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Journal of Hazardous Materials 300 (2015) 546552

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Journal of Hazardous Materials


journal homepage: www.elsevier.com/locate/jhazmat

Citric acid facilitated thermal treatment: An innovative method for


the remediation of mercury contaminated soil
Fujun Ma a , Changsheng Peng b , Deyi Hou c , Bin Wu a , Qian Zhang a , Fasheng Li a ,
Qingbao Gu a,
a

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

content was reduced to


<1.5 mg/kg when treated at 400 C
with citric acid.
The treated soil retained most of its
original soil physicochemical properties.
Proton provided by citric acid facilitates thermal removal of mercury.
This thermal treatment method is
expected to reduce energy input by
35%.

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

Corresponding author. Fax: +86 10 84932813.


E-mail address: guqb@craes.org.cn (Q. Gu).
http://dx.doi.org/10.1016/j.jhazmat.2015.07.055
0304-3894/ 2015 Elsevier B.V. All rights reserved.

Mercury is a highly toxic element which affects human nervous


system, brain, heart, kidneys, and immune systems [1]. During the
recent years, mercury pollution is drawing attention from many
governments, as well as international organizations such as the
United Nations Environment Programme [2]. The main anthropogenic sources contributing to mercury contamination include
mercury mining, gold mining, wood preservation, coal combustion, and chlor-alkali industry [3,4]. The US EPA reported that 290

F. Ma et al. / Journal of Hazardous Materials 300 (2015) 546552

Superfund sites on the National Priorities List were contaminated


by mercury, and 173 of these 290 sites were soil-contaminated
sites [5]. In China, a number of mercury polluted soils have been
reported, the mercury concentrations in some soils are up to 232
times the maximum mercury concentration allowed for soil in
China (1.5 mg/kg, National Standard GB15618-1995) [3], thus representing a serious threat to human health and the environment.
To clean up mercury contaminated soil, mercury concentration
in the soil should be reduced to a low level (e.g., <1.5 mg/kg). The
available remediation technologies for soil contaminated with mercury include phytoremediation [68], stabilization/solidication
[9,10], soil washing [11,12], thermal treatment [1318], and
electrokinetics [19,20]. Stabilization/solidication changes soil
properties dramatically and makes the treated soil unsuitable for
agricultural reuse. Soil washing and electrokinetics are generally
not efcient enough to reach an acceptable decontamination level.
Thermal treatment can achieve an acceptable decontamination
level when mercury-contaminated soils are treated at temperatures above 600 C [13,16]. However, the high heating temperature
requires high energy cost, moreover, dramatic changes in soil properties, including increase in soil pH, dehydration of silicate clay
minerals, and reduction in the content of organic carbon, were
observed when soils were treated at 600 C, thus making the soils
unfavorable for agricultural reuse [14,18]. Therefore, there is a clear
need to develop a method that lowers the temperature at which
mercury can be removed to a low level (e.g., <1.5 mg/kg), thus
reducing energy requirement and life cycle (i.e. cradle to grave)
environmental footprint, which aligns well with the ongoing sustainable remediation movement [21].
Mercury presents in a variety of forms in soils, including metallic mercury, inorganic mercury compounds (chlorides, suldes,
oxides, etc.), organic mercury compounds (methyl mercury, ethyl
mercury), and those captured inside pores of the soil particles
(e.g. dolomite, pyrite, sphalerite). Mercury speciation has a significant effect on the thermal removal of mercury from soil. Mercury
species other than Hg(0) and Hg(I) are not volatile when mercurycontaminated soils are treated at temperatures below 200 C [22].
Therefore, high residual mercury contents were reported when
such soil samples were treated at temperatures <200 C [15]. As
temperature increases, other mercury species start to volatilize
from soil. Huang et al. reported that the residual mercury concentrations were 17 mg/kg and 6 mg/kg when a soil (collected from a
chlor-alkali plant, Hg content: 1320 mg/kg) was thermally treated
at 400 C and 550 C for 1 h, respectively [18]. It is reported that
mercury species including HgO, HgSO4 , and those captured inside
pores of the soil particles release mercury at temperatures above
400 C [23,24]. As HgSO4 is decomposed through hydrolysis, this
compound will not be stable under environmental conditions [23].
To lower the volatile temperature of these hardly volatile mercury
species in contaminated soils, some measures should be taken to
convert them to easily volatile species during thermal treatment.
In our previous study [25], the mercury content in soil was successfully reduced to <1.5 mg/kg when treated with FeCl3 at 400 C. The
removal mechanism involves FeCl3 being partially decomposed to
form HCl at low temperatures. The formed HCl reacts with these
hardly volatile metal species to produce mercury chloride compounds with low boiling points. However, the added chloride ion
may react with organic matters in the soil to form absorbable
organic halogen and dioxins; high Fe content in soil is also harmful
to vegetation.
As a natural, low-molecular-weight organic acids, citric acid
(CA) is often used in soil washing to extract heavy metals including
Pb, Cd, Cu, and Hg due to its chelating ability and acidity [2628].
In this study, mercury removal from contaminated soil by thermal treatment with CA was conducted, and then the mechanism
of CA facilitated thermal treatment was carried out. The results

