Geoderma 363 (2020) 114150

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Geoderma
journal homepage: www.elsevier.com/locate/geoderma

The kinetics of mercury vaporization in soil during low-temperature thermal T

treatment
Min-oh Parka, Moon-Hyun Kimb, Yongseok Honga,
⁎

a
Department of Environmental Engineering, Korea University Sejong Campus, Sejong City 30019, Republic of Korea
b
Department of Environmental Engineering, Daegu University, Geongsan-si 38453, Republic of Korea

ARTICLE INFO ABSTRACT

Handling Editor: David Laird Equilibrium vapor-phase Hg concentrations and vaporization kinetics at temperatures from 100 to 400 °C were
Keywords: evaluated in field soil naturally contaminated with Hg0, as well as sand artificially contaminated with HgCl2,
Thermal treatment HgO, and HgS. The calculated change in the standard enthalpy of Hg vaporization (ΔH0) was 4.73 ( ± 1.52),
Remediation 2.11 ( ± 0.17), 5.59 ( ± 0.25), and 4.87 ( ± 0.46) kcal mol−1 for naturally Hg0-contaminated field soil and sand
Hg-contaminated soil artificially contaminated with HgCl2, HgO, and HgS, respectively. The measured ΔH0 was 30% of the theoretical
Desorption kinetics ΔH0, which suggests that higher temperatures are required to remove Hg from contaminated soil when com-
pared to pure chemical states. Thermal vaporization and desorption kinetics tended to increase upon increasing
the temperature; however, the rates at 300 and 400 °C were similar to each other due to kinetic limitations. Our
theoretical calculations showed that 90% Hg removal from field contaminated soil at 100, 300, and 400 °C
would require 204 days, 3.5 h, and 2.7 h, respectively. At low temperature (i.e., approximately 100 °C), an
unrealistically long time was required for Hg removal from soil; however, increasing the temperature up to
400 °C did not necessarily decrease the remediation time. Thus, optimal remediation temperature needs to be
evaluated based on Hg thermal desorption and volatilization kinetics.

1. Introduction A number of remediation technologies, such as thermal treatment,

Over the past several decades, the toxic and persistent existence of
mercury in environments has given rise to significant health concerns for
humans (Biester et al., 2000; Rice et al., 2014; Skyllberg, 2010; Zhao et al.,
2016; Zhu et al., 2015). Soil can be contaminated with high levels of
mercury originating from various natural and anthropogenic sources, such
as gold mining and chlor-alkali production (UNEP, 2013). Many Hg spe-
cies such as Hg0, HgCl2, HgO, and HgS occur in soil. Further, their spe-
ciation can be affected by environmental redox reactions and adsorption,
as well as complexation with soil humic acids or with inorganic ligands
(Bollen et al., 2008; Kim et al., 2000; Miller et al., 2015; Miller et al.,
2013). HgCl2 is often observed in contaminated soils due to its frequent
industrial use. HgS, also known as cinnabar, is a widely-occurring geolo-
gical species in Hg mining areas. HgO is another Hg species that is often
found in soil; it is produced by the oxidation of Hg0 in spill sites and from
the readsorption of Hg2+ onto oxygen-containing functional groups (Liu
et al., 2011; Miller et al., 2015; Padak et al., 2006). Among the afore-
mentioned Hg species, Hg0 and HgCl2 are highly volatile and can evapo-
rate from soil; therefore, many health problems have been linked to Hg
exposure via inhalation (Baughman, 2006; Bollen et al., 2008).
electro-kinetics, soil flushing/washing, and phytoremediation, have
been applied to remove mercury from soils (He et al., 2015; USEPA,
2007). Sequential extraction methods have suggested that Hg in soils
has a low solubility in dilute acids (Bloom et al., 2003; Issaro et al.,
2009; Kim et al., 2000) and solution pH decrease to 3 only removed
0.3% of total Hg in soil, hence washing was considered to be ineffective
(Cox et al., 1996; Xu et al., 2014). Complexing ligands, such as iodine,
can be used to increase the solubility of Hg in water and promote
electro-kinetic remediation for removing Hg from soils (Cox et al.,
1996). However, this technique is considered to be ineffective as its Hg
removal efficiency is low and its energy demand is quite high (Sierra
et al., 2016). As an alternative, thermal treatment is considered a
promising technique for mercury removal from soils due to high vola-
tility (Park et al., 2015; Sierra et al., 2016).
Upon thermal treatment, soil temperature increases due to heat
conduction; this facilitates contaminant desorption, vaporization, and
removal by an induced gas flow (USEPA, 2007; Vidonish et al., 2016).
In-situ thermal desorption (ISTD) generally uses heating elements and
extraction wells to apply heat and vacuum, respectively; these two
treatments are carried out simultaneously to remove Hg from soil sub-

