,

electro-dialysis, ultrafiltration, solvent extraction, and so on), biological filtration, and

phytoremediation. Among the methods, situ stabilization technology is a

cost-effective, eco-friendly and highly efficient method to immobilize heavy metal

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contaminated soil[3].

The biomass materials as a stabilization material to soil remediation seem

promising[4]. Corncob is an extensive agricultural waste that about 55 million tons are

produced in China a year. Corncob-based biochar was researched as a new bio-sorbent

for its wide distribution, environmentally friend and good capacity to immobilize

metals[5, 6]. Biochar is a black carbon-rich material produced through pyrolysis of

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biomass agricultural bio-waste, restaurant garbage, and sewage sludge under limited

atmospheric conditions[7, 8]. The physical and chemical properties of biochar are

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determined by biomass feedstock and pyrolysis conditions (e.g., temperature, holding
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time, and gas reagents)[9]. Biochar has a larger specific surface area at high pyrolysis
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temperature, and the mineral components of sludge biochar are higher than that of
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vegetation biochar[10]. Due to the positive properties of the extensive surface area,
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good porosity, active surface functional groups and good ion-exchange capacity, it can

be used to immobilize contaminants in soil and water. However, the removal capacity
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of the raw biochar to adsorb pollutants is relatively low, largely restricting practical
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application on a large scale[11, 12]. Therefore, the various treatment and modifications

of biochar are vitally important to raise biochar applications.

Some studies [13, 14] [15, 16]have proved that biochar addition can not only decrease

soil heavy metal and their biotoxicity, but also increase microbial population and

[17]
activities, and improve soil quality and crop yield. Qiao et al. have found that

biochar and lactate in flooded paddy soils can stimulate the active As(V)-respiring

[18]
bacteria Geobacter species for arsenic reduction and release. Xiao et al. show the

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system of biochar increased the proportion of acid-soluble Cd and Cu and improved

the soil microecology. To the best of our knowledge, most studies focused on the

immobilization effects of biochar to soil, few on the change of biochar superficial

qualities. The relationships between the specific surface area, total pore volume and

average pore size of biochar and removal heavy metals are not clear. Besides, the

influence of biochar application on soil properties and the associated microorganisms

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need to be further studied.

In our previous work, we have reported that biochar can be grafted modification

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by acrylonitrile (grafted biochar as MBC350), enhancing the physical adsorption and
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adsorption-complexation of heavy metal[19], and it can be fixed nano-TiO2 (loaded
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biochar as BCTD) to simultaneously remove Cd and As[20] in water. To expand their

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application, it is necessary to continuously research the role of the organic and

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inorganic composition of biochar in soil restoration, through studying the effect of

organic-modified and inorganic-modified biochar on the terrestrial environment.

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Given the preceding consideration, we designed an in-situate rehabilitating

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experiment to examine the performance of biochar. The detailed objectives were: (1)

to evaluate the effects of biochars on the As and Cd immobilization in yellow soil and

cinnamon soil, (2) to investigate the relationships between the specific surface area,

total pore volume and average pore size of biochar and immobilization heavy metals,

(3) to analyze the impacts of biochar components on microbial metabolic functional

diversity. Therefore, in this study, the leaching of As and Cd, metal speciation,

microbial metabolic activity, and soil properties will be extensively discussed with

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various biochar physicochemical characteristics.

2 Materials and methods

2.1 Reagents

All of the chemicals in this study were are analytical purity. Cadmium nitrate

tetrahydrate (Cd(NO3)2·4H2O), sodium dihydrogen arsenate (NaH2AsO4), and so on

were purchased from Sino Pharm Chemical Reagent Co, Ltd, Shanghai, China and

used without further treatment. Deionized water (DW, 18.2MΩ cm-1, Milli-Q) was

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used in all the experiments. Soil experiments were conducted in triplicates and some

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tests were repeated three times to make sure its accuracy.
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2.2 Biochar and soil
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Biochar materials were produced from raw corncobs at settled gradient

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temperatures (350°C, 550°C) in an oxygen-limited condition for 2 h. Both samples

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were hereafter referred to as BC350 and BC550. Preparation of modified biochar

MBC350 and BCTD was described in our previous report[19, 20]

. BC350 was
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successfully grafted with CN group and name it MBC350. And BCTD was
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synthesized by ultrasonic BC550 and nano-TiO2. The surface area, total pore volume,

average pore size, pH and the rate of C/O on BC350 are 0.95 m2/g, 0.003 cm3/g, 7.21

nm, 7.69 and 2.30 respectively; those of BC550 are 3.38 m2/g, 0.008 cm3/g, 9.01 nm,

9.85 and 4.50; those of MBC350 are 4.73 m2/g, 0.009 cm3/g, 10.02 nm, 8.92 and 6.40;

those of BCTD are 450.43 m2/g, 0.052 cm3/g, 0.46 nm, 6.97 and 1.20.

