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Application of solar thermal desorption to remediation of mercury-

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DOI: 10.1016/j.solener.2009.03.013

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Solar Energy 83 (2009) 1405–1414

www.elsevier.com/locate/solener

Application of solar thermal desorption to remediation

of mercury-contaminated soils
A. Navarro a,*, I. Cañadas b, D. Martinez b, J. Rodriguez b, J.L. Mendoza a
a
Department of Fluid Mechanics, Polytechnic University of Catalonia (UPC), ETSEIT, Colón 11, 08222 Terrassa, Barcelona, Spain
b
Plataforma Solar de Almerı́a (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 significant 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 400–500 °C, mercury elimination was significant (41.3–87%). However, the results from heating to 320 °C or below 300 °C,
indicated little or negligible removal, possibly, because the fluid dynamics in the fluidized-bed module and the presence of cinnabar
and pyrite rich-Hg as dominant mineral phases.
These results show the potential for efficiently removing mercury and other pollutants from solid matrices (soil, waste, etc.) at low
temperatures.
Ó 2009 Elsevier Ltd. All rights reserved.

Keywords: Solar energy; Desorption; Mercury; Soil contamination; Mine wastes

1. Introduction The release of mercury into the environment in Hg min-

Mercury is the most hazardous metal for human health
and the environment due to its ability to bioaccumulate, its
toxic effects, 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 Hg0 vapor, derived from industries
such as Au–Ag 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).
*
Corresponding author. Tel.: +34 937398151; fax: +34 7398101.
E-mail address: navarro@mf.upc.edu (A. Navarro).
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; Fernández-Martı́nez 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 (HgSb4S8), corderoite
(Hg3S2Cl2), metacinnabar (cubic HgS), schuetteite
(Hg3(SO4)O2), montroydite (HgO), calomel (Hg2Cl2), tie-
mannite (HgSe) and kleinite (4[Hg2NCl]Hg[SO4,Cl]H2O).
The main process for extracting mercury from cinnabar is
to roast the ore at 500–600 °C, which releases Hg0. Thus,
when the temperature reaches to 600–800 °C, the mercury

0038-092X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2009.03.013
1406 A. Navarro et al. / Solar Energy 83 (2009) 1405–1414
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/solidifi-
cation, thermal desorption, vitrification, soil flushing 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 effectiveness 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 sulfide 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; Effelsberg and Barbknecht, 1991;
Effelsberg 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 effectiveness of STD, and a middle-temperature solar
furnace was used to evaluate the application of a fluid-
ized-bed reactor in thermal desorption.
Table 1
Desorption temperatures of different mercury phases.
Phase Desorption temperature of phase Hg (°C)
Hg0 <100
Hg2Cl2 170
HgCl2 <250, 220
HgO 420–550
HgSO4 450-500
HgS (cinnabar) 310–330
Hg in pyrite >450
Hg in Sphalerite 600
Hg matrix-bound 200–300
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 1873–1890 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), Se–HgS, tiemannite (HgSe),
corderoite (Hg3S2Cl2), shakhovite (Hg4SbO5(OH)3) and
schuetteite (Hg3(SO4)O2). 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 fluorite.
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 0–0.25 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 reflected light microscopy, X-ray diffraction (XRD)
and scanning electron microscopy (SEM) with an attached
energy dispersive X-ray spectroscopy system (EDS) at the
Electronic Microscopy Laboratory of the Universitat
Autònoma de Barcelona.
Hg phases were determined by solid-phase-Hg-thermo-
desorption (SPTD), based on the specific 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 flow of 300 mL/min. The
lowest level of detection under the given conditions is in the
range of 40–50 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.
 A. Navarro et al. / Solar Energy 83 (2009) 1405–1414
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 effective 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 filter 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-flux-density, low-
temperature solar furnace, which consists of five elements:
a solar reflector, a glass furnace (or reactor), a fluid-cooling
system, an Hg gas adsorption system, and a vacuum pump
which mobilizes ambient air from the glass furnace to the
activated-carbon filter (Fig. 1a). The system has a collector
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, FCA: activated-carbon filter.
1407
and rotating base which allows seasonal adjustment to the
solar position. The glass furnace is a high-temperature-
resistant glass flask 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 filter.
Finally, a vacuum pump generates the extraction flow-rate
of Hg-polluted gases.
The treatment procedure consists of placing the polluted
soil sample in the furnace, turning the reflector northward
and directing the center of sunlight reflected 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 2–4 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 fluidized-bed reactor design by CIEMAT and
CENIM-CSIC was used to test the feasibility of high-tem-
1408 A. Navarro et al. / Solar Energy 83 (2009) 1405–1414
perature solar desorption in the Plataforma Solar de
Almerı́a (PSA) Solar Furnace (Fig. 1b). This system has
two main parts, the PSA Solar Furnace facility, and the
solar fluidized-bed module connected to an Hg gas collec-
tion system with a final activated-carbon adsorption bed
(Fig. 2).
The PSA Solar Furnace consists of a flat heliostat, a
parabolic dish, and a louvered flux shutter. The GM140
flat-surface heliostat, which reflects the solar radiation onto
the parabolic dish, has a 140-m2 reflective area, with 93%
reflectivity. It tracks the sun continuously, and is controlled
by a remote system connected to a computer. The flux
shutter, which regulates how much solar radiation arrives
at the fluidized-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 reflecting area
of 98.5 m2 and reflectivity 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 flux of 300 W/cm2
and total power of 68 kw (Monterreal, 2005).
The fluidized-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
fluidized-bed installed in the test assembly” (Cañadas et al.,
2006).
The fluidized-bed module consists of an indirectly-
heated solar fluidized-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 fluidized flow (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 (Ballestrı́n et al., 2008).
The soil samples are inserted in the fluidized-bed cham-
ber for treatment. The fluidized-bed operates at a flow-rate
Fig. 2. Schematic drawing of the fluidized-bed module in the Solar Platform Almerı́a (MT-PSA).
of 50 L/min. As shown in Fig. 2, the fluidized-bed cylindri-
cal chamber is 1 m high and 20 cm in diameter. The conical
base is connected by the fluidized flow circuit to a pump/air
compressor that generates the fluidizing air flow. This
chamber is heated up by another outer module heated by
the absorber. At the top of the fluidized-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 fluidized-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 fluidized-bed chamber
through its steel walls, heating it, and then preheating the
air or gas that fluidizes 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 differ-
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 fluid-
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-
 A. Navarro et al. / Solar Energy 83 (2009) 1405–1414 1409