⁎
Corresponding author.
E-mail address: yongseokhong@korea.ac.kr (Y. Hong).

https://doi.org/10.1016/j.geoderma.2019.114150
Received 26 July 2019; Received in revised form 9 December 2019; Accepted 17 December 2019
Available online 20 January 2020
0016-7061/ © 2019 Elsevier B.V. All rights reserved.
M.-o. Park, et al.
surfaces (Kunkel et al., 2006). Ex-situ techniques generally rely on ro-
tary kiln-type reactors (Sierra et al., 2016; Taube et al., 2008). In both
types of methods, the temperature at which Hg species are vaporized to
gas is considered to be the most important parameter for removing Hg
from soil. Thermal treatment is generally categorized into low tem-
perature (100–350 °C), high temperature (350–600 °C), and destructive
temperature (600–1000 °C) subsets (Falciglia et al., 2011). Previous
studies have suggested that most Hg species found in contaminated soils
can be volatilized in the low-temperature range (Park et al., 2015;
Taube et al., 2008). The remediation potential of Hg-contaminated soil
by low-temperature thermal treatment has been further proved by Hg
pyrolysis experiments (Biester and Scholz, 1997; Reis et al., 2012; Reis
et al., 2015).
Thermodynamic speciation of mercury in soil and gas and de-
termining the temperature at which various Hg species vaporize is
necessary for developing cost-effective remediation strategies (Falciglia
et al., 2011; Smith et al., 2001; Taube et al., 2008). However, thermal
desorption and volatilization processes can be kinetically limited by
intra-particle and/or inter-particle diffusion processes (Lighty et al.,
1990) and these limitations are dependent on the temperature and
chemical status of Hg species in soil (Biester and Scholz, 1997; Falciglia
et al., 2011; Reis et al., 2015; Taube et al., 2008). Such complexities can
significantly affect remediation strategies, i.e., by increasing cost and
treatment time; however, little information is available on these aspects
in existing literature. Hence, in the present study, high-resolution ki-
netic rate constants are evaluated for various mercury species in low
temperature ranges (100–400 °C) to provide insights and fundamental
design parameters and concepts for Hg thermal treatment processes.
2. Materials and methods
2.1. Chemicals and reagents
All the chemicals and reagents used in the experiments described
Fig. 1. Schematic of the experimental setup for the thermal desorption of Hg-contaminated soils.
2
Geoderma 363 (2020) 114150
herein were ACS grade or trace metal grade. Field contaminated soils
were collected from a liquid Hg0 spill site in Korea. The soils were used
as capping materials to prevent the vaporization of Hg0 that con-
tinuously spilled in the basement of a light bulb factory for three
months. Thus, vapor-phase elemental Hg0 was the initial source of Hg
contamination. Soils were collected from the field and passed through a
2 mm sieve to remove large debris and pebbles, after which they were
stored in the dark in polypropylene containers until further use.
Sequential extraction was carried out on these soils to investigate Hg
distribution in various phases – water-soluble fraction 1 (deionized
water), weak acid-soluble fraction 2 (0.1 M CH3COOH + 0.01 M HCl),
organic chelated fraction 3 (1 M KOH), elemental Hg0 fraction 4 (12 M
HNO3), and sulfide-associated fraction 5 (7.5 mL concentrated
HCl + 2.5 mL concentrated HNO3) (Bloom et al., 2003; Kim et al.,
2003). In addition, field contaminated soil was further sieved through
250 μm and 63 μm sieves and Hg concentrations in sand, silt, and clay
fractions were measured by aqua regia extraction (7.5 mL concentrated
HCl + 2.5 mL concentrated HNO3) to investigate soil-particle size-de-
pendent Hg distribution. Artificially contaminated soils were prepared
by spiking HgCl2 (Acros), HgS (Sigma Aldrich), and HgO (Sigma Al-
drich) to extra pure quartz sand (Fisher Chemical). In the first step,
1000 mg Hg/kg sand was prepared by mixing the Hg chemical of in-
terest with 200 g of quartz sand in an end-over-end tumbler for 1 day.
Later, the sand was diluted 10 times by mixing 20 g of the prepared
mixture with 180 g of sand in the tumbler for 1 more day to achieve a
