Chemical Engineering Journal 351 (2018) 1067–1075

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Chemical Engineering Journal

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

Microwave-induced decontamination of mercury polluted soils at low T

temperature assisted with granular activated carbon
⁎ ⁎
Hai-Lei Caoa, , Feng-Ying Caia, Wen-Bin Jiaoa, Yu Wanga, Cheng Liua, Ning Zhanga, Jian Lüa,b,
a
Fujian Provincial Key Laboratory of Soil Environmental Health and Regulation, College of Resources and Environment, Fujian Agriculture and Forestry University, Fuzhou
350002, China
b
Samara Center for Theoretical Materials Science (SCTMS), Samara State Technical University, Molodogvardeyskaya St. 244, Samara 443100, Russia

H I GH L IG H T S

• GAC-assisted microwave remediation of Hg contaminated soils was studied.

• TTemperature
Hgremoval efficiency over 86.9% was achieved at ca. 350 °C in 40 min.
• Four distinguishable
gradient and hotspots are responsible for the efficient Hg removal.
• GAC can be separatedstages were revealed in the microwave-induced process.
• and reused without introducing secondary pollution.

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, a microwave-induced thermal treatment at relatively low temperature (300–350 °C) was in-
Mercury decontamination troduced to the decontamination of polluted soils with high mercury concentration, in the interest of addressing
Soil remediation the issues related to traditional thermal desorption methods i.e. high energy consumption, high cost, and irre-
Granular activated carbon versible damage to the soils. The addition of granular activated carbon (GAC) was found to significantly increase
Mercury speciation
the heating rate and accelerate the decomposition of mercury pollutants. A total mercury (THg) removal effi-
Low temperature remediation
ciency of 86.9% could be achieved at microwave irradiation of 400 W (ca. 350 °C) for 40 min with a GAC/Soil
mass ratio of 3:15. Moreover, the mutual transformation of five mercury fractions in the soils was also in-
vestigated to reveal the decomposition procedure. The environmental risk of THg remained in the soils was
largely reduced by increasing the percentage of inert fractions from 88.1% to 96.1%. Of special importance,
microwave irradiation greatly favoured the electric discharges of GAC, which produced molecular heating re-
sources with excessively higher temperature than the overall soils to realize low damage to soils. Meanwhile, the
specific bulk heating mode reduced the temperature barriers to allow easy release of decomposed mercury
vapours. Furthermore, GAC additives showed negligible changes during the whole decontamination process and
the increase of soil amounts did not affect the heating rate evidently. These results were remarkably promising to
provide fundamental information for practical scaling-up remediation of contaminated soils with high mercury
concentrations at relatively low temperatures that could be both convenient and energy-efficient.

1. Introduction
Mercury is one of the most hazardous pollutants because of its
bioaccumulation, biological toxicity, and long residence time in the en-
vironment [1,2]. The various binding formations of mercury compounds
are likely to be transformed through redox reactions or microbial reac-
tions in soils, and will lead to health risk through diet, respiration, or skin
contact to the human body based on the bioaccumulation and
magnification effects [3,4]. With the increasing attention drawn from
many governments and international organizations, assessment and de-
contamination to the mercury polluted fields, i.e. after the relocation of
chemical industry plants, have become preconditions for further devel-
opment in order to satisfy different criterions [5].
In this context, a wide variety of treatments have been employed to
clean up mercury contaminated soils [1], including phytoremediation
[6], stabilization/solidification [7], soil washing [8], electrokinetic

⁎
Corresponding authors at: Fujian Provincial Key Laboratory of Soil Environmental Health and Regulation, College of Resources and Environment, Fujian Agriculture and Forestry
University, Fuzhou 350002, China.
E-mail addresses: caohailei@163.com (H.-L. Cao), jian_lu_fafu@163.com (J. Lü).

