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State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
The Key Lab of Marine Environmental Science and Ecology, Ministry of Education, Ocean University of China, Qingdao 266100, China
c
Geotechnical and Environmental Research Group, Department of Engineering, University of Cambridge, Cambridge CB2 1PZ, UK
b
h i g h l i g h t s
g r a p h i c a l
a b s t r a c t
Hg
a r t i c l e
i n f o
Article history:
Received 30 April 2015
Received in revised form 15 July 2015
Accepted 21 July 2015
Available online 26 July 2015
Keywords:
Mercury
Contaminated soil
Thermal treatment
Citric acid
a b s t r a c t
Thermal treatment is a promising technology for the remediation of mercury contaminated soils, but
it often requires high energy input at heating temperatures above 600 C, and the treated soil is not
suitable for agricultural reuse. The present study developed a novel method for the thermal treatment of
mercury contaminated soils with the facilitation of citric acid (CA). A CA/Hg molar ratio of 15 was adopted
as the optimum dosage. The mercury concentration in soils was successfully reduced from 134 mg/kg
to 1.1 mg/kg when treated at 400 C for 60 min and the treated soil retained most of its original soil
physiochemical properties. During the treatment process, CA was found to provide an acidic environment
which enhanced the volatilization of mercury. This method is expected to reduce energy input by 35%
comparing to the traditional thermal treatment method, and lead to agricultural soil reuse, thus providing
a greener and more sustainable remediation method for treating mercury contaminated soil in future
engineering applications.
2015 Elsevier B.V. All rights reserved.
1. Introduction
547
548
400 oC
600 oC
400 oC, CA
12
15
15
12
0
20
40
60
80
Treating time (min)
100
Hg (mg/kg)
Untreated
300
400
500
600
700
134 8.2
20 3.5
12 1.8
6.5 0.4
3.8 1.3
0.7 0.2
85.1 2.6
91.0 1.3
95.1 0.3
97.2 1.0
99.5 0.1
20
40
CA/Hg (molar ratio)
60
Fig. 2. Effect of variable amounts of CA on decontamination of mercury in soil samples. The soil samples (mercury concentration: 134 mg/kg) were treated at 400 C
for 30 min.
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Table 2
Soil physiochemical properties before and after thermal treatment.
Soils
pH
CaCO3 (%)
Corg (%)
Soil
color
CEC (cmol/kg)
Fed
(g/kg)
Mnd
(g/kg)
Clay (%)
Silt (%)
Sand (%)
Untreated
400 C, 60 min, with CA
700 C, 30 min, without CA
6.6 0.3
7.6 0.3
10.2 0.4
0.6 0.2
0.2 0.1
0.5 0.3
2.5 0.3
1.6 0.5
ND
10YR 3/3
10YR 4/3
5YR 7/8
11 0.2
9.8 0.5
4.6 0.5
5.2 0.5
6.1 0.5
7.2 0.7
0.13 0.05
0.15 0.01
0.14 0.04
31 3
24 5
12 6
61 5
56 6
55 8
83
20 8
33 9
0
Original
Chloride
Removed
Chloride
Added
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Table 3
Mercury concentrations (mg/kg) in fractions by sequential extraction before and after thermal treatment.
Soils
F1
F2
F3
F4
F5
Untreated
Without CA
400 C for 30 min
400 C for 60 min
400 C for 90 min
600 C for 30 min
600 C for 60 min
700 C for 30 min
With CA
400 C for 30 min
400 C for 60 min
400 C for 90 min
5.98 1.35
9.03 2.00
2.04 0.50
6.77 0.41
99.10 1.63
0.54 0.24
0.11 0.05
0.09 0.06
ND
ND
ND
1.38 0.32
0.20 0.18
0.25 0.12
0.10 0.05
ND
ND
0.28 0.11
0.15 0.07
0.15 0.14
0.07 0.24
ND
ND
0.84 0.00
0.21 0.10
0.24 0.04
0.09 0.04
ND
ND
7.29 0.21
5.66 0.28
5.40 0.21
3.27 0.15
2.24 0.55
0.52 0.13
0.05 0.02
ND
ND
0.16 0.11
0.05 0.01
ND
0.16 0.04
0.07 0.01
0.10 0.03
0.21 0.07
0.09 0.02
0.11 0.03
2.08 0.11
0.80 0.04
0.68 0.04
as substitutes of CA. As shown in Fig. 4, residual mercury content in the soil was 13.1 mg/kg when treated with Na3 CA, which
was comparable with that in soil treated without the additives.
It should be noted that the residual mercury contents in the soil
samples were 9.3 mg/kg and 5.6 mg/kg when treated with Na2 HCA
and NaH2 CA, higher than that in the soil sample treated with
CA, but lower than that in the soil sample treated with Na3 CA.
The acidity of CA, NaH2 CA, Na2 HCA, and Na3 CA is in the order
CA > NaH2 CA > Na2 HCA > Na3 CA, which was consistent with the
order of mercury removal efciency. These results suggest that
the mercury removal mechanism with CA was providing an acidic
environment.
Similar to those in soil washing using an acid solution, several mechanisms may be involved during thermal treatment with
CA: (1) desorption of mercury cations adsorbed on the surface of
soil particles via ion exchange; (2) dissolution of HgO or HgS into
Hg2+ ; and (3) dissolution of soil mineral components (e.g., dolomite,
FeMn oxides) which may contain mercury contaminants [40,41].
At low pH, the protons (H+ ) added can react with soil surface sites
(layer silicate minerals and/or surface functional groups including
Al-OH, Fe-OH, and COOH groups) and enhance desorption of mercury cations, forming species that can be easily volatilized [42],
which was conrmed by the decrease of CaCO3 content when
treated with CA (Table 2). The dissolution of soil mineral components may also cause the reduction of grain size. Moreover, due to
the relatively low boiling point and decomposition temperature,
CA and its decomposition products would volatize during thermal
treatment, and the dissolved soil mineral components would still
exist in the soil. Therefore, changes in soil properties and structures
were less compared with those in acid washing.
15
20
Residual mercury contents (mg/kg)
without CA
12
with CA
15
10
0
Control
CA
7
Soil pH
10
551
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