Application of solar thermal desorption to remediation

of mercury-contaminated soils
A. Navarro
a,
*
, I. Can adas
b
, D. Martinez
b
, J. Rodriguez
b
, J.L. Mendoza
a
a
Department of Fluid Mechanics, Polytechnic University of Catalonia (UPC), ETSEIT, Colo n 11, 08222 Terrassa, Barcelona, Spain
b
Plataforma Solar de Almera (PSA), Solar Platform of Almeria-CIEMAT, P.O. Box 22, Tabernas, E-04200 Almeria, Spain
Received 24 November 2008; received in revised form 19 January 2009; accepted 11 March 2009
Available online 8 April 2009
Communicated by: Associate Editor Gion Calzaferri
Abstract
Solar thermal desorption at temperatures up to 500 C is an innovative technology applied to the removal of mercury and arsenic
from soil polluted by mining operations. As the soil is heated in a low and high-temperature solar system, the pollutant vapor pressure
rises, producing mass transfer to the gas phase, which is then extracted by vacuum pumps and blower systems.
In the UPC low-temperature experiments, removal of mercury from the polluted soil was as much as 76%. The experimental results
show that volatilization of mercury is only signicant when the temperature is above approximately 130 C, which agrees with the pre-
dominant mercury solid phases detected. PSA middle-temperature experiments, showed that when soil and mine waste samples were
heated to 400500 C, mercury elimination was signicant (41.387%). However, the results from heating to 320 C or below 300 C,
indicated little or negligible removal, possibly, because the uid dynamics in the uidized-bed module and the presence of cinnabar
and pyrite rich-Hg as dominant mineral phases.
These results show the potential for eciently removing mercury and other pollutants from solid matrices (soil, waste, etc.) at low
temperatures.
2009 Elsevier Ltd. All rights reserved.
Keywords: Solar energy; Desorption; Mercury; Soil contamination; Mine wastes
1. Introduction
Mercury is the most hazardous metal for human health
and the environment due to its ability to bioaccumulate, its
toxic eects, and the possibility of aqueous mobilization in
concentrations over the maximum levels allowed by most
drinking water standards. Most human exposure to inor-
ganic mercury is from Hg
0
vapor, derived from industries
such as AuAg mining and chlor-alkali plants (Fitzgerald
and Lamborg, 2005), although the main mercury-related
human health concern is exposure to the highly neurotoxic
organomercury compound, monomethylmercury (Fitzger-
ald and Lamborg, 2005).
The release of mercury into the environment in Hg min-
ing areas is generally associated with the abandonment of
mine waste, which is mainly composed of calcines (waste
originated in the metallurgy of Hg) and mining wastes
impoundments, which contain waste rock and low-grade
stockpiles (Gray, 2003; Rytuba, 2003; Higueras et al.,
2003; Fernandez-Mart nez et al., 2006; Qiu et al., 2006;
Navarro et al., 2006). Mercury has mainly been extracted
from cinnabar (HgS), although the following are also mer-
cury phase materials: livingstonite (HgSb
4
S
8
), corderoite
(Hg
3
S
2
Cl
2
), metacinnabar (cubic HgS), schuetteite
(Hg
3
(SO
4
)O
2
), montroydite (HgO), calomel (Hg
2
Cl
2
), tie-
mannite (HgSe) and kleinite (
4
[Hg
2
NCl]Hg[SO
4
,Cl]H
2
O).
The main process for extracting mercury from cinnabar is
to roast the ore at 500600 C, which releases Hg
0
. Thus,
when the temperature reaches to 600800 C, the mercury
0038-092X/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2009.03.013
*
Corresponding author. Tel.: +34 937398151; fax: +34 7398101.
E-mail address: navarro@mf.upc.edu (A. Navarro).
www.elsevier.com/locate/solener
Available online at www.sciencedirect.com
Solar Energy 83 (2009) 14051414
compounds would be converted into gaseous mercury
which could be recovered. Table 1 shows desorption tem-
peratures and their ranking for some mercury compounds
(Biester et al., 1997; Gaona, 2005).
Some treatments processes, such as stabilization/solidi-
cation, thermal desorption, vitrication, soil ushing and
soil washing have been used for mercury-contaminated soil
remediation (Troxler et al., 1997; ITRC, 1998; EPA, 2003;
Chang and Yen, 2006). The thermal desorption treatment
is, usually, an ex situ remedial technology which converts
mercurial compounds into the volatile mercury, and has
been considered as a preferred technology, due of more
safety and less emission of treating substance (Chang and
Yen, 2006). However, the major disadvantages are high
capital costs and eectiveness only at rather high mercury
concentrations (Kucharski et al., 2005).
Several mercury thermal desorption experiments have
demonstrated the feasibility of mercury removal at temper-
atures between 127 and 600 C (Matsuyama et al., 1999;
Chang and Yen, 2006; Kunkel et al., 2006). Experimental
remediation of mercury-polluted soils by low-temperature
thermal desorption has also shown mercury removal of
over 99% in sand (Kunkel et al., 2006) and the volatiliza-
tion of at least 99% of mercuric sulde from polluted soil
(Matsuyama et al., 1999).