https://doi.org/10.1016/j.cej.2018.06.168
Received 8 February 2018; Received in revised form 15 May 2018; Accepted 25 June 2018
Available online 26 June 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
H.-L. Cao et al.
remediation [9], thermal treatment etc. Among them, thermal treat-
ment method is now applied not only in the lab-scale experiments
[10,11] but also in the engineering practice [12] owing to its high ef-
ficiency, convenient operation, and recyclable mercury compounds
[13]. The mercury compounds present in soils require different tem-
peratures to be released from the soil matrices. For example, the re-
moval of residual mercury typically requires temperature over 600 °C
[2,14]. Therefore, the development of thermal treatment method is
undoubtedly energetic for further popularization to overcome dis-
advantages, such as high energy consumption, enormous cost, and ir-
reversible damage to soil textures [3], as far as traditional thermal
desorption is concerned.
In order to reduce physicochemical property variation of soils,
moderate and low temperature thermal treatments (100–350 °C) [15]
turn into realistic demands. Through the addition of inexpensive and
harmless chemical agents to soils, mercury fractions that are difficult to
decompose can be transformed into other less volatile species, such as
HgCl2 and Hg2Cl2. Due to the relatively low boiling point and decom-
position temperature of those mercury species, the soil decontamina-
tion temperature can thus be effectively lowered to ca. 400 °C [16,17].
In addition, microwave technology [18,19] has been introduced as
an alternative to the traditional thermal treatment to realize energy-
saving and low-cost remediation of contaminated soils [20]. Microwave
is able to significantly enhance the reaction efficiency [21] according to
specific volumetric heating modes, selective heating characteristics,
hotspots, and non-thermal effects [22,23]. Consequently, the time and
cost of soil remediation using microwave could be reduced for more
than 50% in contrast to those via conventional heating methods. Mi-
crowave (2.45 GHz) heating relies mostly on the dielectric loss factor of
the materials, that is, substances with large values of loss factor are
good microwave absorbers and are rapidly heated in the electro-
magnetic field, and the heating rate (ΔT/Δt [°C·min−1]) is given by the
following equation:
ΔT 2πfε0 ε′ ′ |E 2|
=
Δt Cρ·ρ (1)
where f is the microwave frequency (Hz); ε0 is the permittivity of free
space (8.85 × 10−12 F·m−1); ε″ is the dielectric loss factor; E is the
internal electric field (V·m−1); Cp is the heat capacity of the medium
(KJ·kg−1·°C−1); ρ is the density of the medium (kg·m−3) [24].
In order to improve the microwave absorption efficiency and reac-
tion temperature of soils, various microwave absorbents, such as MnO2,
Fe3O4, activated carbon (AC) etc. have been introduced to the soil
matrices [22,25]. The addition of microwave absorbent with high po-
larity could further accelerate heating rate and subsequently improve
the remediation efficiency. More recently, in situ microwave-assisted
soil remediation has been applicable thanks to the development of
large-scale microwave apparatus [26].
Given the above considerations, we focus on the exploration of viable
pathways for mercury removal in contaminated soils at relatively low
temperatures. Herein, a microwave-induced thermal remediation method
has been advanced to achieve effective decontamination of mercury
contaminated soils at ca. 300–350 °C, in the presence of granular acti-
vated carbon (GAC) as microwave absorbent. The GAC dosage and con-
dition of microwave irradiation for soil remediation have been in-
vestigated as main influential factors deciding mercury removal and
speciation transformation at bench-scale. Furthermore, the interplay
among microwave irradiation, GAC, and soil matrices has been revealed
to interpret the possible mechanism of this new methodology.
2. Material and methods
2.1. Soil sampling
Mercury polluted soil samples (average total mercury (THg)
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concentration of 234.2 mg kg−1) were collected from mercury mining
sites (N:27°32′3.13″, E:109°14′14.86″, Wanshan District, Tongren City,
Guizhou Province, China) at ca. 0–20 cm depths. Samples collected
from five serpentine points were mixed and then chosen by inquarta-
tion. Plant roots and visible foreign matter were removed manually
from the samples. After air-drying and sieving (20 meshes), the soil
samples were reserved in plastic bottles for further characterization and
microwave treatment.
2.2. Determination of mercury speciation in soil samples by sequential
chemical extraction
A modified Tessier sequential extraction procedure [27] was per-
formed to analyze the mercury speciation in soil samples treated at
various temperatures and irradiation time. Soils before and after
treatments were separated through sieving to screen the GAC, and
mixed thoroughly for homogenization. The procedure included the
following steps: (a) 1.0 g of soil was accurately weighed into a cen-
trifuge tube and shaken in 8.0 mL Mg(NO3)2 solution (1.0 mol·L−1) for
1 h at room temperature. The exchangeable fraction of mercury (F1)
was obtained after centrifugation; (b) the above residue was transferred
into 8.0 mL NaAC solution (1.0 mol·L−1) and shaken for another 5 h at
room temperature, and the specially sorbed fraction of mercury (F2)
was obtained after centrifugation; (c) by shaking the residue under
96 °C for 6 h in 20 mL NH2OH·HCl solution (0.4 mol·L−1) in a water
bath, the oxide bound fraction (F3) was obtained after centrifugation;
(d) by shaking the residue in 8 mL H2O2 in a water bath at 80 °C for 2 h,
and adding 3 mL H2O2 and shaking in the water bath at 80 °C for an-
other 3 h. The organic bound fraction (F4) was obtained after cen-
trifugation; (e) the residue was finally digested in 10 mL aqua regia at
95 °C in a water bath for 2 h, and the residual fraction (F5) was ob-
tained. The mercury concentration was determined by using a cold
atomic fluorescence spectrometry at 253.7 nm (AF-610B, Ruili Analy-
tical Ltd. Corp., Beijing, China). Each test was repeated for 3 times and
the standard deviation was ± 50%, ± 20%, ± 10% for results
being < 0.02, 0.02–0.3, and > 0.3 mg.kg−1, respectively, according to
the precision of the method.
2.3. Characterization
The pH was measured by using a pH meter (Sartorius, PB-10,
Germany) in ultrapure water with a soild to liquid ratio of 1:2.5 ac-
cording to a National Standard of China (No.: GB 15618-1995). The
total organic carbon (TOC) was determined on an organic element
analyzer (Elementar, vario Max cube, Germany). The soil texture was
determined according to the particle size distribution determined on a
laser particle size analyser (Bettersize, BT-9300ST, China). Thermal
decomposition behaviour of the soil samples were recorded using a