Hg concentration of 100 mg kg−1. The final spiking concentrations of
various Hg species were confirmed by aqua regia extraction.
2.2. Hg vaporization kinetic experiments
Mercury thermal desorption experiments were conducted in a
custom-built experimental setup (Fig. 1). More detailed schematics of
the setup are shown in Figs. S1 and S2. Experiments were conducted in
10 cm (length) × 7.0 mm (o.d) × 5.0 mm (i.d.) quartz column reactors
M.-o. Park, et al.
under two conditions – batch system without gas flow and continuous
system with nitrogen gas flow. A quartz column containing 0.1 g of Hg-
contaminated soil was heated using a 70 cm-long 22 gauge nichrome
wire coiled to a final length of 5 cm. Four quartz column reactors were
constructed, which allowed us to conduct four thermal desorption ex-
periments at once. The temperature of the quartz column reactor was
controlled by changing the voltage applied to the nichrome wire coil.
Temperature inside the quartz column was measured using high-tem-
perature K-type thermocouples with fiberglass insulation and connected
to a DAQ Pro 5300 portable meter (Omega, England). The relationship
between voltage applied to the wire coil and temperature of soil in the
quartz column was also determined in this study. The soil temperature
of soil was controlled in the range of 100 to 400 °C by controlling the
applied voltage.
For batch-type experiments, both sides of the quartz column were
tightly sealed with 5 mm-thick silicone septa. Temperature was in-
creased from 100 to 400 °C by controlling the applied voltage. After
30 min, during which the gas-phase Hg concentration equilibrated,
50 μL of the gas containing vapor-phase Hg samples in the head space
was sourced using a 50 μL needle-type SGE® gas tight syringe. The Hg
gas sample in the syringe was immediately purged into a KMnO4 so-
lution (prepared by mixing 1.8 g of KMnO4 (Sigma Aldrich), 7.5 mL of
trace-metal grade H2SO4 (Fisher), 7.5 mL of trace-metal grade HNO3
(Fisher), and 285 mL deionized water) at a flow rate of 20 mL min−1. In
the solution, vapor-phase Hg was absorbed and oxidized to Hg2+
(Wiatrowski et al., 2009). Hg levels in KMnO4 were determined using a
cold vapor-atomic fluorescence spectroscopy (CV-AFS) system
(BrooksRand, USA) according to the US EPA method 1631.
For thermal desorption kinetic experiments with N2 gas flow, one
end of the quartz column was connected to 99.9999% nitrogen gas
using an Aalborg® ball flow controller and the other end was connected
to a Hg trap made of gold beads (BrooksRand, USA). Later, the column
temperature was increased from 100 to 400 °C. Additionally, the ni-
trogen flow rate was regulated at 0.56, 5.6, and 56 mL min−1, which
was within the range of typical soil vapor extraction technology pro-
cesses (Dixon and Nichols, 2006).
Vaporized Hg was transported to the gold-coated glass bead trap by
N2 gas where volatilized Hg was captured. The trap was changed after
0.5, 1, 2, 3, 4, and 6 h to analyze time-dependent Hg vaporization. Hg
in the trap was thermally desorbed at 450 °C for 20 min and the va-
porized Hg was allowed to flow through 10 mL of KMnO4 for oxidation
and trapping; Hg trapped by these reactions was subsequently analyzed
using a CV-AFS system according to the US EPA method 1631. Time-
dependent Hg concentrations in soil were calculated by subtracting the
concentration of Hg captured in the gold bead trap and KMnO4 solution
from the initial Hg concentration in soil. To determine the mass balance
of Hg, the residual Hg in the soil was measured by aqua-regia extraction
after completion of 6-h thermal desorption.
2.3. Thermal treatment modeling
The released Hg was converted to residual Hg in soil from mass
balance calculation. Subsequently, the kinetics of Hg removal from soil
were modeled using the following equation (Falciglia et al., 2011),
C = C0exp ( kt n ) (1)
where C is Hg concentration in soil (mg kg−1) at time t (h), C0 is the
initial Hg concentration in soil (mg kg−1), and k is the thermal deso-
rption kinetic rate constant (h1/n); n is a parameter that represents the
non-linearity of thermal desorption kinetics. Taking natural log on both