Yellow soil (YS) was collected from the upper layer of a farmland field near a

smelter in Guiyang city, south China. Cinnamon soil (CS) was collected from the

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surface layer of farmland near the sewage irrigation area in Beijing, north China. The

soil samples were air-dried, homogenized, sieved before use, and the main properties

are presented in Table 1.

2.3 Experimental design

The biochars were used to immobilize the heavy metal polluted soils. 250 g of

prepared soil was conducted in 500 mL plastic beakers. BC350, MBC350, BC550,

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BCTD were applied to cinnamon soil and yellow soil at a rate of 1.0%(w/w) (the

abbreviation of the corresponding soil: BC350-soil, MBC350-soil, BC550-soil,

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BCTD-soil). Both soils without biochars were designated as the control (CK). The
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soils and the biochars were mixed evenly, maintained at 70% the water holding
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capacity by adding deionized water and incubated for 30 days under 25°C. Every kind
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of soil remediation experiment forms a group with three parallel tests. After
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incubation, soil properties, heavy metals and microbial metabolic parameters were

determined. About 25 g of soil was collected from each beaker at 15, 30 days for pH,
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soil organic matter, soil fertility, and metals fractions determination. Toxicity
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characteristic leaching procedure (TCLP) was conduct to quantify the stabilization of

heavy metals by biochars.

2.4 Chemical analysis

To analyze the Cd and As concentrations, the soil samples were digested with a

mixture of HCl-HNO3-HClO4 and measured by ICP-OES/MS (PerkinElmer, USA).

Soil pH was measured using pH meter (METTLER TOLEDO, SevenCompact pH)

with a soil: water ratio of 1:2.5 (w/v)[21]. Organic matter of soils was measured using

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the K2Cr2O7 oxidation method. The contents of total nitrogen (TN), available

phosphorus (Ava-P), and potassium (Ava-K) were measured using a reference method

[22]
. The metals fractions in soil samples from 15 d and 30 d were measured by the

four-step European Community Bureau of Reference (BCR) sequential extraction

process, including acetic acid extractable, reducible, oxidizable, and residual

fractions[1]. Toxicity characteristic leaching procedure (TCLP) reflecting

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bioavailability of heavy metals, were measured using the soil samples with deionized

water (1:10 w/v) for 8h[23]. The extracts collected from the experiment of BCR and

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TCLP were filtered by chemical analytical filter paper and stored at 4°C before being
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measured using ICP-OES/MS.
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2.5 Microbial metabolic activity

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Biolog system with Biolog EcoPlate™ which was used to measure the metabolic
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functional diversity of soil microorganism includes 31 of the widely useful carbon

sources, and it was specifically designed for community analysis and microbial
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ecological studies[24]. To be brief, 150 μL diluted soil extracts (10-3) were inoculated
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in each well of MicroPlates. Then, the plates were incubated in the incubator for 15 d

at 28°C and analyzed by the Microplate Reader (dual-wavelength data: OD590–

OD750) every 24 hours[25]. Average Well Color Development (AWCD) was used to

estimate the integral fingerprinting of carbon source utilization and was calculated as

the arithmetic mean of the OD values of each microplate wells per reading time[26].

The EcoPlate readings at 15 d were used to analyze the Shannon and McIntosh

indices, which assessed the diversity and evenness of the soil microbes, respectively.

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And the calculating formulation of indices referred to this study[27].

2.6 Statistical analyses

Soil data were calculated as the average value of the three replicates. The data

shown in the tables and figures were performed by Origin 8.5 and Excel 2010. SPSS

version 23.0 software was carried out to analyze the linear relationship between soil

physicochemical characteristics, microbial metabolic parameters, heavy metals

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immobilization effects and biochar physicochemical properties. Besides, the data

were utilized principal component analysis (PCA) to illustrate the major variation and

covariation by varimax rotation.