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 Almadén 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 affected 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: 200–250 °C and
300–330 °C (Fig. 3). The first 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 Hg0 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 (Hg3S2Cl2), mercury
dichloride (I) (Hg4O2Cl2), hypercinnabar (HgS), laffittite
(AgHgAsS3), metacinnabar ((Hg)S), shakhovite (Hg4SbO5
(OH)3), schuetteite (Hg3(SO4)O2) 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/m2 and no
more than 300 W/m2. 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 efficiency 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 significant when the temperature is above
approximately 130 °C, which is in agreement with the dom-
inant solid phases of mercury: cinnabar and Hg0 bound to
the solid matrix. Both phases have a volatilization temper-
ature of 300–330 °C and 200–250 °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, 91–130 °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
1410 A. Navarro et al. / Solar Energy 83 (2009) 1405–1414

B01 - furnace calcine

a 1800 200

1600 180
B0102
B0101 160
1400

140
1200

120
Extinktion

1000
100
800
80

600
60

400
40

200 20

0 0
0 100 200 300 400 500 600 700
°C

B02 - alluvial soil

b 200 100

180 90

160 80
B0202
B0201
140 70

120 60
Extinktion

100 50

80 40

60 30

40 20

20 10

0 0
0 100 200 300 400 500 600 700
°C

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 Hg0 matrix-bound dominant. (b) Soil sample B02 which shows cinnabar as dominant phase mineral.

M07, Hg is associated to mineral compounds matrix, and
possibly derived from the atmospheric deposition of Hg0
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 effectiveness, moving high amounts of gaseous Hg
to activated-carbon filter.
In the middle-temperature experiments (MT-PSA) the
global radiation was approximately 900 W/m2 (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 400–500 °C, mercury removal was sig-
nificant. 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 significative 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
 A. Navarro et al. / Solar Energy 83 (2009) 1405–1414 1411

Sample A03
300 1000

900

250
800

700
200
Temperature ºC

Radiation W/m2
600

150 500

400

100
300

T 170506 200
50

R 170506 100

0 0
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

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 heat and mass transport together with the filter-block for-
Data tests made in a solar furnace LT-UPC. mation may also explain the low Hg-removal of MT-PSA
Sample Initial Hg Final Hg % T Operation experiences, despite the high-temperature reached. In all
(mg/kg) (mg/kg) Desorption (mean) temperatures the samples treated in the MT-PSA experiences, the best
(°C) (°C)
results were obtained with samples that present dominant
A01 530 506 4.5 128.0 45–145 Hg0 bound to the solid matrix (Az21, M02 to M07), except
A02 1000 >1000 – 91.0 38–125
the sample B02, which is coincident with the LT-UPC
A03 210 >200 – 113.0 55–165
A04 540 >500 – 130.9 65–187 results.
A06 600 176 70.6 129.2 80–168 As content shows this metalloid was removed in heating
M04 4000 2800 30.0 203.3 68–247 tests in the same samples which have significant mercury
M05 50 12 76.0 213.0 110–280 desorption, except for Sample M07, and Samples B01
M06 399 240 39.8 168.5 128–197
and AZ22 (Table 5). As removal was between 5.5 and
M07 23 12 47.8 131.2 88–149
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
large percentage of mercury may be encapsulated in pyrite, operating temperatures are over 400 °C, although mercury
which has a high volatilization temperature (Table 1). The removal may differ depending on the minerals containing it
possible presence of HgSO4 or HgO (Sample A03), com- and exposure time. Results also suggest that mercury con-
pounds releasing Hg at above 400 °C, may also explain tained in cinnabar and pyrite is not efficiently removed by
the absence of mercury removal in some samples. Another desorption caused by the solar treatment in the experimen-
factor that may determine the efficiency of mercury tal conditions, although removal may be complete at
removal in the fluidized-bed experience is the velocity of higher temperatures (500–600 °C).
the solid particles inside the furnace. Thus, the terminal
velocity of material particles calculated from Stokes equa- 4. Conclusions
tion was comprised between 0.16 m/s (silty particles) and
4.15 m/s (sandy particles). Since entry velocity of particles This article reports the first time a solar thermal concen-
was 2.65 m/s, the silty particles, possibly, move to the trated facility has been used for remediation of mercury-
upper part of the furnace, accumulating in the filter. There- contaminated soils. Two different concentrated facilities
fore, the transport of dominant fine particles inside the flu- were employed with satisfactory results in different temper-
idized-bed furnace and the consequent low efficiency in the ature ranges.
1412 A. Navarro et al. / Solar Energy 83 (2009) 1405–1414