thermogravimetric analyser (TGA, Netzsch STA449C, Germany) in the
temperature range of 30 °C to 1000 °C under argon atmosphere with a
heating rate of 5 °C min−1. Specific surface area, pore volume, and pore
size of the soil samples were measured using Micrometritics TriStar II
3020 (USA) and calculated based on the N2 adsorption/desorption
isotherms. Scanning electron microscopy (SEM) images and energy
dispersive spectrometer (EDS) mapping of GAC were obtained using
scanning electron microscope (Phenom Prox-SED, Netherland). Total
mercury (THg) concentration of the soil samples was determined on a
fluorescence spectrometry at 253.7 nm (Ruili, AF-610B, China) after
digested in aqua regia at 100 °C in boiling water bath for 2 h, according
to a National Standard of China (No: GB/T 22105.1-2008).
2.4. Microwave-induced thermal treatment
Granular activated carbon (GAC, coal based, with average particle
size of 0.9 mm, specific surface area of 321.2 m2 g−1) was mixed with
6.0 g polluted soil samples (grounded to pass 40 meshes sieve) and put
H.-L. Cao et al.
into a three-necked flask. The mixture was then placed into a 2.45 GHz
microwave reactor (MAS-II, Xinyi Ltd. Corp., China) under set power
(ranging from 300 W to 600 W) and temperature (from 150 °C to
350 °C). After reaching the programmed reaction temperature, the soil
was kept under microwave irradiation for a certain time (0–60 min).
The power of microwave irradiation was auto-regulated and monitored
through a temperature feedback system. The temperature change of
soils was measured using an infrared thermometer, and the temperature
distribution was recorded using an infrared thermal imager (Ti450,
Fluke Corp., USA) immediately after thermal treatment. The con-
centration of mercury (CHg, μg·m−3) in the effluent during thermal
treatment was detected spontaneously using a mercury vapour monitor
(VM-3000, Mercury Instruments GmbH, Germany). The vaporized gas
was condensed in a cold trap and finally flew through an adsorption
tank filled with activated carbon to fully remove the residual pollutants.
3. Results and discussion
3.1. Microwave-induced thermal treatment of mercury polluted soil samples
with GAC
3.1.1. Influence of GAC addition
The pristine soil samples are of weak microwave absorbents under
direct microwave irradiation and could barely reach a reaction tem-
perature (230 °C at 800 W irradiation, Fig. 1a) for sufficient mercury
removal. Accordingly the total mercury (THg) removal efficiency
reached a maximum of around 37% (Fig. 1b) by employing microwave
irradiation (800 W) for over 45 min. The soil texture classified as sandy
loam (compromising of 67. 7% sand, 28. 4% silt and 3.9% clay) is of
low ε″ (between 0.4 and 1.2 under 2.45 GHz at 20 °C), and thus the
temperature increasing rate (ΔT/Δt) was slow according to Eq. (1).
Besides, the ε″ would fall dramatically according to the temperature
increasing, and the final reaction temperature would be constant even
after long microwave irradiation [28].
Concerning cost and technical operability of the process, GAC
(20–40 mesh numbers, ε″ ca. 30 under 2.45 GHz at 20 °C) [29] was used
to increase the microwave absorption efficiency of soils. It was
Fig. 1. Temperature profile and THg removal efficiency without (a and b) or with (c and d) the addition of GAC at 400 W microwave irradiation and a set reaction
temperature of 300 °C (Rm represents mass ratio of GAC/soil).
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remarkable that small amount of GAC/Soil (mass ratio, 1:15) could
effectively raise the final temperature of soil matrices from ca. 150 °C to
ca. 220 °C at 400 W microwave irradiation and significantly increase
the released mercury vapour in comparison with the control experiment
without GAC (as shown in Fig. S1).
GAC/Soil mass ratio (Rm) was further studied to investigate the
impacts to temperature profiles and to the total mercury (THg) removal
under a set reaction temperature of 300 °C. As shown in Fig. 1c, high Rm
generally accounted for an increased heating rate and shortened time
demanded to reach the set reaction temperature. It was found that a
minimum Rm of 2:15 was required to reach the set reaction temperature
of 300 °C. Further increase of Rm, i.e. from 2:15 to 5:15, could sig-
nificantly shorten the time demanded to reach the reaction temperature
at 400 W microwave irradiation (Fig. 1c). Accordingly, the THg removal
efficiency increased rapidly with the addition of GAC, and reached a
maximum value of ca. 80.1% at a Rm of 3:15 (Fig. 1d). Successive ad-
dition of GAC (in dosages of 4:15 and 5:15) might lead to special mi-
crowave adsorption effect concentrate mainly on GAC components
[30], by which the spontaneous bulk heating mode could completely
switch to the heating diffusion mode, equivalent to the conventional
heating method. In such a way, the specific microwave effect was lar-
gely reduced or even vanished with excessive GAC addition. Besides,
overdose of GAC utilization might extend the releasing path, and result
in the decrease of THg removal efficiency.
3.1.2. Influence of reaction temperature
The thermogravimetry was first carried out to obtain the thermal
decomposition characteristics of the pristine soil samples. As shown in
Fig. 2a, four major DTG peaks attributable to the loss of water (before
200 °C), the pyrolysis of soil organic matters (SOMs) and the release of
low volatile mercury species (220–720 °C) were recognized [14]. Of
special note, the quick weight loss after 400 °C indicates high tem-
perature may result in the fast loss of SOMs and thus the damage to soils
occurs at high temperature in view of the change on their physico-
chemical properties. Therefore, influence of temperature below 400 °C
on the removal of mercury compounds were tested based on the ex-
periments conducted under 400 W microwave irradiation.
H.-L. Cao et al.
Fig. 2. (a) TG-DTG curves of a representative soil sample; (b) temperature monitoring plots at set temperatures from 150 to 350 °C (inset is a magnification of
heating duration set at 300 °C); and (c) total mercury (THg) removal at various temperatures.
As expected, increase of reaction temperature was effective for en-
hanced THg removal efficiency. The temperature profiles plotted in Fig. 2b
suggested that longer time was generally needed to reach a higher reac-
tion temperature. In addition, the THg removal efficiency increased ra-
pidly with temperature increase, and the preferable temperature range
was determined to be 300–350 °C, which was significantly lowered [31]
by microwave-induced thermal treatment in the presence of GAC, with a
THg removal over 86.8% (Fig. 2c). However, treatment with higher
temperature is not preferable since heating can lead to the production of
harmful by-products (i.e. dioxins) apart from the total damage to soil
physical-chemical characteristics [32]. As far as the energy consumption
and removal efficiency were concerned, a set temperature of 300 °C was