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3 Results and discussion
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3.1 Effect of biochars on soil property

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3.1.1 Soil pH
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The initial pH of Beijing CS and Guiyang YS was 7.98 and 6.87, respectively.

After pretreatment, the pH was 7.32 and 7.24, respectively. BC350, MBC350, BC550,
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BCTD were added to both soils, and soil pH was measured on the 15th day and 30th
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day, the results are shown in Figure 1.

In CS, the pH on the 30th day was higher than the 15th day, and it was related to

the temperature, moisture, and nitrogen content[28]. Soil pH is a dynamic balancing

process during incubation, Xu, et al. found a similar trend[29]. The 15th day pH of

BJ-CK, BC350, BC550, MBC350, and BCTD soil was 7.18, 7.09, 7.07, 7.39 and 6.96,

respectively. And 30th day pH was 7.73, 7.77, 7.76, 8.08 and 7.26, respectively.

BJ-soil pH was significantly increased by MBC350 and decreased by BCTD. In YS,

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figure 1b showed that the pH for 30 d was less than the 15th day. The BCTD-soil pH

was reduced from 7.53 to 7.25, and compared with other materials, MBC350-soil was

the less decreased. It is positively induced by MBC350 application and negatively

induced by BCTD. The increments of soil pH may be related to the pH of biochar.

After biochar addition, elements such as Ca, Mg, and K found on biochar adsorption

sites can be released and replaced with heavy metals such as Cd, causing a change in

soil pH[30].

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3.1.2 Soil organic matter (SOM)

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SOM content can affect the binding of heavy metals to soil and decrease
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bioavailability and toxicity of heavy metals[31].The results are shown in Figure 2. It
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can be seen that the total organic matter (TOM) content of cinnamon soil was higher
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than that of yellow soil. Beijing cinnamon soil contain plant roots in the experiment,
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which was difficult to separate. The root can rot and increase the soil TOM during

incubation. After incubation, the soil TOM was positively induced by 4 biochars
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application and the content increased along with incubation time. During 30 d
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incubation, the TOM content was increased about 40% by biochars for yellow soil

and about 30% for cinnamon soil. The increment rate of TOM in both soils was

MBC350 ＞ BC350 ＞ BC550 ＞ BCTD, which was consistent with the variation

of biochars organic C content. In other words, the content of MBC350 was the highest,

which was good for soil improvement. This observation showed that there was a

positive correlation between SOM and the content of organic on biochar. And the

organic modification and low temperature biochar can improve the soil

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microorganism environment, especially in yellow soil.

3.2 Effect of biochars on soil fertility

3.2.2 Effect of biochars on total nitrogen (TN)

The TN in both soils was increased with incubation time (Figure 3). Biochars

application to the soils had good effects on the TN compared with control soils. On

the 30th day, the TN increased from 6.87 mg/kg to 8.28 mg/kg by MBC350 addition in

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cinnamon soil, from 6.37 mg/kg to 8.29 mg/kg by MBC350 addition in yellow soil.

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The increment rate of TN in both soils was MBC350＞BC550＞BC350＞BCTD.

Because the grafting modification in lignin of biochar using acrylonitrile introduced

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the -CN group, and increased the C and N content of biochar (MBC350). The
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inorganic modification biochar (BCTD) decreased the TN content per unit mass. Like
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pH, the increments of TN may be related to the N content of biochar. Biochar addition
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can release the N and C elements during incubation and increase soil TN and TOC

contents.
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3.2.3 Effect of biochars on available phosphorus (Ava-P)

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As shown in Figure 4, after 30 d, the amount of available phosphorus in soils was

decreased by biochar addition compared with unamended soils. The materials showed

different influences on both soils. The content of Ava-P from yellow soil decreased

along with incubation time, while cinnamon soil increased. For Guiyang yellow soil,

the modified biochars and raw biochars had an inverse effect on the Ava-P. Figure7b

showed there was more acid extractable Cd fraction in yellow soil, effective groups

(PO43-) can be reacted to immobilize Cd. Besides, MBC350 and BCTD presented

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strong sorption capacities for a variety of contaminants and both available phosphorus

can be adsorbed by it[31]. For cinnamon soil, MBC350 and BCTD had a positive

influence on the Ava-P under 30 d, while BC350 and BC550 reduced the Ava-P content.