Therefore, solar thermal desorption, using solar energy
as the primary energy source in a low-to-medium-tempera-
ture solar furnace may be an option for soil treatment. The
use of solar energy in these environmental applications is
new, although the natural mobilization of mercury from
soil by incident solar radiation is well-known (Gustin
et al., 2002). Moreover, the majority of the experiences
based on the application of solar energy do not use solar
radiation in thermal desorption processes (Funken et al.,
1999; Flamant et al., 1999; Steinfeld and Palumbo, 2001;
Nakamura et al., 2000; Eelsberg and Barbknecht, 1991;
Eelsberg et al., 1992; Kaneko et al., 2004).
The main objective of this research was to evaluate the
potential of solar thermal desorption (STD) for removal
of mercury from mining contaminated soils. A low-temper-
ature laboratory system was designed and used to evaluate
the eectiveness of STD, and a middle-temperature solar
furnace was used to evaluate the application of a uid-
ized-bed reactor in thermal desorption.
2. Materials and methods
2.1. Characterization of soil and mine waste
Samples of soils and mine waste were collected in the
Valle del Azogue and Bayarque mines (SE, Spain). The
Valle del Azogue mine was the principal mercury mine
in the Betic Ranges from approximately 18731890 and
the ore is composed of stibnite, cinnabar, As minerals
(realgar and orpiment), sphalerite, siderite, chalcopyrite,
pyrite, quartz, calcite and baryte (Navarro et al., 2006).
Other mineral phases detected (Mendoza et al., 2005)
include metacinnabar (HgS), SeHgS, tiemannite (HgSe),
corderoite (Hg
3
S
2
Cl
2
), shakhovite (Hg
4
SbO
5
(OH)
3
) and
schuetteite (Hg
3
(SO
4
)O
2
). The Bayarque mine is located
near the valley of the Almanzora River and the town of
the same name. Its underground mines were exploited
until approximately 1973. The mineralogy mainly consists
of cinnabar, malachite, azurite, hematites, galena, goe-
thite, siderite, chalcopyrite, bornite, chalcosine, covellite
and uorite.
Approximately 1.5-kg samples of mine waste and soil
were manually extracted and crushed to 10 mesh in a jaw
crusher, quartered, and pulverized in an agate mortar,
rehomogenized and repacked in plastic bags. Soil samples
were taken from a depth of approximately 00.25 m and
were sent to Actlabs (Ontario, Canada) with other mine
samples. Au, Ag, As, Ba, Br, Ca, Ce, Co, Cr, Cs, Eu, Fe,
Hf, Hg, Ir, La, Lu, Na, Ni, Nd, Rb, Sb, Sc, Se, Sm, Sn,
Sr, Ta, Th, Tb, U, W, Y and Yb were quantitatively ana-
lyzed by instrumental neutron activation analysis (INAA)
and Mo, Cu, Pb, Zn, Ag, Ni, Mn, Sr, Cd, Bi, V, Ca, P,
Mg, Tl, Al, K, Y and Be were analyzed by inductively cou-
pled plasma emission spectroscopy (ICP-OES). The ther-
mal treated samples were analyzed in the same way. The
accuracy of analytical data may be evaluated around
10%, because the heterogeneity of solid samples.
The mine waste samples were studied using transmitted
and reected light microscopy, X-ray diraction (XRD)
and scanning electron microscopy (SEM) with an attached
energy dispersive X-ray spectroscopy system (EDS) at the
Electronic Microscopy Laboratory of the Universitat
Auto` noma de Barcelona.
Hg phases were determined by solid-phase-Hg-thermo-
desorption (SPTD), based on the specic thermal desorp-
tion or decomposition of Hg compounds from solids at dif-
ferent temperatures (Biester and Scholz, 1997; Navarro
et al., 2006). Mercury thermo-desorption curves were
determined by means of an in-house apparatus, consisting
of an electronically controlled heating unit and an Hg
detection unit. Measurements were carried out at a heating
rate of 0.5 C/s and nitrogen-gas ow of 300 mL/min. The
lowest level of detection under the given conditions is in the
range of 4050 ng if all Hg is released within a single peak
(Biester and Scholz, 1997). Results are depicted as Hg
thermo-desorption curves (Hg-TDC) which show the
release of Hg(0) versus temperature.
Table 1
Desorption temperatures of dierent mercury phases.
Phase Desorption temperature of phase Hg (C)
Hg
0
<100
Hg
2
Cl
2
170
HgCl
2
<250, 220
HgO 420550
HgSO
4
450-500
HgS (cinnabar) 310330
Hg in pyrite >450
Hg in Sphalerite 600
Hg matrix-bound 200300
1406 A. Navarro et al. / Solar Energy 83 (2009) 14051414
2.2. Furnaces
In this study, two systems of solar thermal desorption,
an experimental low-temperature solar furnace (LT-UPC)
and a middle-temperature solar furnace (MT-PSA), were
used to treat mercury-polluted soil and mine waste from
the Valle del Azogue and Bayarque mines.