sides of the equation would yield the following equation.
lnC = lnC0 kt n (2)
Using this equation, k and n were evaluated by a SigmaPlot® non-
linear least-squares method and the goodness of fit was evaluated in
terms of the correlation coefficient, R2.
3
Geoderma 363 (2020) 114150
3. Results
3.1. Thermal treatment – Temperature control
Controlling temperature in the quartz column reactor surrounded by
a nichrome wire coil was critical in evaluating Hg thermal treatment
kinetics. The results of temperature control are shown in Fig. S3.
Changes in temperature in response to changes in the applied voltage
were rapid and steady-state temperatures could be obtained within
3 min in the temperature range of 50 to 400 °C. In addition, steady-state
temperatures in the quartz tubing reactor were found to exhibit a linear
trend with respect to the applied voltage. The relationship between
applied voltage and soil temperature in the quartz column is as follows.
temp( °C) = 23.8 + 56.1 × voltage(V), R2 = 0.99 (3)
This observation confirmed that the custom-built experimental
setup was appropriate for our Hg thermal desorption experiments in
soils.
3.2. Field and laboratory Hg-contaminated soil
The average Hg concentration in the field contaminated soil was ap-
proximately 35.1 ( ± 0.78; i.e., standard deviation) mg kg−1. The frac-
tions of sand (250 μm < , < 2 mm), silt (63 μm < , < 250 μm), and clay
(63 μm <) were 79.1%, 19.2%, and 1.7%, respectively, and the total Hg
(THg) concentrations at these different sediment sizes were 29.4 ( ± 0.29),
53.5 ( ± 1.15), and 63.9 ( ± 0.21) mg kg−1, respectively. THg con-
centration was high in silt and clay fractions; however, the sandy fraction
also contained a high Hg concentration that exceeded the 10 mg kg−1
regulatory soil contamination limit mandated in Korea (http://eng.me.go.
kr/eng/web/index.do?menuId=311). Sequential extraction results from
fractions 1, 2, 3, 4, and 5 resulted in 1.47 ( ± 0.67), 0.03 ( ± 0.01), 0.63
( ± 0.25), 82.1 ( ± 6.9), and 15.8 ( ± 6.5) %, respectively, suggesting that
most of the Hg was strongly associated with the soil. The relatively high
levels of Hg in the sand fraction and poor Hg extraction in dilute acidic
solutions further suggested that solution-based remediation technologies
(e.g., soil washing and electro-kinetics) are not effective for Hg removal
from soil (Xu et al., 2014). In the case of artificially contaminated sand,
THg concentrations in HgCl2, HgO, and HgS-spiked quartz sands were
97.2 ( ± 2.43), 93.4 ( ± 3.45), and 104.0 ( ± 7.6) mg kg−1, respectively
(these values were obtained from four replicates). It must be noted that
these values were close to the target concentration of 100 mg kg−1, which
implies that the Hg spiking method produced relatively homogeneous Hg-
contaminated soil.
3.3. Hg thermal treatment in the batch system
The kinetics of Hg desorption and vaporization at 200 °C for Hg-
contaminated soils are shown in Fig. S4 and Table S1. In the closed
system, vapor-phase Hg concentrations reached equilibrium within
40 min. The first-order rate constants for field contaminated soil and
HgCl2, HgO, and HgS-spiked sand were 0.05, 0.04, 0.034, and
0.041 min−1, respectively, suggesting that the desorption kinetics were
distributed in a relatively narrow range within a factor of two. How-
ever, equilibrium gas-phase Hg concentrations varied by an order of
magnitude, i.e., 0.65, 1.2, 0.14, and 0.15 g m−3 for Hg-contaminated
soil and HgCl2, HgO, and HgS-spiked sand, respectively, at 200 °C.
Equilibrium gas-phase Hg concentrations were further evaluated at
various temperatures and the results are shown in Fig. 2(A). The figure
shows that the measured concentrations increased upon increasing the
temperature. Hg concentrations measured in the gas phase were similar
for field contaminated soil and HgCl2-spiked sand; they varied from 0.2
to 2 g m−3 when the temperature was increased from 100 to 400 °C. Hg
concentrations measured in the gas phase for HgO and HgS-spiked sand
were similar and they were about an order of magnitude lower than
those of field contaminated soil and HgCl2-spiked sand. Using the
M.-o. Park, et al. Geoderma 363 (2020) 114150