The reason can be less acid extractable Cd in CS, the change was more depending on

the content of biochar[32]. The results above indicated that the change of Ava-P content

was related to heavy metal fraction, soil property and material characteristics.

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3.2.4 Effect of biochars on available potassium (Ava-K)

The available potassium content under different treatments from soils was shown

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in Figure 5. The content of Ava-K in cinnamon soil was higher than that of yellow soil.
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Compared with the CK soils without biochars, the Ava-K in both soils was increased
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by 4 biochars application during incubation. The Ava-K content in cinnamon soil

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increased nearly twice by BC350, BC550, MBC350 and BCTD, and yellow soil
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increased about 50%. It was evident to us that Beijing cinnamon soil contained plant

roots in the experiment, which was difficult to separate. The Ava-K content on the
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30th day was higher than the 15th day. During incubation, the root can rot and
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increase the soil TOM and Ava-K content. The increment of Ava-K by raw

biochars-amended (BC350 and BC550) soils was higher than modified biochars

(MBC350 and BCTD). The reason for this phenomenon was that probably the

modification has decreased the biochar K element content or strong adsorption

capacity of biochar can adsorb soil potassium ions. In general, the biochars had a

positive influence on the content of available potassium from both soils.

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3.3 Heavy metals immobilization in soil

3.3.1 Leaching Characteristics of HMs.

In this study, the TCLP method was used to evaluate the stabilization of heavy

metals in soils by biochars. Figure 6 presented the effect of TCLP-leachable HMs and

its stabilization efficiency in BC350, BC550, MBC350 and BCTD treated soil

samples, respectively. TCLP-leachable Cd and As were significantly reduced with

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incubation time, indicating that the environmental risk of HMs in soils declined

significantly.

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For arsenic, figure 6a showed the leaching concentration from cinnamon soils
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was far higher than yellow soils. Compared with cinnamon soil control, the leaching
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concentration of As in BCTD treated soil was reduced from 162.5 to 45.45 μg/L
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(72.03%) on 30 days, and BC350 treated soil was reduced from 162.5 to 138.5 μg/L
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(14.77%). The possible reason was that the biochar and As emerged the

adsorption-complexation[33]. While the BC550 and MBC350 had a negative effect on

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the stabilization of arsenic in cinnamon soil. The possible reason was that both
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biochars had higher pH, leading to the release of As in the soil. The BC350, BC550,

MBC350 and BCTD materials had a similar influence on the leaching As

concentration in yellow soil. In a word, BCTD and BC350 were effective in

immobilizing soil As, but BC550 and MBC350 were not effective. This phenomenon

showed that the stabilization of arsenic could relate to the physic-chemical properties

of biochar. For cadmium, figure 6b presented the Cd concentration of cinnamon and

yellow soils in extracts is less than 2 μg/L on 30 days. And leaching concentration was

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reduced in MBC350 and BCTD treated soils. In our previous work, we have proved

that modified biochars (MBC350[19] and BCTD[20]) had a strong bonding force

between their surface and Cd2+, showing a good potential of modified biochar to

reduce Cd risks of leaching.

These results suggest that the BCTD and MBC350 may be responsible for more

retention of Cd through surface sorption. A similar conclusion was also described in

Cao’s study[34]. The small pH and C/O rate of BCTD and BC350 had a positive

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influence on the stabilization of arsenic, due to the adsorption complexation of

oxygen-containing groups[33].
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3.3.2 Heavy metals fractions
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The fractions of As and Cd in soils after incubation were measured by BCR

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sequential extraction process and the results were presented in figure 7. Figure 7a
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showed that the residual fraction of As in yellow soils was higher than cinnamon soils,

indicating arsenic in cinnamon soil is easy to leach. The content of residual As was
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high (＞99%) and changed only slightly when biochars were added, because of the
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short incubation time the amended materials had a little effect on the residual fraction

of As. On the 30th day, compared with the CS-CK, the acid extractable decreased

from 2.29% to 0.2% for the BCTD amended treatment, and the reducible decreased

from 1.72% to 0.64%. Besides, the oxidizable increased from 1.21% to 1.8%. A part

of exchangeable and reducible As fractions transformed into the oxidizable and

residual fractions by BCTD. The functional groups (Ti-O) on BCTD could form

complexes with As. In BC550 soil, the reducible decreased from 2.86% to 1.0%, and

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the extractable increased from 2.29% to 2.6%. The fractions of As with other biochars

treatment didn’t change compared to CK. In a word, BCTD and BC550 can decrease

the activity of As in Cinnamon soil.