Besides, since the use of activated-carbon is eective in
mercury vapor adsorption (Spiric and Hraste, 1999; Kara-
tza et al., 2000; Vitolo and Seggiani, 2002; Li et al., 2002;
Lee et al., 2002; Meij et al., 2002; Lee and Park, 2003),
an activated-carbon lter was used in the treatment of gas-
eous mercury compounds.
2.2.1. Low-temperature solar furnace (LT-UPC)
The experiments were done in a low-ux-density, low-
temperature solar furnace, which consists of ve elements:
a solar reector, a glass furnace (or reactor), a uid-cooling
system, an Hg gas adsorption system, and a vacuum pump
which mobilizes ambient air from the glass furnace to the
activated-carbon lter (Fig. 1a). The system has a collector
and rotating base which allows seasonal adjustment to the
solar position. The glass furnace is a high-temperature-
resistant glass ask that is connected to a thermometer to
measure the temperature inside it. An air-cooled coil gas-
cooling system lowers the temperature in case it should
exceed 400 C, before the gas enters the carbon lter.
Finally, a vacuum pump generates the extraction ow-rate
of Hg-polluted gases.
The treatment procedure consists of placing the polluted
soil sample in the furnace, turning the reector northward
and directing the center of sunlight reected by the collec-
tor onto the base of the glass furnace. When it is ready, the
vacuum pump is put into operation to start up extraction
of the polluted gas. The temperature is measured at 10-
min intervals for 24 h. When the sample has cooled, it is
taken out of the furnace, packed and sent to be analyzed
for Hg content, metals and rare earth elements.
2.2.2. Middle-temperature solar furnace (MT-PSA)
A uidized-bed reactor design by CIEMAT and
CENIM-CSIC was used to test the feasibility of high-tem-
Fig. 1. (a) Scheme of operation of the low-temperature solar furnace (LT-UPC). (b) Scheme of operation of the middle-temperature solar furnace (MT-
PSA). SC: system cooling, F
CA
: activated-carbon lter.
A. Navarro et al. / Solar Energy 83 (2009) 14051414 1407
perature solar desorption in the Plataforma Solar de
Almer a (PSA) Solar Furnace (Fig. 1b). This system has
two main parts, the PSA Solar Furnace facility, and the
solar uidized-bed module connected to an Hg gas collec-
tion system with a nal activated-carbon adsorption bed
(Fig. 2).
The PSA Solar Furnace consists of a at heliostat, a
parabolic dish, and a louvered ux shutter. The GM140
at-surface heliostat, which reects the solar radiation onto
the parabolic dish, has a 140-m
2
reective area, with 93%
reectivity. It tracks the sun continuously, and is controlled
by a remote system connected to a computer. The ux
shutter, which regulates how much solar radiation arrives
at the uidized-bed, is 11.5 m wide and 11.2 m high, and
consists of 30 slats arranged in two columns in the module
wall. The concentrator or parabolic dish consists of 89
spherical sandwich-type facets, with a total reecting area
of 98.5 m
2
and reectivity of 94%. The concentrator dish
is the main component of the solar furnace. It concentrates
incident light from the heliostat, multiplying the radiant
energy in the focal zone, to a peak ux of 300 W/cm
2
and total power of 68 kw (Monterreal, 2005).
The uidized-bed reactor, with indirect solar heating
and open volumetric receiver, is a new device developed
by CENIM and CIEMAT for installation in the PSA Solar
Furnace. Fig. 2 shows a schematic diagram of the modular
uidized-bed installed in the test assembly (Can adas et al.,
2006).
The uidized-bed module consists of an indirectly-
heated solar uidized-bed reactor, with two independent
circuits, one for heating, through which air from the absor-
ber module is forced by a blower located at the end of the
test assembly, and another for the uidized ow (com-
pressed air or gas). All the equipment is insulated to mini-
mize heat loss. The surface temperature of the absorber
module is measured by a pyrometer (Ballestr n et al., 2008).
The soil samples are inserted in the uidized-bed cham-
ber for treatment. The uidized-bed operates at a ow-rate
of 50 L/min. As shown in Fig. 2, the uidized-bed cylindri-
cal chamber is 1 m high and 20 cm in diameter. The conical
base is connected by the uidized ow circuit to a pump/air
compressor that generates the uidizing air ow. This
chamber is heated up by another outer module heated by
the absorber. At the top of the uidized-bed chamber,
the Hg gas collector system is connected to a cooling sys-
tem that lowers the Hg gas temperature to below 400 C.
The treatment procedure for each sample consists of
placing a soil sample in the uidized-bed chamber, sealing
the cover and connecting it to the gas recovery system. The
heliostat controller automatically directs the solar radia-
tion onto the concentrator dish, which in turn beams the
concentrated solar rays onto a focal point located on the
optical axis. The absorber module in the focal zone, is
gradually heated by concentrated solar radiation as the
shutter is gradually opened to the reference temperature
of 400 C, and this temperature is maintained for approxi-
mately 30 min.
During the treatment, a blower forces air through the
absorber module, where it is heated, and part of the energy
in this air is transferred into the uidized-bed chamber
through its steel walls, heating it, and then preheating the
air or gas that uidizes the bed as it passes through the coil
behind it. When this has been accomplished, the digital
data is saved. At the end of the experiment, when the sam-
ple is cold, it is taken out to be analyzed. The main dier-
ence between the LT-UPC and the MT-PSA furnaces, was
in the operation system, thus the low-temperature furnace
is static, while the middle-temperature furnace is a uid-
ized-bed reactor.