547

obtained in this study are expected to provide an environmental


friendly technique for treating mercury contaminated soil in future
engineering applications.

2. Materials and methods


2.1. Soil sample preparation
Soil samples were collected from a farm land near a mercury
mining area in Tongren, Guizhou Province of China. Soil samples
were air-dried and grounded. Subsequently, particles with sizes
larger than 2 mm were removed using a standard 10-mesh sieve.
Soil samples were then thoroughly mixed. The mixed soil samples were stored properly before sample characterization (shown in
Supplementary material (SM)) and thermal decontamination tests.
Mercury concentration in the soil was determined to be 134 mg/kg.

2.2. Thermal treatment and mercury determination


Thermal treatment was performed in a laboratory-scale rotary
kiln with a mercury vapor gas treatment system. The rotary kiln was
heated by electricity. The kiln was 2 m long with an internal diameter of 0.2 m. In each test, CA was premixed with soil in a mortar
mixer before introduced into the rotary kiln, 1 kg of prepared soil
sample with or without CA was used under different conditions. The
temperature in the kiln was measured by a thermocouple (NiCr-Ni)
in the hot zone near the inner wall. Treatment time of soil samples
in the hot zone of the kiln (900 mm) was adjusted by changing the
speed of the kiln. The inclination angle of the kiln was 3.5 . At the
end of the kiln, a collecting container was set up. Mercury vapor gas
would ow into a condenser and condense into liquid mercury at
25 C. The liquid mercury was collected in a tank, and the vapor gas
would ow through an activated carbon adsorption tank to further
remove uncondensed mercury vapor gas. The mercury concentration in the exhaust gas met China Integrated Emission Standard of
Air Pollutants (12 g/m3 , National Standard GB16297-1997).
Mercury contents in soil samples were determined according to
the method of Biester and Scholz [29]. Briey, mercury contents
were analyzed by cold vapor atomic absorption spectroscopy after
reduction of Hg2+ to Hg0 with SnCl2 solution. Total mercury was
determined by digesting 5 g of soil sample in 28 mL of aqua regia for
3 h at 160 C. All analyses were conducted in triplicates. The total
Hg concentration was found to be within the condence interval
for certied values with recoveries in the range of 81113%. The
relative standard deviation among replicates was <10%. The detection limit for mercury in soil was 1.0 102 mg/kg dry weight. The
quality control of Hg measurements was conrmed by analyzing
0.25 g of standard reference material SRM 2710a produced by
NIST. Triplicate measurements of the certied reference material
yielded 10.02 0.35 mg/kg, corresponding well with the certied
value 9.88 0.21 mg/kg.

2.3. Sequential extraction


To better understand the effect of CA on the thermal decontamination of mercury, sequential extractions of soil samples
treated at various temperatures and treatment times with or
without CA were conducted. Mercury in soil samples before and
after thermal treatment were separated into water-soluble fraction (F1), exchangeable fraction (F2), humic/fulvic fraction (F3),
organic/sulde fraction (F4), and residual fraction (F5) [29]. The
operational denition of the fractions and the compositions of the
extraction solutions are given in Table S1 in SM.

548

F. Ma et al. / Journal of Hazardous Materials 300 (2015) 546552

Residual mercury contents (mg/kg)

400 oC
600 oC
400 oC, CA

12

Residual mercury contents (mg/kg)

15

15

12

0
20

40

60
80
Treating time (min)

100

Fig. 1. Effect of treatment time and temperature on decontamination of mercury in


soil samples. The soil samples were thermally treated with or without CA (CA/Hg:
15). Dash line represents the maximum mercury concentration allowed for soil in
China (1.5 mg/kg, National Standard GB15618-1995).