selected for further investigation on the influence of microwave power
and irradiation time to the THg removal efficiency.
3.1.3. Influence of microwave irradiation power and time
Microwave irradiation is able to realize simultaneously bulk heating
in the whole penetrating depth to convert kinetic energy of the mole-
cules into heat energy. At a given frequency, the energy absorbed is
related to the electric field strength [33] and irradiation time. The
temperature increase curve and removal of mercury under various ir-
radiation power and time were investigated.
As shown in Fig. 3a, irradiation power ranged from 300 W to 600 W
was necessary to reach and maintain a set reaction temperature of
300 °C. The highest THg removal efficiency was obtained at a micro-
wave irradiation power of 400 W (Fig. 3b, the red line), and higher
irradiation power contributed to a comparable total removal of mercury
in a shortened reaction time as the time demanded to achieve the set
temperature 300 °C was reduced (Fig. 3b, the column bar). However,
application of higher irradiation power, i.e. at 500 W and 600 W, might
result in less controllable reaction processes, and microwave surplus
could cause unnecessary damage to the reactor. Therefore, medium
irradiation power (400 W) was viable for future applications.
Effects of microwave irradiation time to the removal of different
mercury fractions in soils were studied at 400 W, as plotted in Fig. 3c.
The THg removal efficiency increased gradually from ca. 54.2% to ca.
82.9% within 1 h. In this condition, soil treatment for 40 min, giving a
residual THg of ca. 46.7 mg kg−1, could easily satisfy the National
Standard of Soil Quality Assessment for Exhibition Sites in China (HJ
Fig. 3. (a) Temperature profiles at various irradiation powers; (b) time demanded to achieve 300 °C and THg removal at various powers; and (c) THg removal
efficiency with irradiation time.
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350-2007) for future development as exhibition sites, green area,
commercial land and public municipal land.
3.2. Evolution of mercury speciation
Evolution of the mercury speciation during soil treatment was fur-
ther investigated based on the results obtained from the sequential
chemical extraction. Herein, five mercury fractions, namely the ex-
changeable fraction (F1), the specially sorbed fraction (F2), the oxide
bound fraction (F3), the organic bound fraction (F4) and the residual
fraction (F5), were extensively studied.
As shown in Fig. 4, the detected concentration of F1, F3, F4 and F5
decreased gradually with the increase of temperature, whereas the con-
centration of F2 displayed a wavy plot with a maximum at ca. 200 °C. Of
special notice, the detected F1 and F3 contents below 200 °C were con-
siderably higher in comparison with that of pristine soil samples. It was
possible that transformation of mercury compounds from F3/F4/F5 to F1
and F2 took place owing to the interaction of microwave irradiation and
GAC which resulted in the higher concentration of F1 and F2 than the
pristine soil. Moreover, mutual transformation of mercury fractions might
occur during this stage, which was responsible for the relatively slow
temperature increase (stage 2; Fig. 2b, inset) and the concentration valley
between 500 and 800 s in the released gaseous atmosphere (Fig. 5). It is
noteworthy that the residual fraction (F5) increased from ca. 88.4% (in
pristine soils) to ca. 94.0% and ca. 96.1% after microwave-induced
thermal treatment at 300 °C and 350 °C for 40 min, respectively, sug-
gesting a lowered environmental risk.
Effect of irradiation time on the mercury speciation was also eval-
uated and plotted in Fig. 6. It was clear that the concentration of F5
decreased gradually with time, while the other four fractions showed
serious fluctuation over the whole treatment process. The residual
fraction (F5) was speculated to interact with air and soil components,
i.e. organic matters or the added GAC, through microwave induced
thermal treatment at a starting stage to form mercury fractions that
could be removed more easily. Following reciprocal transformation of
the five mercury fractions showed a dynamic alteration with regards to
the contents extracted from the soil samples, of which the residual
fraction was remarkably improved to ca. 96.9% within 50 min of mi-
crowave induced thermal treatment.
H.-L. Cao et al.
Fig. 4. The removal of mercury fractions at various temperatures (dotted lines represent the initial concentration of mercury fractions in the pristine soil samples).
Fig. 5. CHg detected in the released vapour with the irradiation time.
3.3. Removal process
The microwave induced thermal treatment process was tentatively
divided into four distinguishable stages based on the temperature and
mercury release profiles: i) the rapid desorption stage defines the removal
of mercury compounds which can be easily desorpted (ie. HgCl2,
Hg2Cl2, HgBr2, etc.) from room temperature to ca. 185 °C; ii) the
transformation stage defines mercury compounds to be transferred to
other speciation from ca. 185 °C to ca. 200 °C, in which the detected CHg
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Chemical Engineering Journal 351 (2018) 1067–1075
of certain mercury fractions starts to decrease while temperature re-
mains almost unchanged; iii) the decomposition stage defines the deso-
rption of HgS cinnerbar (red) or other mercury compounds which are
difficult to be decomposed (i.e. HgO, HgSO4, etc.) from the soil matrices
[30,34]; iv) the specific vibrating stage defines a stage reaching the set
reaction temperature, in which the microwave power auto-adjusts to
maintain the required temperature. In this stage, the mercury con-
centration in the desorption effluent can vibrate greatly as demon-
strated in Fig. 5 which is significantly different from that obtained via
conventional heating method [35]. In particular, the mercury con-
centration in the effluent drops rapidly when power turns down, and
vice versa. Overall, microwave irradiation is effective in continuously
driving mercury pollutants out of the systems.
3.4. Soil organic matters
The content of total organic carbon (TOC) in the soil was detected to
evaluate the effect of irradiation temperature and time on the soil or-
ganic matters (SOMs). As shown in Fig. 7a, the content of SOMs re-
duced ca. 19.2% after microwave irradiation at 300 °C for 10 min.
Further microwave irradiation showed negligible decrease of SOMs. As
far as the reaction temperature was concerned (Fig. 7b), the content of
SOMs decreased gradually with temperature increasing from 150 °C to
350 °C. Even though, only 29.2% of SOMs loss was observed under
microwave irradiation for 30 min at 350 °C, which is overall superior to
conventional heating methods that revealed 35–65% of SOM loss [36].
H.-L. Cao et al. Chemical Engineering Journal 351 (2018) 1067–1075