As shown in Figure 7b, the residual fractions of Cd in both soils increased with

incubation time. In Cinnamon soils, MBC350 and BCTD decreased the acid

extractable fraction which was transformed into the residual fraction during

incubation. In yellow soils, on the 15th day the acid extractable Cd fraction of

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BC350-soil, MBC350-soil and BCTD-soil decreased from 29.92% to 24.04%, 29.92%

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to 18.29 %, and 29.92% to 27.71%. And the reducible Cd fraction of BC350-soil,
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MBC350-soil and BCTD-soil decreased from 13.78% to 11.58%, 13.78% to 9.6%,
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and 13.78% to 12.82%. On the 30th day, the change of Cd fractions was within 1%.
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The reason may be that the biochars were reacted completely at the early stage in
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incubation. And biochar application can increase the soil pH and CEC, which were

significantly related with the concentration of exchangeable HMs[23]. These findings

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indicated MBC350 and BCTD can stabilize arsenic in cinnamon soil and yellow soil.
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3.4 Microbial metabolic activity

3.4.1 Analysis of AWCD

To analyze the microbial metabolic functional diversity in soils, the change of

average well color development (AWCD) were measured[35, 36]. Figure 8 had shown

the effects of BC350, BC550, MBC350 and BCTD on changes in AWCD.

In cinnamon soils, Figure 8a showed that all biochars decreased AWCD, which

increased with incubation time and remained stable in the last days. Zhu et al.[37]

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found a similar phenomenon when they studied the influence of biochars on soil

microbes. The 5th day of incubation could distinguish clear differences amongst the

treatments. AWCD increased after 10 d in the order of BJ-CK＞BC350＞BCTD＞

BC550 ≈ MBC350. In yellow soil, All AWCD were nearly zero with no difference

amongst soils during 3 days of incubation. After a period, the order of stable AWCD

was BCTD＞BC550＞BC350＞MBC350 ≈ GZ-CK. Among them, BCTD had greatly

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increased the amount of AWCD (108 times). These results showed that biochars

decreased the AWCD of cinnamon soil and increased that of yellow soil. The

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phenomenon indicated that the influence of microbial metabolic diversity by biochars
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was related to soil style, heavy metal species and biochar physicochemical
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characteristics.
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3.4.2 Analysis of diversity indices

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The effects of biochars on the soil Shannon and McIntosh indices are shown in

Table 2. The Shannon index of cinnamon soil decreased 10% by BC350 and BCTD,
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and 40% by BC550 and MBC350. The McIntosh index of BC350, BC550, MBC350,
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and BCTD soil decreased from 4.242 to 3.011, 1.658, 1.813 and 1.951, respectively.

According to the results, the diversity and evenness of the microbial cinnamon soil

community were inhibited by biochars. In yellow soil, The Shannon index of BC350,

BC550, MBC350, and BCTD increased from 0.834 to 1.128, 1.727, 0.899, and 2.312,

respectively. The McIntosh index of BC350, BC550, and BCTD increased from 0.026

to 0.083, 0.216, and 2.819, respectively. Biochars addition had a positive effect on

diversity indices in yellow soil. The decrease in AWCD and diversity indices of

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cinnamon soil illustrated carbon-source utilization rate and microbial diversity was

reduced by biochars compared to the control. However, biochars improved the soil

environment and enhanced the activity, diversity and evenness of yellow soil

microbes. In conclusion, biochar addition maybe has varied effects on community

diversity of soil microorganisms; physiological differences of the microorganisms and

diverse soil textures could lead to the differences of the studies[38].

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3.5 Correlation analysis of parameters

To understand the mechanisms of biochar to heavy metals immobilization, the

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correlation analysis was used to analyze the associations among biochars
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physicochemical characteristics (surface area, total pore volume, average pore size
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and the C/O rate), soil properties (pH, TOM, TN, Ava-P and Ava-K), metals leaching
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and microbial diversity indices (AWCD, Shannon and McIntosh indices). The two
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main factors of the principal component analysis (PCA, Fig. 9) explained 81.18% of

the variance in Beijing cinnamon soils (53.27% PC1 and 27.91% PC2) and 89.9% in
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Guiyang yellow soil (60.3% PC1 and 29.6% PC2).