3. Results and discussion
3.1. Geochemistry of soils and mine waste
The mean concentrations of mercury and other metals
in the soil and mine waste samples from the Valle del Azo-
Fig. 2. Schematic drawing of the uidized-bed module in the Solar Platform Almer a (MT-PSA).
1408 A. Navarro et al. / Solar Energy 83 (2009) 14051414
gue and Bayarque mines is shown in Table 2. The total
mercury concentration in waste from the Valle del Azogue
mine varies between 1 and 4000 mg/kg, and at the Bayar-
que mine between 33 and 4600 mg/kg. In the waste samples
from the Valle del Azogue and Bayarque mines, the aver-
age is 649.1 mg/kg and 1247.7 mg/kg, respectively. Total
mercury in surface soil from the Valle del Azogue ranged
from 1.0 to 2300 ppm, concentrations which are below
those detected near the Almaden mine (Higueras et al.,
2003, 2006). Due to the mining activities, along with the
impact of high Ag, As, Pg, Sb and Zn, plants in most of
the area have disappeared or are severely aected by the
very high mercury and metal content found in them (Vila-
devall et al., 1999).
Hg-thermo-desorption curves (Hg-TDC) found for min-
ing wastes, soils and calcine samples showed predominant
release of Hg in two temperature ranges: 200250 C and
300330 C (Fig. 3). The rst temperature range was
assigned to release Hg from the soil matrix components
based on the Hg-TDCs of standard materials (Biester
and Scholz, 1997). Thus, we assume that most Hg in the
calcine material is bound to mineral components mainly
by iron oxides, which were formed when the cinnabar-bear-
ing ore was being roasted. It has been suggested in earlier
studies, that Hg
0
formed during thermal breakdown of cin-
nabar is re-condensed during cooling of the material and
adsorbed to dehydrated iron oxide surfaces (Biester et al.,
1999). Sample B01, which was taken directly from the
Bayarque mine furnace outlet shows the matrix-bound
Hg mainly formed during roasting. In addition to matrix-
bound Hg, some calcine samples contain at least traces of
cinnabar. This could be explained by incomplete break-
down of cinnabar ore during the roasting process.
The second temperature range was assigned to Hg
release from cinnabar, which was the predominant mineral
Hg-phase in contaminated soils (Fig. 3b) and mining
wastes (host rock and low-grade stockpiles). Cinnabar
and a possible Hg sulfate were also detected in several sam-
ples (Navarro et al., 2006). No free metallic Hg, which is
typically released at temperatures below 100 C (Biester
and Scholz, 1997), was found in any of the samples studied.
Mercury phase characterization by soil sample X-ray
showed cinnabar (HgS), corderoite (Hg
3
S
2
Cl
2
), mercury
dichloride (I) (Hg
4
O
2
Cl
2
), hypercinnabar (HgS), lattite
(AgHgAsS
3
), metacinnabar ((Hg)S), shakhovite (Hg
4
SbO
5
(OH)
3
), schuetteite (Hg
3
(SO
4
)O
2
) and tiemannite (HgSe).
The proportionally predominant phase is cinnabar, which
is concordant with the SPTD analyses.
3.2. Thermal desorption experiments
The low-temperature experiments (LT-UPC) were con-
ducted under global radiation at least 30 W/m
2
and no
more than 300 W/m
2
. The variation in temperature and
global radiation, the time, and the duration of some tests
may be observed in Fig. 4. Peak temperatures of 280 C
were reached. The temperature ranges and average temper-
ature are shown in Table 3.
Mercury removal eciency in the soil and waste samples
is up to 76% and was negligible in samples A01 to A04
(Table 3). The experimental results show that mercury vol-
atilization is only signicant when the temperature is above
approximately 130 C, which is in agreement with the dom-
inant solid phases of mercury: cinnabar and Hg
0
bound to
the solid matrix. Both phases have a volatilization temper-
ature of 300330 C and 200250 C, respectively. The low
Hg removal in the samples A01 to A04 may be associated
to their mineralogical characteristics, since these samples
were mining wastes and soils with a great percentage of cin-
nabar and pyrite. The volatilization of Hg from cinnabar
particles needs a mean temperature above 300 C, approx-
imately, and the mean temperature of the LT-UPC exper-
iment reached, only, 91130 C. The greater Hg-removal
was reached in the sample A06, which showed high con-
tents of volatile-Hg-phase minerals, such as calomel and
kuzminite (Navarro et al., 2009). In the samples M04 to
Table 2
Concentrations of metals in mine waste and soils in the Valle del Azogue mine. Values in mg/kg except Ba (%). NIL (): The Netherlands soil intervention
values (): indicative level of contamination (): soils and mine wastes. NCD: non-polluted soils.