10 8
(A) 0 0
H measured =0.31* H theoretical -3.9
Hg conc. in gas phase (g m-3)

2
r =0.98

(kcal mol )
6

-1
1
Hg0 HgS
4 contaminated HgO
soil

measured
0.1 soil
HgCl2

0
2

H
HgO
HgS HgCl2
0.01
0 100 200 300 400 500 0
12 15 18 21 24 27 30 33
Temperature (oC) 0 -1
H theoretical (kcal mol )
Fig. 3. Comparison between theoretically calculated ΔH0 of pure chemicals and
106 experimentally measured ΔH0 for field Hg0-contaminated soil and HgCl2, HgO,
(B) and HgS-spiked sand.
Hg conc. in gas phase (g m )
-3

103
ΔH0 values corresponding to Hg vaporization were 4.73 ( ± 1.52),
2.11 ( ± 0.17), 5.59 ( ± 0.25), and 4.87 ( ± 0.46) kcal mol−1 for field
100 contaminated soil and HgCl2-, HgO-, and HgS-spiked sand, respectively.
These positive values indicate that the thermal treatment processes
were endothermic; thus, an increase in temperature would enhance Hg
10-3 0 removal from soil. The measured ΔH0 values were compared with the
Hg
HgCl2 theoretical ΔH0 values of pure Hg compounds, as illustrated in Fig. 3. A
low ΔH0 value indicates that a higher Hg vaporization can be achieved
10-6 HgO
HgS in response to small changes in temperature. Therefore, compounds like
HgCl2 could be effectively removed by slight temperature increases.
10-9 However, compounds such as HgO and HgS require larger increases in
0 100 200 300 400 500 temperature to achieve Hg vaporization and removal. Overall, the
o measured ΔH0 accounted for only 30% of the theoretical estimations,
Temperature ( C)
suggesting that higher temperatures are required to remove Hg from
Fig. 2. (A) Experimentally determined and (B) theoretically calculated vapor- contaminated soil when compared to Hg in pure chemical states. The
phase Hg concentrations in Hg0-contaminated soils and HgCl2, HgO, and HgS- presence of soil may be responsible for these lower standard enthalpy
spiked sand. values. Notably, a similar result was reported in an earlier study
whereby temperatures higher than those theoretically calculated were
Table 1
required to volatilize mercury compounds in soils (He et al., 2015).
Phase transition reactions of Hg and the related thermodynamic values.
Reactions Log K (25 °C) ΔH0 (kcal mol−1) 3.4. Hg thermal treatment in the gas flowing system

Hg0(l) = Hg0(g) –5.59 14.67 The temperature-dependent and species-dependent thermal deso-
HgCl2(s) = HgCl2(g) –6.84 20.04
rption kinetic behaviors of Hg are summarized in Fig. 4. After com-
HgO(s) = HgO(g) –14.41 31.70
HgS(s) = HgS(g) –13.64 27.57 pleting 6 h-long thermal desorption experiments, residual Hg con-
centrations in different soils were measured by aqua regia digestion.
Mass balance calculation was performed by adding the mass of residual
equations shown in Table 1, the vapor-phase Hg concentrations of pure Hg adsorbed in soil to the mass of thermally desorbed Hg in KMnO4
Hg chemicals, such as Hg0, HgCl2, HgO, and HgS, were calculated solution; the obtained result showed that the mass balance is greater
(Fig. 2(B)). It can be observed that the measured gas-phase Hg con- than 90%. In general, below 300 °C, the desorption kinetics were slow
centrations were significantly lower (by 2 to 3 orders of magnitude) and at temperatures greater than 300 °C, the kinetics were particularly
than the theoretically calculated values. From the measured data, fast for the first two hours, after which they slowed down and exhibited
change in standard enthalpy, ΔH0, which represents the amount of heat significant non-linearity. Several other researchers also observed this
absorbed in the thermal desorption reaction was calculated using the trend in thermal desorption experiments (Barnier et al., 2014; Falciglia
following equation, et al., 2011; Smith et al., 2001; Tse and Lo, 2002).
As shown in Fig. 4(A), for the field contaminated soil, removal ki-
KT2 H 0 T1 T2 netics were relatively slow at ~100 and 150 °C and became rapid at
ln =
KT1 R T1 T2 (4) temperatures greater than 200 °C. However, at 200 °C, the kinetics were
slow and residual Hg concentration in the soils approached a plateau
where KT1 and KT2 are the equilibrium constants of phase-transition at ~10 mg kg−1. To remove 90% of Hg from soil, it may be necessary to
reactions at temperatures T1 (K) and T2 (K), respectively, ΔH0 is the increase the temperature to 300 °C; this operation resulted in a Hg re-
standard change in the enthalpy of the reaction (kcal mol−1), and R is moval of 3 mg kg−1 in 6 h. Increasing the temperature beyond 300 °C
the universal gas constant (0.00198 kcal K−1 mol−1). did not increase the rate of kinetics significantly and thermal desorption