3. Results and discussion


3.1. Thermal treatment without CA
The effect of temperature on the thermal removal of mercury
was investigated in the range of 300700 C. The heating time was
kept at 30 min. As shown in Table 1, the residual mercury concentrations in the soil samples decreased as temperatures increased.
More than 85% of mercury was removed from the contaminated
soil when the temperature was higher than 300 C. As temperature increased from 300 C to 500 C, an additional 10% of mercury
volatilized from the soil. However, the mercury content was not
reduced to <1.5 mg/kg until 700 C. These results are consistent
with those of a previous study [16].
Fig. 1 shows the effect of treatment time on the thermal removal
of mercury. Soil samples were treated at 400 and 600 C with
treatment time ranged 3090 min. Mercury contents gradually
decreased as the treatment time increased. For example, when the
soil was treated at 400 C for 30 min, the residual mercury content
was 12.0 mg/kg, when the treatment time was extended to 60 min,
the residual mercury content was reduced to 6.7 mg/kg. It should be
noted that the residual mercury contents were similar for 60 min of
treatment (6.7 mg/kg at 400 C and 2.7 mg/kg at 600 C) and 90 min
of treatment (6.7 mg/kg at 400 C and 2.5 mg/kg at 600 C). These
results indicate that simply increasing treatment time cannot effectively reduce residual mercury contents to an acceptable level.
3.2. Thermal treatment with CA
To investigate the effect of CA addition on the thermal decontamination of mercury, soil samples were treated at 400 C for
Table 1
Total mercury concentrations and mercury removal efciency as a function of treatment temperature. The treatment time was kept at 30 min. The soil samples were
treated without CA.
Temperature ( C)

Hg (mg/kg)

Removal efciency (%)

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.

3090 min with the molar ratio of CA to mercury (CA/Hg) at 15.


Mercury removal was greatly enhanced when treated with CA
(Fig. 1). The residual mercury content in soil sample treated at
400 C for 30 min with CA (2.6 mg/kg) was only 22% of that treated
without CA, even lower than that treated at 600 C for 30 min without CA. Residual mercury was further removed as the treatment
time extended. The residual mercury concentration decreased to
1.1 mg/kg after 60 min of treatment, reaching the cleanup criterion
of 1.5 mg/kg. These results indicate that thermal treatment with CA
can reduce the residual mercury contents to an acceptable level at
a relatively low heating temperature (i.e. 400 C).
To investigate CA dosage on the thermal removal of mercury,
soil samples were treated at 400 C for 30 min with CA/Hg at 0.5,
2, 5, 15, and 50 (Fig. 2). Compared with thermal treatment without
CA, an initial CA/Hg of 0.5 reduced the residual mercury concentration by 19%, the reduction of residual mercury was enhanced when
CA was added at higher dosages, reaching 78% at an CA/Hg dosage
of 15. CA/Hg higher than 15 did not result in additional mercury
removal, suggesting that CA/Hg molar ratio of 15 was an optimum
dosage ratio under the given experimental conditions, resulting in
the maximum reduction of mercury.
3.3. Changes in soil physicochemical properties
In this study, the contents of residual mercury in two soil samples, namely, the soil sample treated at 700 C for 30 min without
CA and that treated at 400 C for 60 min with CA, were successfully
reduced to levels below the cleanup criteria of 1.5 mg/kg. To evaluate whether the treated soils are suitable for reuse on agricultural
land, the changes in soil physiochemical properties of these two
soil samples were studied.
As shown in Table 2, organic carbon content in the soil sample treated at 400 C was 1.6%, retaining the majority of its organic
carbon (65%), whereas organic carbon content could hardly be
detected in the soil sample treated at 700 C (i.e. <0.02%). Soil pH
remained near neutral (pH 7.6) when treated at 400 C, while that
treated at 700 C resulted in a pH that was much basic (pH 10.2).
The changes in pH may be attributed to the oxidation of certain
elements [30], the dehydration of colloids, the decrease of buffer
capacity, and the release of ions from organic matters in the treatment process [14,31]. The soil color (determined in SM) changed
slightly from dark brown (10YR 3/3) to brown (10YR 4/3) after
thermal treatment at 400 C, whereas the soil color changed dramatically to moderate orange (5YR 7/8) when the soil sample was