Fig. 6. The removal of mercury fractions with time (dotted lines represent the initial concentration of mercury fractions in the pristine soil samples).

3.5. Synergetic effects of microwave irradiation and GAC
EDS analysis demonstrated no specific mercury characteristics in
GAC recovered after the thermal treatment (Fig. 8 and Table S1).
However, GAC is known to stabilize mercury compounds in soils to
satisfy the toxicity characteristic leaching procedure (TCLP) to reduce
environmental risk [37]. In this context, we deduced that GAC plays a
key role of initiator, instead of stabilizer, for inducing specific micro-
wave effects to remove mercury at low temperature. In fact, tempera-
ture distribution in microwave irradiation systems is rather complicated
due to the significantly different dielectric loss factors of the compo-
nents in soil samples. In addition to the examination of central tem-
perature in soil matrices by using the infrared testing method, a thermal
infrared imager was applied to probe the overall temperature dis-
tribution (Fig. S2). The surface temperature determined by a thermal
infrared imager varied largely, from ca. 160 °C to ca. 220 °C, while the
central temperature measured using an infrared thermometer was
around 280 °C. It was clear that the interior temperature was much
higher (over 60 °C) than the exterior temperature although microwave
could heat the reaction system simultaneously. In this way, the external
heat transfer resistance would be eliminated and the off gas would
migrate out from the soil matrices much easier than using the tradi-
tional heating method due to the temperature gradient [38].
Besides, carbon [39] or other microwave absorbers [40] are prone
to exhibit electric discharges under microwave irradiation to form
hotspots [41]. Arcing phenomena could be observed at the edge of