As Ba Cd Cr Cu Hg Pb Se Sb Sr Zn
Valle del Azogue mine
Wastes
Mean 526.1 6.0 5.7 70.5 47.5 649.1 901.6 4325.6 945.3 2631.0
Min 12.9 0.07 <0.3 <50 8.0 <1 28.0 <5 8.0 102.0 70.0
Max 1650 17.0 29.9 161 208.0 4000 3422 23.0 22200 3321 14925
Soil
Media 299.4 0.89 6.5 99.7 23.1 348.0 222.4 7.8 2669.3 446.8 433.8
Min 18.0 0.02 0.5 10.0 4.0 1.0 7.0 5.0 19.0 0.5 50.0
Max 1200 5.3 106 430 55.0 2300 1308 36.0 32000 1500 2970
Bayarque mine()
Mean 24.7 0.035 0.7 87 34.5 1274.7 30.5 14.9 240 90
Min 5.1 <0.005 0.3 77 17 33 20 <3 6 134 87
Max 63.6 0.052 1.3 96 51 4600 38 <5 34.4 344 103
NCD 24.1 0.08 0.8 35 12 <1 19 <3 2.1 300
NIL () 55 0.0625 12 380 190 10 530 100 15 720
A. Navarro et al. / Solar Energy 83 (2009) 14051414 1409
M07, Hg is associated to mineral compounds matrix, and
possibly derived from the atmospheric deposition of Hg
0
evaded from old roasting plant emissions. Moreover, the
vacuum pumping system used in this experiment, which
carried atmospheric air from the glass furnace, showed a
great eectiveness, moving high amounts of gaseous Hg
to activated-carbon lter.
In the middle-temperature experiments (MT-PSA) the
global radiation was approximately 900 W/m
2
(Fig. 5) with
an exposure time of between 75 and 315 min (Table 5).
Based on the results of the heating tests, when soil and
waste were heated to 400500 C, mercury removal was sig-
nicant. However, when heated to 320 C or below 300 C,
there is little or negligible removal of mercury (Table 4).
Thus, in mercury removal in Samples M02, M03, M05
and M07 was between 41.3 and 87.0%, when heated to over
approximately 400 C, (Table 4), whereas removal from
Samples B02 and AZ21 was only between 12.1 and
36.3%, because the furnace temperature was just over
300 C. Mercury removed was negligible in Samples A01
to A05, Az22 and B01, possibly because of the low temper-
atures reached, the short experiment exposure time and the
presence of signicative amounts of cinnabar and Hg-rich
pyrite in these samples. Thus, in sample A02, which was
heated up to 479 C, there may have been no removal
due to its mineralogical nature. In fact, in sample A02, a
B01 - furnace calcine
0
200
400
600
800
1000
1200
1400
1600
1800
0 100 200 300 400 500 600 700
C
E
x
t
i
n
k
t
i
o
n
0
20
40
60
80
100
120
140
160
180
200
B0102
B0101
B02 - alluvial soil
0
20
40
60
80
100
120
140
160
180
200
0 100 200 300 400 500 600 700
C
E
x
t
i
n
k
t
i
o
n
0
10
20
30
40
50
60
70
80
90
100
B0202
B0201
a
b
Fig. 3. Examples of mercury thermo-desorption curves. The two curves in each graphic represent a SPTD experience on the same material. (a) Calcine
sample B01 which shows Hg
0
matrix-bound dominant. (b) Soil sample B02 which shows cinnabar as dominant phase mineral.
1410 A. Navarro et al. / Solar Energy 83 (2009) 14051414
large percentage of mercury may be encapsulated in pyrite,
which has a high volatilization temperature (Table 1). The
possible presence of HgSO
4
or HgO (Sample A03), com-
pounds releasing Hg at above 400 C, may also explain
the absence of mercury removal in some samples. Another
factor that may determine the eciency of mercury
removal in the uidized-bed experience is the velocity of
the solid particles inside the furnace. Thus, the terminal
velocity of material particles calculated from Stokes equa-
tion was comprised between 0.16 m/s (silty particles) and
4.15 m/s (sandy particles). Since entry velocity of particles
was 2.65 m/s, the silty particles, possibly, move to the
upper part of the furnace, accumulating in the lter. There-
fore, the transport of dominant ne particles inside the u-
idized-bed furnace and the consequent low eciency in the
heat and mass transport together with the lter-block for-
mation may also explain the low Hg-removal of MT-PSA
experiences, despite the high-temperature reached. In all
the samples treated in the MT-PSA experiences, the best
results were obtained with samples that present dominant
Hg
0
bound to the solid matrix (Az21, M02 to M07), except
the sample B02, which is coincident with the LT-UPC
results.
As content shows this metalloid was removed in heating
tests in the same samples which have signicant mercury
desorption, except for Sample M07, and Samples B01
and AZ22 (Table 5). As removal was between 5.5 and
77.3%, indicating the feasibility of As desorption from
the polluted soil and mine waste. These results show that
more mercury and arsenic is removed by heating when
operating temperatures are over 400 C, although mercury
removal may dier depending on the minerals containing it
and exposure time. Results also suggest that mercury con-
tained in cinnabar and pyrite is not eciently removed by
desorption caused by the solar treatment in the experimen-
tal conditions, although removal may be complete at
higher temperatures (500600 C).