F. Ma et al. / Journal of Hazardous Materials 300 (2015) 546552

549

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

treated at 700 C. The observed color change was attributed to the


oxidation of iron and manganese compounds in a high-temperature
environment. It has been shown that Fe-laden minerals in soils tend
to transform into hematite when they become completely dehydrated, which reddens the soil [30]. The removal or pyrolysis of
organic carbon may also attribute to the color change [32]. Fed
amount slightly increased from 5.2 g/kg to 6.1 g/kg when treated
at 400 C, while higher Fed amount was found when treated at
700 C which possibly due to the formation of hematite [30]. Thermal treatment at 400 C caused a few decrease in clay content from
31% to 24% and an increase in sand content from 8% to 20%. In
contrast, the 700 C treated soil sample had a dramatic increase
in sand content and decrease in clay content. Similar grain-size
distributions were found for soil samples treated at 400 C with
or without CA (Fig. S1 in SM), the volume percentage of <0.5 m
grains in soil treated 400 C was lower than that in untreated soil,
while <0.5 m grains disappeared during thermal treatment at
700 C. The aluminum oxides and hydroxides released during clay
decomposition might act as cementing agents in the formation of
sand-sized particles [32,33]. The cation exchange capacity (CEC)
in the 400 C treated soil sample was slightly lower than that of
untreated soil sample, while signicantly lower CEC was found in
the 700 C treated soil sample. The decrease in CEC was expected
because of the oxidation of organic matter and the destruction of
clay structures. The dehydration of mineral lattice and the resulting breakdown of lattice structures were probably also important
causes of CEC reduction [34].
Overall, soil characterization results indicated that the 400 C
treated soil sample retained most of its original soil physiochemical
properties, suggesting the treated soil may be suitable for reuse
on agricultural land. In comparison, the 700 C treated soil sample
showed drastic changes in its physicochemical characteristics and
mineralogy, which makes it much more difcult to reuse.

3.5. Removal mechanism


In this study, hardly volatile mercury species in contaminated
soils were successfully converted to easily volatile species (metallic mercury, Hg2 Cl2 , HgCl2 , etc.) when thermally treated with CA.
However, the reaction mechanism of CA and the hardly volatile
mercury species is still an open question. In this section, the interaction of CA and mercury in the soil is discussed.
In thermochemical removal of heavy metals (Cu, Zn, Pb, Cd) from
sewage sludge ash, MgCl2 , CaCl2 and gaseous HCl are often used as
chloride donors [3539], the removal mechanism involves forming
volatile heavy metal chlorides. In this study, the chloride concentration was 17.4 mg/kg in untreated soil, the corresponding molar ratio
of chloride to mercury in soil was 0.73:1. To investigate whether
the added CA facilitates the formation of mercury chlorides, the
soil samples were pretreated as follows: (1) washed with ultrapure
water to remove the chloride (Hg concentration: 124 mg/kg); or (2)
added the same molar of NaCl as CA. Then the pretreated soil samples were added CA (CA/Hg: 15) and treated at 400 C for 30 min. As
shown in Fig. 3, the residual mercury concentrations were comparable in these two soil samples, and also comparable with that in the
original treated soil sample. These results suggest that the mercury
removal mechanism with CA addition was not due to the formation of mercury chlorides. The chloride concentration in treated soil
sample was determined to be 16.9 mg/kg, which was similar to that
in untreated soil sample (17.4 mg/kg), further suggesting that most
of the volatile mercury was not in the form of mercury chlorides.
CA is often used in soil washing to extract heavy metals including Pb, Cd, Cu, and Hg, the removal mechanism is that CA has
a chelating ability for cationic heavy metals and providing protons (H+ ) [2628]. Since the decomposition temperature of CA is
175 C, CA should be decomposed during thermal treatment. Therefore, the acidic environment provided by CA was probably the
removal mechanism during thermal treatment. In order to conrm this hypothesis, Na3 CA, Na2 HCA, and NaH2 CA were selected

3.4. Changes in mercury speciation

Residual mercury contents (mg/kg)

As shown in Table 3, for thermal treatment without CA, 91% of


F1, 85% of F2, 86% of F3, 88% of F4, and 93% of F5 were removed
when soil sample was treated at 400 C for 30 min. When treatment time was extended to 60 min, 98% of F1, 98% of F2, 93% of F3,
97% of F4, and 94% of F5 were removed, which also demonstrates
that the residual mercury can be further removed (especially F1F4) by extending treatment time. Similar mercury contents in each
fraction were found when the time was extended to 90 min. After
treatment at 600 C or 700 C, mercury was mainly found in F5,
suggesting that the residual fraction of mercury was the most thermally stable form in soil. For thermal treatment with CA, 99% of
F1, 98% of F2, 92% of F3, 97% of F4, and 98% of F5 were removed
when soil sample was treated at 400 C for 30 min. When treatment time was extended to 90 min, mercury in F1 and F2 was totally
removed and mercury in other fractions was further reduced. These
results indicate that CA addition during thermal treatment not only
accelerated the volatilization of mercury in the easily removed fraction (F1 and F4), but also reduced the volatilization temperature of
mercury in the hardly removed fraction (F5).