Fig. 7. Effect of irradiation temperature (a) and time (b) on the content of SOMs.

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H.-L. Cao et al.
Fig. 8. Surface EDS analysis to the recycled GAC after thermal treatments.
these materials during the heating process (Video_clip_S1), and hotspots
are easily generated under this circumstance. It is concluded that short
operational time together with the generated hotspots prevented mer-
cury compounds from accumulating on GAC. In other words, the partial
overheating zones behave as molecular heating sources that can be
100–300 °C higher than the overall temperature [42]. These areas are
beneficial to induce the residual mercury compounds to be transferred
into other fractions that are easily desorpted. Moreover, the ultra-high
temperature at the edge of GAC prevents the attachment of mercury
compounds, and keeps the GAC non-toxic and harmless. In short,
elimination of the thermal barrier, together with the generation of
hotspots, are responsible for the efficient decontamination of mercury
polluted soil samples at low temperature of ca. 300 °C.
Video S1.
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Chemical Engineering Journal 351 (2018) 1067–1075
3.6. Cost estimation and influence to the GAC property
The energy consumption (as shown in Fig. S4) was preliminarily
calculated according to the integration of output power (the output
power was ca. 70% of that input power [43]) versus time. It was de-
termined that 0.17 kW·h (ca. 0.022 USD) [17] was demanded to treat
6.0 g contaminated soil with 1.2 g GAC to obtain 86.9% of mercury
removal, whereas 0.57 kW·h (ca. 0.074 USD) was demanded without
GAC to obtain 22.3% of mercury removal. In other words, microwave
induced treatment with the addition of GAC was able to cut ca. 70.3%
of energy consumption to achieve approximately three times of mer-
cury removal efficiency, compared to that without GAC. The cost of
GAC of 20–40 meshes was ca. 786 USD per ton, which was ca.
9.4 × 10−4 USD in the lab-scale experiments with ca. 4.3% of energy
H.-L. Cao et al.
consumption. Overall, the preliminary cost estimation suggested that
the GAC addition helped to provide a cost effective and removal effi-
cient method for the decontamination of mercury contaminated soils.
Moreover, SEM images of GAC separated from soil samples showed
negligible change on the surface morphology after microwave irradia-
tion (Fig. S3). Further BET analysis revealed that the specific surface
area remained nearly unchanged and the pore size and the pore volume
decreased slightly possibly due to the local ashing of GAC upon mi-
crowave heating. The GAC after the treatment could either recovered
from the soil by simple sieving for further utilization as the morphology
was barely affected, or remain in the soil to without bringing secondary
pollution to the environment.
4. Conclusions
In this study, microwave-induced thermal remediation of con-
taminated soils with high Hg concentration has been achieved at rela-
tively low temperature (300–350 °C) through the addition of granular
activated carbon (GAC) as the microwave absorbent. A total mercury
(THg) removal efficiency as high as 86.9%, with an increased percentage
(96.1%) of residual fractions, has been realized after microwave irra-
diation at 400 W for 40 min, by which the environmental risk is largely
reduced. Four distinguishable stages have been recognized to rationa-
lize the mercury removal process. The mercury fractions of F3/F4/F5
were found to transform into F1 or F2, the less volatile species that
could be removed at low temperature, during the microwave induced
treatment assisted with GAC. The GAC with high polarity behaves as
microwave absorbent and tends to produce electric discharges at the
edge of substances to form hotspots through the selective heating mode
under microwave irradiation. The mercury compounds in contaminated
soils could be fast eliminated according to the identical temperature
gradient and diffusing velocity and direction by means of specific bulk
heating mode. It has also been demonstrated that the GAC additive after
soil remediation contains no mercury residues and is harmless to the
environment. In comparison to conventional thermal treatment
methods, the microwave-induced thermal treatment with the addition
of GAC provides a more efficient and less harmful platform for the re-