4. Conclusions
This article reports the rst time a solar thermal concen-
trated facility has been used for remediation of mercury-
contaminated soils. Two dierent concentrated facilities
were employed with satisfactory results in dierent temper-
ature ranges.
Sample A03
0
50
100
150
200
250
300
13:33 13:48 14:02 14:16 14:31 14:45 15:00 15:14 15:28 15:43 15:57 16:12 16:26 16:40 16:55
Time
T
e
m
p
e
r
a
t
u
r
e

C
0
100
200
300
400
500
600
700
800
900
1000
R
a
d
i
a
t
i
o
n

W
/
m
2
T 170506
R 170506
Fig. 4. Temperatures and global radiations of some tests from low-temperature experiments (LT-UPC): T indicates temperature of DDMMYY and R
indicates the global radiation of DDMMYY.
Table 3
Data tests made in a solar furnace LT-UPC.
Sample Initial Hg
(mg/kg)
Final Hg
(mg/kg)
%
Desorption
T
(mean)
(C)
Operation
temperatures
(C)
A01 530 506 4.5 128.0 45145
A02 1000 >1000 91.0 38125
A03 210 >200 113.0 55165
A04 540 >500 130.9 65187
A06 600 176 70.6 129.2 80168
M04 4000 2800 30.0 203.3 68247
M05 50 12 76.0 213.0 110280
M06 399 240 39.8 168.5 128197
M07 23 12 47.8 131.2 88149
A. Navarro et al. / Solar Energy 83 (2009) 14051414 1411
The SPTD determinations showed two dierent temper-
ature ranges in which Hg was released from the samples,
200250 C and 300330 C. From previous interpretation,
the rst Hg release peak indicates Hg released from the
matrix, whereas the second peak at higher temperatures
indicates presence of cinnabar (Biester and Scholz, 1997;
Navarro et al., 2006). The rst release of Hg was typically
found for calcinated samples, where cinnabar was broken
down, but some Hg is re-adsorbed onto the calcinated
material during cooling. The second peak release is domi-
nant in the mining wastes and soils.
The low-temperature experiments (LT-UPC) showed
up to 76% mercury removal eciency in soil and mine
waste samples. Experimental results indicate that volatili-
zation of mercury is only signicant when the temperature
is above approximately 130 C, which is in agreement
with the predominant mercury solid phases (Hg
0
bound
to solid matrix in samples A06 and M04 to M07). The
middle-temperature experiments (MT-PSA) showed that
when soil and mine waste were heated to 400500 C,
mercury removal was signicant. However, the results
from heating to 320 C or below 300 C, show little or
negligible removal of mercury, mainly, in the samples
with signicative amounts of cinnabar and Hg-rich pyrite.
The As solar desorption tests showed that between 5.5
and 77.3% of this metalloid was removed, indicating the
feasibility of As desorption from polluted soil and mine
waste.
The thermal desorption technique was successfully
applied to polluted samples from the Valle del Azogue
and Bayarque mines, and was demonstrated to be an alter-
native method for decontaminating hazardous waste sites
where mercury is present because of its volatility.
Sample B01T
0
100
200
300
400
500
600
700
800
900
1000
14:51 15:06 15:21 15:36 15:51 16:06
TIME
R
a
d
i
a
t
i
o
n


W
/
m
2
;




T
e
m
p
e
r
a
t
u
r
e

C
0
10
20
30
40
50
60
70
80
90
100
P
e
r
c
e
n
t
a
g
e
T furnace Radiation shutter
Fig. 5. Temperatures, global radiations at percentage of shutter opening in B01 sample test in the middle-temperature solar furnace in PSA.
Table 4
Results of Hg elimination from the experiments in the middle-temperature
solar furnace (MT-PSA).
Sample Initial
Hg
(mg/kg)
Final
Hg
(mg/kg)
%
Desorption
Exposition
time (min)
Temperature
(C)
A01 530 >500 174 23332
A02 1000 >1000 156 57479
A03 210 >200 159 24309
A04 540 >500 115 20337
Az21 330 290 12.1 101 100315
Az22 1 >1 79 93318
M02 450 200 55.6 129 20485
M03 470 60.9 87.0 315 38482
M05 50 9.48 81.0 185 29502
M07 23 13.5 41.3 214 55359
B02 33 21 36.3 90 25320
B01 66 >60 75 70326
A05 400 >400 90 70347
Table 5
Results of As elimination from the experiments in the middle-temperature
solar furnace (MT-PSA).
Sample Initial As (mg/kg) Final As (mg/kg) Desorption (%)
A01 300 >300
A02 620 >600
A03 184 199
A04 680 >700
A05 320 >300
B01 9.6 7 27.0
AZ22 12.9 7 45.7
B02 20.8 13 37.5
AZ21 448 423 5.5
M02 296 67 77.3
M03 1610 578 64.0
M05 129 114 11.6
M07 233 297
1412 A. Navarro et al. / Solar Energy 83 (2009) 14051414
Acknowledgements
This work was funded by The Spanish Ministry of Sci-
ence and Technology (project REN2003-09247-C04-03
and ENE2006-13267-C05-01/ALT) in collaboration with
the PSA-CIEMAT (Centro de Investigaciones Energeticas,
Mediombientales y Tecnolo gicas), and the 20032004
Technical and Scientic Infrastructure Program (FEDER
CIEM-E008). The authors wish to thank Dr. Ursula Kelm
and Mo nica Uribe for ray X analyses and their interpreta-
tion, to Alfonso Vazquez and Bernardo Fernandez of the
CENIM-CSIC for their participation in the design and
development of the uidized-bed, and nally to the PSA
Furnace personnel, especially Jose Galindo, for their tech-
nical support in this project.