4
M.-o. Park, et al. Geoderma 363 (2020) 114150

40 120
(A) soil (B) HgCl2
100
30
Hg in soil (mg kg )

Hg in soil (mg kg )
-1

-1
80

20 60

40
10
20

0 0
0 2 4 6 0 2 4 6
Time (h) Time (h)

120 120
(C) HgO (D) HgS
100 100
Hg in soil (mg kg )

Hg in soil (mg kg )
-1

-1
80 80

60 60

40 40

20 20

0 0
0 2 4 6 0 2 4 6
Time (h) Time (h)

100 oC
150 oC
200 oC
300 oC
400 oC

Fig. 4. Kinetics of Hg removal in (A) Hg0-contaminated soil and (B) HgCl2, (C) HgO, and (D) HgS-spiked sand at 100, 150, 200, 300, and 400 °C. The values shown
are the averages of four replicates; N2 flow rate to the quartz column was 5.6 mL min−1.

seemed to be kinetically limited. The kinetics of Hg removal from
HgCl2, HgO, and HgS-spiked sand are shown in Fig. 4(B), (C), and (D),
respectively. HgCl2 was removed rapidly even at temperatures < 150
°C; 50% removal was achieved in 6 h of thermal treatment. The re-
moval kinetics of HgO and HgS were slow below 150 °C; however, they
increased when the temperature was raised to 200 °C and became rapid
at temperatures higher than 300 °C. Roughly 90% removal
(10 mg kg−1) could be achieved within 6 h when the temperature was
greater than 300 °C.
The fitted kinetic rate constant k and n used in Equation (1) are
summarized in Fig. 5. In general, k shows significant temperature de-
pendence; it was observed that k increased with an increase in tem-
perature. However, the rate of increase reduced when the temperatures
were greater than 400 °C. Fundamental thermal desorption and va-
porization processes can be divided into inter-particle diffusion and
intra-particle diffusion, which represent the thermal desorption of
pollutants from adsorbed sites or volatilization of individually present
Hg solids and the transport of thermally desorbed or volatilized Hg
species through soil pores, respectively (Keyes and Silcox, 1994; Lighty
et al., 1990). This observation is consistent with a previous study that
showed that the evaporation of mercury from soil may be diffusion
controlled, rather than by its chemical and physical properties (vapor
pressure and volatility) and adsorption strength; the mercury remaining
at temperatures greater than 300 °C is not affected by an increase in
heating time (Taube et al., 2008).
It was found that the value of k was greater for Hg0 contaminated
soil and HgCl2-spiked sand when compared to HgO and HgS-spiked
sand at the same temperature. A previous study showed that the tem-
perature at which vaporized mercury was released from the original
mercury compound followed the trend of
Hg0 ≈ HgCl2 < HgS < HgO (Teršič et al., 2014) and interestingly,
the thermal desorption kinetic rate constants also followed the same
trend. The value of n increased slightly with an increase in temperature,
suggesting enhanced non-linear thermal desorption (Smith et al.,
2001). Moreover, it was previously observed that n is the least accurate
parameter (Smith et al., 2001). As our data showed relatively less
variation for n among different test Hg-contaminated soils, n was fitted
across different soils and temperatures as follows.
n = 1.3 × 10 3·T( °C) + 0.35, R2 = 0.35 (5)
The k values shown in Fig. 5 were evaluated again at fixed n values
of 0.45, 0.50, 0.55, 0.65, and 0.75 when the temperatures were 100,
150, 200, 300, and 400 °C, respectively. The values of reevaluated k,
which is defined as k’, are shown in Fig. 6. There was a clear difference
in the k’ of different tested samples. Desorption kinetics were found to
be the fastest in HgCl2-spiked sand and slowest in HgS-spiked sand. The

5
M.-o. Park, et al. Geoderma 363 (2020) 114150

1.5
(A)
soil soil
HgCl2
HgCl2
1.2 1.2 HgO
HgO HgS
HgS

0.9

k' (h )
k (h )