mediation of mercury polluted soils, due to its relatively low reaction
temperature and energy consumption, which shows prospective po-
tentials in future engineering applications.
Acknowledgements
The authors gratefully acknowledge the National Natural Science
Foundation of China (NSFC, Grant 91622114), the National Key
Research and Development Program of China (Grant
2017YFD0800900), the State Key Laboratory of Structural Chemistry
(Grant 20170032), the Foundation of Fujian Educational Committee
(Grant JA15150), the New Century Excellent Talents in Fujian Province
University, and the International Science and Technology Cooperation
and Exchange Project of Fujian Agriculture and Forestry University
(Grant KXGH17010) for funding. We thank Prof. Christopher Rensing
(Fujian Agriculture and Forestry University, China) for his help with
proof reading.
References
[1] J. Wang, X. Feng, C.W.N. Anderson, Y. Xing, L. Shang, Remediation of mercury
contaminated sites-a review, J. Hazard. Mater. 221–222 (2012) 1–18.
[2] T.C. Chang, J.H. Yen, On-site mercury-contaminated soils remediation by using
thermal desorption technology, J. Hazard. Mater B. 128 (2006) 208–217.
[3] C.L. Miller, D.B. Watson, B.P. Lester, K.A. Lowe, E.M. Pierce, Characterization of
soils from an industrial complex contaminated with elemental mercury, Environ.
Res. 125 (2013) 20–29.
[4] S.E. Rothenberg, L. Windham-Myers, J.E. Creswell, Rice, methylmercury exposure
1074
Chemical Engineering Journal 351 (2018) 1067–1075
and mitigation: A comprehensive review, Environ. Res. 133 (2014) 407–423.
[5] Y. Lin, R. Vogt, T. Larssen, Environmental mercury in China: a review, Environ.
Toxicol. Chem. 31 (2012) 2431–2444.
[6] J. Wang, J. Xia, X. Feng, Screening of chelating ligands to enhance mercury accu-
mulation from historically mercury-contaminated soils for phytoextraction, J.
Environ. Manage. 186 (2017) 233–239.
[7] D. O’Connor, T. Peng, G. Li, S. Wang, L. Duan, J. Mulder, G. Cornelissen, Z. Cheng,
S. Yang, D. Hou, Sulfur-modified rice husk biochar: A green method for the re-
mediation of mercury contaminated soil, Sci. Total Environ. 621 (2018) 819–826.
[8] J. Xu, D.D. Kleja, H. Biester, A. Lagerkvist, J. Kumpiene, Influence of particle size
distribution, organic carbon, pH and chlorides on washing of mercury contaminated
soil, Chemosphere 109 (2014) 99–105.
[9] M. Vocciante, R. Bagatin, S. Ferro, Enhancements in electrokinetic remediation
technology: focus on water management and wastewater recovery, Chem. Eng. J.
309 (2017) 708–716.
[10] A.M. Kunkel, J.J. Seibert, L.J. Elliott, R. Kelley, L.E. Katzet, Remediation of ele-
mental mercury using in situ thermal desorption, Environ. Sci. Technol. 40 (2006)
2384–2389.
[11] C.M. Park, L.E. Katz, H.M. Liljestrand, Mercury speciation during in situ thermal
desorption in soil, J. Hazard. Mater. 300 (2015) 624–632.
[12] T.C. Chang, S.J. You, B.S. Yu, C.M. Chen, Y.C. Chiu, Treating high-mercury-con-
taining lamps using full-scale thermal desorption technology, J. Hazard. Mater. 162
(2009) 967–972.
[13] J. Xu, A.G. Bravo, A. Lagerkvist, S. Bertilsson, R. SjÖblom, J. Kumpiene, Sources
and remediation techniques for mercury contaminated soil, Environ. Int. 74 (2015)
42–53.
[14] Y.T. Huang, Z.Y. Hseu, H.C. Hsi, Influences of thermal decontamination on mercury
removal, soil preoperties, and repartitioning of coexisting heavy metals,
Chemosphere 84 (2011) 1244–1249.
[15] A.L.N. Cruz, R.L. Cook, S.M. Lomnicki, B. Dellinger, Effect of low temperature
thermal treatment on soils contaminated with pentachlorophenol and en-
vironmentally persistent free radicals, Environ. Sci. Technol. 46 (2012) 5971–5978.
[16] F. Ma, Q. Zhang, D. Xu, D. Hou, F. Li, Q. Gu, Mercury removal from contaminated
soil by thermal treatment with FeCl3 at reduced temperature, Chemosphere 117
(2014) 388–393.
[17] F. Ma, C. Peng, D. Hou, B. Wu, Q. Zhang, F. Li, Q. Gu, Citric acid facilitated thermal
treatment: an innovative method for the remediation of mercury contaminated soil,
J. Hazard. Mater. 300 (2015) 546–552.
[18] Z. Kawala, T. Atamanczuk, Microwave-enhanced thermal decontamination of soil,
Environ. Sci. Technol. 32 (1998) 2602–2607.
[19] R.A. Abramovitch, C.Q. Lu, E. Hicks, J. Sinard, In situ remediation of soils con-
taminated with toxic metal ions using microwave energy, Chemosphere 53 (2003)
1077–1085.