References
Ballestr n, J., Can adas, I., Rodr guez, J., 2008. Testing a Solar-Blind
Pyrometer, 14th SolarPACES International Symposium on Concen-
trated Solar Power and Chemical Energy Technologies. Las Vegas,
USA.
Biester, H., Scholz, C., 1997. Determination of mercury phases in
contaminated soils Hg-pyrolysis versus sequential extractions.
Environment Science Technology 31, 233239.
Biester, H., Hess, A., Mu ller, G., 1997. Investigations on dierent
mercury-phases in soils of a Hg-mining area by a temperature-
controlled-pyrolysis technique. In: Reuther, R. (Ed.), Environmental
Science. Geochemical Approaches for the Environmental Engineering
of Metals. Springer, Heidelberg, pp. 3343.
Biester, H., Gosar, M., Mu ller, G., 1999. Mercury speciation in tailings of
the idrija mercury mine. Journal of Geochemical Exploration 65, 195
204.
Can adas, I., Tellez, F., Rodr guez, J., Mart nez, D. 2006. SOLARPRO: a
survey of feasible high temperature industrial applications of concen-
trated solar energy. In: Proceedings of 13th International Symposium
on Concentrated Solar Power and Chemical Energy Technologies.
ISBN: 84-7834-519-1. Seville, Spain.
Chang, T.C., Yen, J.H., 2006. On-site mercury-contaminated soils
remediation by using thermal desorption technology. Journal of
Hazardous Materials 128, 208217.
Eelsberg, H., Barbknecht, B., 1991. The use of thermal solar energy to
treat waste materials. Part 1. In: Becker, M., Funken, K.H., Schneider,
G. (Eds.), . In: Solar Thermal Energy Utilization, vol. 5. Springer
Verlag, Berlin, pp. 413482.
Eelsberg, H., Kirchner, E., Barbknecht, B., 1992. The use of thermal
solar energy to treat waste materials. Part 2. In: Becker, M., Funken,
K.H., Schneider, G. (Eds.), . In: In Solar Thermal Energy Utilization,
vol. 6. Springer Verlag, Berlin, pp. 239326.
EPA, 2003. Evaluation of Chemically Bonded Phosphate Ceramics for
Mercury Stabilization of a Mixed Synthetic Waste. EPA/600/R-03/
113, p. 70.
Fernandez-Mart nez, R., Loredo, L., Ordo n ez, A., Rucandio, M.I.,
2006. Physicochemical characterization and mercury speciation of
particle-size soil fractions from an abandoned mining area in
Mieres, Asturias (Spain). Environmental Pollution 142 (2), 217
226.
Fitzgerald, W.F., Lamborg, C.H., 2005. Geochemistry of mercury in the
environment. In: Lollar, B.S. (Ed.), . In: Environmental Geochemistry,
Treatise on Geochemistry, vol. 9. Elsevier-Pergamon, Oxford, pp. 107
148.
Flamant, G., Ferriere, A., Laplaze, D., Monty, C., 1999. Solar processing
of materials: opportunities and new frontiers. Solar Energy 66 (2),
117132.
Funken, K.H., Pohlmann, B., Lu pfert, E., Dominik, R., 1999. Application
of concentrated solar radiation to high temperature detoxication and
recycling processes of hazardous wastes. Solar Energy 65, 2531.
Gaona, X. 2005. El mercurio como contaminante global: Desarrollo de
metodolog as para su determinacio n en suelos contaminados y
estrategias para la reduccio n de su liberacio n al medio ambiente.
Thesis PhD, Universidad Auto noma de Barcelona, Departamento de
Qu mica, Unidad de Qu mica Anal tica, p. 138.
Gray, J.E., 2003. Leaching, transport, and methylation of mercury in and
around abandoned mercury mines in the Humboldt River basin and
surrounding areas, Nevada. US Geological Survey Bulletin 2210-C, 15.
Gustin, M.S., Biester, H., Kim, C.S., 2002. Investigation of the light-
enhanced emission of mercury from naturally enriched substrates.
Atmospheric Environment 36, 32413254.
Higueras, P., Oyarzun, R., Biester, H., Lillo, J., Lorenzo, S., 2003. A rst
insight into mercury distribution and speciation in soils from the
Almaden mining district, Spain. Journal of Geochemical Exploration
80, 95104.
Higueras, P., Oyarzun, R., Lillo, J., Sanchez-Hernandez, J.C., Molina,
J.A., Esbri, J.M., Lorenzo, S., 2006. The Almaden district (Spain):
anatomy of one of the worlds largest Hg-contaminated sites. Science
of the Total Environment 356, 112124.