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Figure 9A illustrated that SA, TV, PS, the C/O rate, Shannon, the leaching

concentration of As and Cd, pH and TN had high loadings on PC1 in cinnamon soil,

which showed a correlation among these factors. While SA, TV and Shannon showed

high negative loadings on PC1, which indicated their opposite behavior. Ava-P and

Ava-K had high loadings on PC2. TN and the leaching concentration of Cd had high

loading on the two components, indicating that they were influenced by two factors.

As we all know, the SA, TV, PS and the C/O rate rely on the production condition of

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biochar, so the PC1 can be classified as biochars application factor. Similarly, Ava-P

and Ava-K are mainly dependent on soil texture, the PC2 can be classified into soil

properties factor. The microbial diversity indices were a positive correlation with the

SA and TV of biochar, and a negative correlation with the C/O rate, which suggested

the larger surface area, total pore volume and the O/C rate of biochars are beneficial

to the microbial diversity. A positive correlation was found between soil pH, TN and

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the C/O rate, PS of biochars. The leaching concentration of As and Cd had a negative

correlation with the SA and TV, and a positive correlation with the C/O rate and PS.

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Among of them, the leaching concentration of As was a better correlation with the
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C/O rate and PS, and that of Cd was a better correlation with SA and TV. These
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results indicated that the arsenic immobilization was heavier affected by the
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oxygen-containing functional groups and average pore size of biochar, and cadmium
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immobilization was heavier influenced by surface area and total pore volume of

biochar.
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For yellow soil (Fig. 9b), SA, TV, PS, the C/O rate, AWCD, Shannon, McIntosh,
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had high loadings on PC1. TOM, Ava-K, and pH had high loadings on PC2. The

leaching concentration of As and Cd, Ava-P, and TN had high loadings on the two

components. The SA and TV of biochar were found positively correlated with

microbial diversity indices and negatively correlated with the leaching concentration

of As and Cd, soil pH, TN an Ava-P. The C/O rate and PS of biochar were negatively

correlated with AWCD, Shannon, McIntosh, and positively correlated with soil OM,

the leaching concentration of As and Cd. The leaching concentration of As and Cd

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had a better correlation with the C/O rate in all biochars properties. These phenomena

were similar to cinnamon soil. A high C/O rate of biochars inhibited the microbial

diversity and decreased the effect of metals immobilization.

Summarizing, the results of PCA in both soils indicated that the C/O of

corncob-based biochars had strong influences on the leaching concentration of As,

and the smaller C/O rate was favorable to heavy metal stabilization in soil. The SA

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and TV of biochar were negatively correlated with the leaching concentration of Cd.

The SA, TV and O/C rate were positively correlated with the development of soil

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microbial diversity. The larger SA, TV and O/C rate of biochars provided a good
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habitat and available carbon sources for soil microbes.
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4 Conclusions
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This work showed that the biochar application was a more important function for
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the reduction of HMs bioavailability, the increase of soil fertility and the improvement

eco-environment. In cinnamon and yellow soils, BCTD and MBC350 had a positive
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influence on Cd immobilization; BCTD and BC350 contributed to As stabilization.

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Total nitrogen, organic matter and available potassium increased in both soils after

biochar application. The increments of soil pH and organic matter were positively

related to the properties of biochar. The principal component analysis presented that

the smaller C/O rate was favorable to As stabilization in soil; the SA and TV of

biochar were negatively correlated with the leaching concentration of Cd. The larger

surface area, higher porosity and organic matters of biochar were more beneficial to

soil microbial diversity. The modified biochars transformed acid extractable and

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reducible fraction of Cd into the residual fraction in cinnamon soil. In yellow soil,

biochars addition could adsorb the available phosphorus which was used to

immobilize Cd; and increase AWCD (BCTD: 108 times), Shannon (BCTD: 2.8 times)

and McIntosh (BCTD: 108 times) indices, which improved yellow soil microbial

diversity. The research has the potential for developing the remediation technique of

heavy metals contaminated soils.

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Acknowledgments

This work was supported by the Fundamental Research Funds for the Central

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Universities (FRF-TP-18-073A1) and Beijing Key Laboratory on Resource-oriented
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Treatment of industrial Pollutants in University of Science and Technology Beijing.
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Conflict of interest statement

We declare that we do not have any commercial interest that represents a conflict
of interest in connection with the work submitted. Neither the entire paper nor any
part of its content has been published or has been accepted elsewhere. All authors
agree to submission.