0.8

1/n
1/n

0.6

0.4
0.3
o
n=0.35+ 0.001* temp( C)
0.0
0.0
0 100 200 300 400 500
100 150 200 300 400
o
o
Temperature ( C)
Temperature ( C)
Fig. 6. Linear regression of n fitted with the equation n = 0.35
( ± 0.08) + 0.001 ( ± 0.0003) × temp (°C) and R2 = 0.40; k’ is reevaluated
using the fitted n.
1.6
soil (B) Table 2
HgCl2 The logistic curve parameters for k’ described as a function of temperature
HgO when n = 0.35 + 0.001 × temp (°C), R2 = 0.40. Note that k’ = a/(1 + exp
1.2 HgS (–(temp – x0)/b)). The values shown are averages (standard deviation) obtained
from 5 data points.
a b x0 R2
0.8
n

Soil 1.08 (0.03) 34.5 (4.5) 204 (5) 0.99

HgCl2 1.46 (0.09) 64.4 (9.5) 218 (13) 0.99
HgO 0.78 (0.07) 29.8 (14.3) 204 (15) 0.97
HgS 0.59 (0.04) 28.1 (10.1) 203 (10) 0.99
0.4

desorption kinetics and hence, in this study, N2 flow rate into the
0.0 thermal desorption column was controlled at 0.56, 5.6, and
100 150 200 300 400 56 mL min−1. The area of the quartz tubing reactor was 0.2 cm2 and the
measured porosity of soil and sand packed in the quartz tubing was
o
Temperature ( C) around 0.5; hence, a gas flow rate of 5.4 mL min−1 was equivalent to a
pore gas velocity of 0.1 cm s−1, which is a typical gas pore velocity in
Fig. 5. Fitted (A) k and (B) n for thermal desorption of Hg in Hg0-contaminated
soil vapor extraction processes (Dixon and Nichols, 2006). The results
soil and HgCl2, HgO, and HgS-spiked sand at different temperatures.
of thermal desorption kinetics experiments at various flow rate condi-
tions are summarized in Figs. S7 and S8. In the case of HgCl2-spiked
k’ values for field contaminated soil and HgCl2, HgO, and HgS-spiked sand, changing the flow rate from 5.6 mL min−1 to 0.56 and
sands followed a so-called S-curve between 100 and 400 °C, as shown in 56 mL min−1 changed k from 0.72 to 0.47 and 0.96, respectively. Ex-
Fig. S6. Finally, the behavior of k’ can be described using the following cept for HgCl2-spiked sand, the values k and n were not affected by the
logistics curve, flow rate, which further supports our hypothesis that thermal deso-
a rption kinetics are limited by inter-particle diffusion rather than intra-
y= (x x 0 )
(6) particle diffusion.
1+e b

where a is the maximum thermal desorption kinetic rate constant 4. Discussion

(h1/n), x0 is the midpoint of the curve, and b is the steepness of the
curve. Table 2 summarizes the parameters. The maximum thermal
desorption kinetic rate constant a as well as the steepness b were the
highest for HgCl2-spiked sand, suggesting that these Hg species were
the most reactive among the investigated samples. The values of a and b
were the lowest for HgS-spiked sand, which implies that these Hg
species were resistant to thermal desorption and volatilization pro-
cesses. Eqs. (5) and (6) can be very useful in understanding and mod-
eling Hg removal kinetics at temperatures in the range of 100 to 400 °C
(Table 3).
3.5. Effects of flow rate on Hg thermal treatment
Thermally desorbed and volatilized Hg needs to be removed by
induced gas flow which is usually varied from 0.01 to 0.12 cm s−1
(Dixon and Nichols, 2006). This variation could affect Hg thermal
Thermodynamic simulations of Hg thermal desorption suggest that
Hg vaporization is possible even at temperatures as low as the boiling
point of water; however, as shown in the present study, such vapor-
ization can be kinetically limited. Using Eq. (5) for n and Eq. (6) for k’,
the time for 70, 80, 90, and 99% Hg removal from contaminated soils
was calculated at various temperatures and the results are summarized
in Fig. 7. For example, to lower Hg levels in field contaminated soil by
90%, 204 days would be required if the soil is heated at 100 °C. If the
temperature is raised to 300 °C, then the time required may be shor-
tened to 3.5 h; upon further increasing the temperature to 400 °C, the
time required would be further reduced to 2.7 h, which is not very
different to the time required to remove 90% of Hg in soil at 300 °C. In
the case of HgS, the time required to lower Hg levels by 90% at 100,
300, and 400 °C is 3 days, 132 days, 8.5 h, and 6.2 h, respectively.
Increasing the thermal desorption temperature could increase Hg