[20] P.P. Falciglia, G. Urso, F.G.A. Vagliasindi, Microwave heating remediation of soils
contaminated with diesel fuel, J. Soil. Sediment. 13 (2013) 1396–1407.
[21] H. Lei, S. Ren, L. Wang, Q. Bu, J. Julson, Microwave pyrolysis of distillers dried
grain with solubles (DDGS) for biofuel production, Bioresour. Technol. 102 (2011)
6208–6213.
[22] X. Liu, G. Yu, Combined effect of microwave and activated carbon on the re-
mediation of polychlorinated biphenyl-contaminated soil, Chemosphere 63 (2006)
228–235.
[23] N. Wang, P. Wang, Study and application status of microwave in organic waste-
water treatment – A review, Chem. Eng. J. 283 (2016) 193–214.
[24] P.P. Falciglia, G.D. Guidi, A. Catalfo, F.G.A. Vagliasindi, Remediation of soils con-
taminated with PAHs and nitro-PAHs using microwave irradiation, Chem. Eng. J.
296 (2016) 162–172.
[25] G.Y. Huang, L. Zhao, Y.H. Dong, Q. Zhang, Remediation of soils contaminated with
polychlorinated biphenyls by microwave-irradiated manganese dioxide, J. Hazard.
Mater. 186 (2011) 128–132.
[26] A.A. Barba, D. Acierno, M. D’Admore, Use of microwaves for in-situ removal of
pollutant compounds from solid matrices, J. Hazard. Mater. 207–208 (2012)
128–135.
[27] Z. Bao, J. Wang, X. Feng, L. Shang, Distribution of mercury speciation in polluted
soils of Wanshan mercury mining area in Guizhou, Chin. J. Ecol. 30 (2011)
907–913.
[28] J.P. Robinson, S.W. Kingman, C.E. Snape, H. Shang, R. Barranco, Separation of
polyaromatic hydrocarbons from contaminated soils using microwave heating, Sep.
Purif. Technol. 69 (2009) 249–254.
[29] H. Liu, L. Xu, Y. Jin, B. Fan, X. Qiao, Y. Yang, Effect of coal rank on structure and
dielectric properties of chars, Fuel 153 (2015) 249–256.
[30] D. Obermayer, B. Gutmann, C.O. Kappe, Microwave chemistry in silicon carbide
reaction vials: separating thermal from nonthermal effects, Angew. Chem. Int. Ed.
48 (2009) 8321–8324.
[31] A.B. Navarro, I. Canadas, D. Martinez, J. Rodriguez, J.L. Mendoza, Application of
solar thermal desorption to remediation of mercury-contaminated soils, Sol. Energy
83 (2009) 1405–1414.
[32] C. Comuzzi, B. Lesa, E. Aneggi, G. Dolcetti, D. Goi, Salt-assisted thermal desorption
of mercury from contaminated dredging sludge, J. Hazard. Mater. 193 (2011)
177–182.
[33] S.U. Bayca, Microwave radiation leaching of colemanite in sulfuric acid solutions,
Sep. Purif. Technol. 105 (2013) 24–32.
[34] M. Rumayor, M.A. Lopez-Anton, M. Díaz-Somoano, M.M. Maroto-Valer, J.-
H. Richard, H. Biester, M.R. Martínez-Tarazona, A comparison of devices using
H.-L. Cao et al.
thermal desorption for mercury speciation in solids, Talanta 150 (2016) 272–277.
[35] M. Rumayor, M. Diaz-Somoano, M.A. Lopez-Anton, M.R. Martinez-Tarazona,
Mercury compounds characterization by thermal desorption, Talanta 114 (2013)
318–322.
[36] F. Tatano, F. Felici, F. Mangani, Lab-scale treatability tests for the thermal deso-
rption of hydrocarboncontaminated soils, Soil Sediment Contam. 22 (2013)
433–456.
[37] D. Hou, Q. Gu, F. Ma, S. O’Connell, Life cycle assessment comparison of thermal
desorption and stabilization/solidification of mercury contaminated soil on agri-
cultural land, J. Clean. Prod. 139 (2016) 949–956.
[38] J.I. Lombraña, R. Rodríguez, U. Ruiz, Microwave-drying of Sliced Mushroom.
Analysis of temperature control and pressure, Innov. Food Sci. Emerg. 11 (2010)
652–660.
[39] Z. Yang, H. Yi, X. Tang, S. Zhao, Q. Yu, F. Gao, Y. Zhou, J. Wang, Y. Huang, K. Yang,
1075
Chemical Engineering Journal 351 (2018) 1067–1075
Y. Shi, Potential demonstrations of ‘‘hotspots” presence by adsorption desorption of
toluene vapor onto granular activated carbon under microwave radiation, Chem.
Eng. J. 319 (2017) 191–199.
[40] J. Chen, H. Pan, H. Hou, H. Li, J. Yang, L. Wang, High efficient catalytic degradation
of PNP over Cu-bearing catalysts with microwave irradiation, Chem. Eng. J. 323
(2017) 444–454.
[41] W. Chen, B. Gutmann, C.O. Kappe, Characterization of microwave-induced electric
discharge phenomena in metal-solvent mixtures, Chem. Open 1 (2012) 39–48.
[42] A. de la Hoz, A. Diaz-Ortiz, A. Moreno, Microwaves in organic synthesis. Thermal
and non-thermal microwave effects, Chem. Soc. Rev. 34 (2005) 164–178.
[43] W.M. Cheng, G.S.V. Raghavan, M. Ngadi, N. Wang, Microwave power control
strategies on the drying process I. Development and evaluation of new microwave
drying system, J. Food Eng. 76 (2006) 188–194.