ITRC, 1998. Technical guidelines for on-site thermal desorption of solid
media and low level mixed waste contaminated with mercury and/or
hazardous chlorinated organics. Interstate Technology and Regulatory
Cooperation Work Group, p. 68.
Kaneko, H., Kodama, T., Gokon, N., Tamaura, Y., Lovegrove, K.,
Luzzi, A., 2004. Decomposition of Zn-ferrite for O
2
generation by
concentrated solar radiation. Solar Energy 76, 317322.
Karatza, D., Lancia, A., Musmarra, D., Zucchini, C., 2000. Study of
mercury absorption and desorption on sulfur impregnated carbon.
Experimental Thermal and Fluid Science 21, 150155.
Kucharski, R., Zielonka, U., Sas-Nowosielska, A., Kuperberg, J.M.,
Worsztynowicz, A., Szdzuj, J., 2005. A method of mercury removal
from topsoil using low-thermal application. Environmental Monitor-
ing and Assessment 104, 341351.
Kunkel, A.M., Seibert, J.J., Elliot, L.J., Ricci, K., Lynn, E.K., Pope, G.A.,
2006. Remediation of elemental mercury using in situ thermal
desorption (ISTD). Environmental Science & Technology 40, 2384
2389.
Lee, S.H., Park, Y., 2003. Gas-phase mercury removal by carbon-based
sorbents. Fuel Processing Technology 84, 187206.
Lee, S.H., Rhim, Y., Park, Y., 2002. Preparation of novel sorbents for gas-
phase mercury removal. Carbon Science 3 (4), 187191.
Li, Y.H., Lee, C.W., Gullet, B.K., 2002. The eect of activated carbon
surface moisture on low temperature mercury adsorption. Carbon 40,
6572.
Matsuyama, A., Iwasaki, H., Higaki, K., Yabuta, H., Sano, T., Akagi, H.,
1999. Basic study on the remediation technology of mercury com-
pound-contaminated soil by low-temperature thermal treatment. In:
Ebingahus, R. (Ed.), Mercury Contaminated Sites. Springer-Verlag,
Berlin, pp. 421440.
Meij, R., Vredenbregt, L.H.J., te Winkel, H., 2002. The fate and behavior
of mercury in coal-red power plants. Air & Waste Management
Association 52, 912917.
Mendoza, J.L., Navarro, A., Viladevall, M., Dome`nech, L.M., 2005.
Caracterizacio n y tratamiento termico de suelos contaminados por
mercurio. SIAGA, tomo II, Sevilla, pp. 10771088.
Monterreal, R. 2005. Preliminar Analysis of Irradiance Distribution
Shutter-100%. PSA-CIEMAT internal document.
Nakamura, T., Senior, C.L., Burns, E.G., Bell, M.D., 2000. Solar-
powered soil vapor extraction for removal of dense nonaqueous phase
organics from soil. Journal of Environmental Science and Health 35,
795816.
Navarro, A., Biester, H., Mendoza, J.L., Cardellach, E., 2006.
Mercury speciation and mobilization in polluted soils of the Valle
del Azogue Hg mine (SE, Spain). Environmental Geology 49,
10891101.
A. Navarro et al. / Solar Energy 83 (2009) 14051414 1413
Navarro, A., Cardellach, E., Corbella, M. 2009. Mercury mobility in mine
waste from Hg-mining areas in Almer a, Andalusia (SE Spain). Journal
of Geochemical Exploration. doi: 10.1016/j.gexplo.2008.08.004.
Qiu, G., Cabrera, J., Marshla, A., Cai, Y., 2006. Mercury characterization
in a soil sample collected nearby the DOE Oak Ridge Reservation
utilizing sequential extraction and thermal desorption method. Science
of the Total Environment 369, 384392.
Rytuba, J.J., 2003. Mercury from mineral deposits and potential
environmental impact. Environmental Geology 43, 326338.
Spiric, Z., Hraste, M., 1999. Mercury saturation prole across the sulphur-
impregnated activated carbon bed. In: Ebingahus, R. (Ed.), Mercury
Contaminated Sites. Springer-Verlag, Berlin, pp. 409417.
Steinfeld, A., Palumbo, R., 2001. Solar thermochemical process technol-
ogy. In: Meyers, R.A. (Ed.), . In: Encyclopedia of Physical Science &
Technology, vol. 15. Academic Press, pp. 235256.
Troxler, W., Alperin, E.S., de Percin, P.R., Hutton, J.H., Lighty, J.S.,
Palmer, C.R., 1997. In: Thermal Desorption. Wastech, vol. 5.
American Academy of Environmental Engineers.
Viladevall, M., Font, X., Navarro, A., 1999. Geochemical mercury survey
in the Azogue Valley (Betic area, SE Spain). Journal of Geochemical
Exploration 66, 2735.
Vitolo, S., Seggiani, M., 2002. Mercury removal from geothermal exhaust
gas by sulfur-impregnated and virgin activated carbons. Geothermics
31, 431442.
1414 A. Navarro et al. / Solar Energy 83 (2009) 14051414