6
M.-o. Park, et al. Geoderma 363 (2020) 114150

Table 3
Fitted k and n for the thermal desorption data obtained from field contaminated soil and HgCl2, HgO, and HgS-spiked sand at 200 °C at flow rates of 0.56, 5.6, and
56 mL min−1. The values shown are averages (standard deviation) of four replicates.
Flow rate 0.56 mL min−1 5.6 mL min−1 56 mL min−1

k n R2 k n R2 k n R2

Soil 0.38 (0.080) 0.59 (0.10) 0.98 0.53 (0.13) 0.42 (0.12) 0.94 0.59 (0.15) 0.45 (0.12) 0.94
HgCl2 0.47 (0.096) 0.54 (0.098) 0.97 0.72 (0.19) 0.46 (0.12) 0.95 0.96 (0.32) 0.42 (0.15) 0.90
HgO 0.31 (0.074) 0.51 (0.11) 0.96 0.38 (0.092) 0.48 (0.11) 0.96 0.44 (0.11) 0.53 (0.12) 0.96
HgS 0.21 (0.018) 0.67 (0.042) 0.99 0.26 (0.024) 0.56 (0.044) 0.99 0.28 (0.036) 0.69 (0.064) 0.99

thermal desorption kinetics and faster remediation can be expected.
However, increasing the temperature to very high levels (for e.g.,
300 °C in this study) did not significantly increase the rate of Hg re-
moval from soil due to kinetic limitations. In addition, raising the
temperature increases remediation costs and deteriorates the physical
and chemical properties of soil (O'Brien et al., 2018). Although low-
ering the thermal desorption temperature may be considered cost-ef-
fective, it will significantly increase the remediation time, which will
also lead to an increase in the process cost. Our study showed that the
heating temperature and time are negatively correlated with each
other. An optimal heating temperature and remediation time that
minimize cost and enhance remediation effectiveness are desirable; in
this regard, the relationship between thermal desorption temperature
and the time to achieve a certain removal efficiency can provide useful
insight and information.
In addition, kinetic information can be used to optimize the per-
formance of thermal desorption processes (Gilot et al., 1997; Keyes and
Silcox, 1994). For ISTD, heating elements can be installed as vertical
wells or as blankets. In this case, heat is mainly transferred by con-
duction, thus generating an uneven temperature distribution around

6 6
(A) soil (B) HgCl2
5 5

4 4
Log time (h)
Log time (h)

3 3

2 2

1 1

0 0
100 150 200 250 300 350 400 100 150 200 250 300 350 400
o
Temperature (oC) Temperature ( C)

6 6
(C) HgO (D) HgS
5 5

4 4
Log time (h)
Log time (h)

3 3

2 2

1 1

0 0
100 150 200 250 300 350 400 100 150 200 250 300 350 400
o o
Temperature ( C) Temperature ( C)

99%
90%
80%
70%

Fig. 7. Time necessary to achieve different removal efficiencies at temperatures from 100 to 400 °C for (A) field contaminated soil and (B) HgCl2, (C) HgO, and (D)
HgS-spiked sand.

7
M.-o. Park, et al.
the heat source, i.e., high temperature near the heat source and low
temperature further away from the source. Spatially heterogeneous
temperature distribution could lead to spatially uneven removal effi-
ciencies. In such scenarios, efficient and cost-effective removal would
be dependent upon the number of heating elements installed in con-
taminated areas. ISTD also employs a soil vapor extraction system,
which is often limited by the transportation of vaporized contaminants
in soil pores (Rathfelder et al., 1991). This limitation highlights the
importance of optimizing heating elements arrays for soil vapor ex-
traction systems (Sun et al., 1996). In these cases, information on
temperature-dependent desorption kinetics may help in determining
the methods to be employed for effective remediation.
Lastly, off-gas treatment is inevitable after thermal desorption
(Vidonish et al., 2016). The present study shows that increasing the gas
flow during thermal desorption does not increase the rate of Hg deso-
rption. Large volumes of off gas with low levels of Hg could lower the
performance of off-gas treatment processes and increase the overall
remediation cost. Therefore, an optimized gas flow rate, i.e., the
minimum gas flow rate that does not cause inter-particle diffusion, is
necessary (Zhao et al., 2019) for cost-effective remediations.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
This work was supported by the Korea Environmental Industry and
Technology Institute (2016000550002, 2018002480002) in Ministry of
Environment and by the Korea Institute of Energy Technology
Evaluation and Planning (20193410100050) in Ministry of Trade,
Industry and Energy in Korea.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.geoderma.2019.114150.
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