Prof Lin Hai

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28 Oct 2019

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The influence of corncob-based biochar on remediation of arsenic and

cadmium in yellow soil and cinnamon soil

Figure caption

Fig. 1. Soil pH responses to BC350, BC550, MBC350 and BCTD amendment: (a)

cinnamon soil, (b)Guiyang soil.

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Fig. 2. Soil OM responses to BC350, BC550, MBC350 and BCTD amendment.

Fig. 3. Soil TN responses to BC350, BC550, MBC350 and BCTD amendment.

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Fig. 4. Soil Ava-P responses to BC350, BC550, MBC350 and BCTD amendment.
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Fig. 5. Soil Ava-K responses to BC350, BC550, MBC350 and BCTD amendment.
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Fig. 6. The TCLP-leachable Cd and As in biochars treated soil.

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Fig. 7. Proportions of different metals fractions in biochars (BC350, BC550, MBC350

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and BCTD) treated soils (a)As (b)Cd.

Fig. 8. Effects of BC350, BC550, MBC350 and BCTD on AWCD based on the
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Biolog EcoPlate data (16days).

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Fig. 9. Principal components analysis of soil properties, metals mobility and microbial

diversity, (A)Beijing cinnamon soil (B) Guiyang yellow soil. SA: surface area, TV:

total pore volume, PS: average pore size.

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Fig. 1. Soil pH responses to BC350, BC550, MBC350 and BCTD amendment: (a)

Beijing cinnamon soil, (b)Guiyang yellow soil

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Fig. 2. Soil OM responses to BC350, BC550, MBC350 and BCTD amendment
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Fig. 3. Soil TN responses to BC350, BC550, MBC350 and BCTD amendment
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Fig. 4. Soil Ava-P responses to BC350, BC550, MBC350 and BCTD amendment
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Fig. 5. Soil Ava-K responses to BC350, BC550, MBC350 and BCTD amendment
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Fig. 6. The TCLP-leachable Cd and As in biochars treated soil

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Fig. 7. Proportions of different metals fractions in biochars (BC350, BC550, MBC350

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and BCTD) treated soils (a)As (b)Cd.

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Fig. 8. Effects of BC350, BC550, MBC350 and BCTD on AWCD based on the
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Biolog EcoPlate data (16 days).

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Fig. 9. Principal components analysis of soil properties, metals mobility and microbial
diversity, (a)Beijing cinnamon soil (b) Guiyang yellow soil. SA: surface area, TV:
total pore volume, PS: average pore size

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The influence of corncob-based biochar on remediation of arsenic and

cadmium in yellow soil and cinnamon soil

Table caption

Table 1 Physicochemical properties of soils.

Table 2 Diversity indices of soil microorganism based on the Biolog EcoPlate data of

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different treatments (16days).

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Table 1 Physicochemical properties of soils.

Beijing Guiyang
Properties
Cinnamon soil Yellow soil

pH 7.98 6.87

Organic matter (%) 1.53 2.47

Ava-N（mg/kg） 79.63 23.91

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Ava-P（mg/kg） 86.48 26.67

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Ava-K（mg/kg） 191.83 362.53

As（mg/kg） 16.8 51.61

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Cd（mg/kg） 0.94 3.12
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Table 2 Diversity indices of soil microorganism based on the Biolog EcoPlate data of

different treatments (16days).

Soil sorbents AWCD Shannon McIntosh

BJ-CK 0.452 2.456 4.242

BC350 0.279 2.198 3.011

Beijing
BC550 0.101 1.511 1.658
Cinnamon soil

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MBC350 0.114 1.493 1.813

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BCTD 0.167 2.151 1.951

GZ-CK 0.003
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BC350 0.004 1.128 0.083

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Guiyang
BC550 0.015 1.727 0.216
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Yellow soil
MBC350 0.001 0.899 0.018
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BCTD 0.325 2.312 2.819

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Graphical abstract
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Highlights
1.Biochars addition improved soil microbial diversity and fertility in poor

soil.

2. Lower C/O rate of biochar was more favorable to As stabilization in

soil.

3.Negative correlation between surface area, total pore volume and Cd

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stabilization.
4.Modified biochar (BCTD) reduced the As and Cd toxicity in contaminated soils.

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