Sample B01T
1000 100

900 90

800 80
Temperature ºC

700 70

600 60

Percentage
500 50
Radiation W/m2;

400 40

300 30

200 20

100 10

0 0
14:51 15:06 15:21 15:36 15:51 16:06
TIME
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 The SPTD determinations showed two different temper-

Results of Hg elimination from the experiments in the middle-temperature
solar furnace (MT-PSA).
ature ranges in which Hg was released from the samples,
200–250 °C and 300–330 °C. From previous interpretation,
Sample Initial Final % Exposition Temperature
Hg Hg Desorption time (min) (°C)
the first Hg release peak indicates Hg released from the
(mg/kg) (mg/kg) matrix, whereas the second peak at higher temperatures
A01 530 >500 – 174 23–332
indicates presence of cinnabar (Biester and Scholz, 1997;
A02 1000 >1000 – 156 57–479 Navarro et al., 2006). The first release of Hg was typically
A03 210 >200 – 159 24–309 found for calcinated samples, where cinnabar was broken
A04 540 >500 – 115 20–337 down, but some Hg is re-adsorbed onto the calcinated
Az21 330 290 12.1 101 100–315 material during cooling. The second peak release is domi-
Az22 1 >1 – 79 93–318
M02 450 200 55.6 129 20–485
nant in the mining wastes and soils.
M03 470 60.9 87.0 315 38–482 The low-temperature experiments (LT-UPC) showed
M05 50 9.48 81.0 185 29–502 up to 76% mercury removal efficiency in soil and mine
M07 23 13.5 41.3 214 55–359 waste samples. Experimental results indicate that volatili-
B02 33 21 36.3 90 25–320 zation of mercury is only significant when the temperature
B01 66 >60 – 75 70–326
A05 400 >400 – 90 70–347
is above approximately 130 °C, which is in agreement
with the predominant mercury solid phases (Hg0 bound
to solid matrix in samples A06 and M04 to M07). The
Table 5
middle-temperature experiments (MT-PSA) showed that
Results of As elimination from the experiments in the middle-temperature
solar furnace (MT-PSA). when soil and mine waste were heated to 400–500 °C,
mercury removal was significant. However, the results
Sample Initial As (mg/kg) Final As (mg/kg) Desorption (%)
from heating to 320 °C or below 300 °C, show little or
A01 300 >300 –
negligible removal of mercury, mainly, in the samples
A02 620 >600 –
A03 184 199 – with significative amounts of cinnabar and Hg-rich pyrite.
A04 680 >700 – The As solar desorption tests showed that between 5.5
A05 320 >300 – and 77.3% of this metalloid was removed, indicating the
B01 9.6 7 27.0 feasibility of As desorption from polluted soil and mine
AZ22 12.9 7 45.7
waste.
B02 20.8 13 37.5
AZ21 448 423 5.5 The thermal desorption technique was successfully
M02 296 67 77.3 applied to polluted samples from the Valle del Azogue
M03 1610 578 64.0 and Bayarque mines, and was demonstrated to be an alter-
M05 129 114 11.6 native method for decontaminating hazardous waste sites
M07 233 297 –
where mercury is present because of its volatility.
 A. Navarro et al. / Solar Energy 83 (2009) 1405–1414
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 Energéticas,
Mediombientales y Tecnológicas), and the 2003–2004
Technical and Scientific Infrastructure Program (FEDER
CIEM-E008). The authors wish to thank Dr. Ursula Kelm
and Mónica Uribe for ray X analyses and their interpreta-
tion, to Alfonso Vázquez and Bernardo Fernández of the
CENIM-CSIC for their participation in the design and
development of the fluidized-bed, and finally to the PSA
Furnace personnel, especially Jose Galindo, for their tech-
nical support in this project.
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