0
Original

Chloride
Removed

Chloride
Added

Fig. 3. Effect of variable amounts of chloride donors on decontamination of mercury


in soil samples. The soil samples (mercury concentration: 134 mg/kg) were treated at
400 C for 30 min with CA (CA/Hg: 15). The soil samples were (1) original; (2) washed
to remove chloride; and (3) added the same molar of NaCl as CA, respectively.

550

F. Ma et al. / Journal of Hazardous Materials 300 (2015) 546552

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.

3.6. Effects of soil pH


Since the mercury removal mechanism with CA was providing
an acidic environment, it is reasonable to speculate that soil pH has
a great effect on the removal of mercury in the soil. The inuence
of soil pH on the removal of mercury was investigated by adjusting
the soil pH to 3, 7, and 10 and being treated at 400 C for 30 min with
or without CA (CA/Hg: 15). As shown in Fig. 5, the residual mercury
contents in soil samples increased with increasing soil pH. At pH
3, the residual mercury contents in soil samples were comparable
when treated with or without CA (the residual mercury content
was 1.5 mg/kg), possibly due to a relatively small amount of CA
which changed little of the soil pH (pH 2.9 after addition of CA).
At pH 7, the soil pH changed to 5.6 after adding CA before thermal
treatment, which resulted in signicantly more mercury removal
(2.6 mg/kg residual mercury with CA versus 12 mg/kg residual mercury without CA). The residual mercury content was higher than
that in the soil samples treated at pH 3, which is also consistent
with the hypothesis that enhanced mercury removal was mainly
due to the acidic environment. The mercury removal efciencies in
soil samples of pH 10 were relatively low, also consistent with the
above hypothesis.
3.7. Energy and cost saving
A preliminary cost assessment was conducted to compare the
treatment with CA (400 C for 60 min) to that without CA (700 C
for 30 min). The energy demand was calculated using the specic
heat of soil minerals, water, and soil organic matter, as well as heat
losses when maintaining the kiln at high temperatures. The param-

15

20
Residual mercury contents (mg/kg)

Residual mercury contents (mg/kg)

without CA
12

with CA
15

10

0
Control

CA

NaH2CA Na2HCA Na3CA

Fig. 4. Effect of different additives on decontamination of mercury in soil samples.


The molar ratio of each additive to mercury was 15. The soil samples (mercury
concentration: 134 mg/kg) were treated at 400 C for 30 min.

7
Soil pH

10

Fig. 5. Effect of soil pH on decontamination of mercury in soil samples. The soil


samples were treated at 400 C for 30 min with CA (CA/Hg: 15).

F. Ma et al. / Journal of Hazardous Materials 300 (2015) 546552

eters used in the calculation were based on literature and industrial


knowledge (see SM). It was estimated that 1.05 106 kJ of energy is
required to heat 1 m3 of soil at 400 C for 60 min; and 1.60 106 kJ
of energy is required to heat the soil at 700 C for 30 min. Therefore, CA facilitated thermal treatment can render an energy saving
of 35%. Moreover, it is estimated that 1.9 g of CA is required for treating every 1 kg of soil. Based on market price of CA, it is estimated CA
facilitated thermal treatment reduces marginal cost from 57 US$ to
38 US$, or 34%. Overall, the preliminary cost assessment suggests
that the CA facilitated thermal treatment provides an energy efcient and cost effective method for treating mercury contaminated
soil.
4. Conclusions
In this study, a novel method for the thermal treatment
of mercury-contaminated soils with the facilitation of CA was
developed. 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. To achieve the same cleanup level, the
traditional thermal treatment method requires heating at 700 C
for 30 min, which would signicantly increase soil pH and sand
content, decrease organic carbon content, and change soil color.
During the treatment process, CA was found to provide an acidic
environment which enhanced the volatilization of mercury. The
thermal treatment method facilitated by CA 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.
Acknowledgements
Financial support from the National High Technology
Research and Development Program of China (863 Program)
(2013AA06A207) and the State Key Laboratory of Environmental Criteria and Risk Assessment (No. SKLECRA 2013FP12) are
gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jhazmat.2015.07.
055
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