Environ Geochem Health (2006) 28:529–540
DOI 10.1007/s10653-006-9049-x
ORIGINAL PAPER
Atmospheric mercury emissions from polluted gold mining
areas (Venezuela)
A. Garcı́a-Sánchez Æ F. Contreras Æ M. Adams Æ
F. Santos
Received: 26 April 2005 / Accepted: 6 April 2006 / Published online: 21 November 2006
 Springer Science+Business Media B.V. 2006
Abstract Soil, waste rock and mud from mer-
cury-gold amalgamation mining areas of El
Callao (Venezuela) are highly enriched in Hg
(0.5–500 lg g–1) relative to natural background
concentrations ( < 0.1 lg g–1). Mercury fluxes to
the atmosphere from twelve polluted sites of this
area were measured in situ (6 a.m. to 8 p.m.)
using a Plexiglas flux chamber connected to a
portable mercury analyzer (model RA-915+;
Lumex, St. Petersburg, Russia). Mercury fluxes
ranged between 0.65 and 420.1 lg m–2 h–1, and
the average flux range during the diurnal
hours was 9.1–239.2 lg m–2 h–1. These flux values
are five orders of magnitude higher than both
reported world background Hg fluxes
(1–69 ng m–2 h–1) and the regional values, which
are in the range 2–10 ng m–2 h–1. The flux results
obtained in this study are, however, similar to
those measured at Hg polluted sites such as
A. Garcı́a-Sánchez (&) Æ F. Contreras
Department of Environmental Geochemistry, IRNA-
CSIC, Aptdo. 257, Salamanca, Spain
e-mail: misfis@usal.es
M. Adams
Faculty of Agronomy, University Central
of Venezuela, Maracay, Venezuela
F. Santos
Faculty of Environmental Sciences, University
of Salamanca, Salamanca, Spain
chloro-alkali plants or polymetallic ore mining
districts (>100,000 ng m–2 h–1). The results from
this study also show that Hg emissions from the
soil are influenced by solar radiation, soil tem-
perature and soil Hg concentration. Our data
suggest that solar radiation may be the dominant
factor affecting Hg
emission since the major
species of mercury in polluted soil is Hg

(85–97% of total Hg). The simple release of Hg

vapor is probably the dominant process occurring
with incident light in the field. The apparent
activation energy for mercury emission indicates
that the volatilization of mercury mainly occurred
as a result of the vaporization of elemental mer-
cury in soil. The degree of Hg emission differed
significantly among the soil sites studied, which
may be due to variations in soil texture, organic
matter content and soil compaction.
Keywords Mercury volatilization Æ Hg-Au
amalgamation Æ Polluted mining soils Æ
Chamber flux
Introduction
Mercury (Hg) is an ubiquitous toxic element
present at trace concentrations in the environ-
ment. Its chemical forms, mobilization and
redistribution are influenced by both abiotic and
biotic processes. Mercury contamination of soil,
123
530
stream sediment and surface or groundwater
represents a threat to human health and may be
regarded as a global issue. Symptoms of chronic
exposure to Hg in air or food (mainly fish) include
serious dysfunctions of the central and peripheral
nervous systems, neuromuscular disorder, trem-
ors, severe kidney damage, autoimmunity, among
others (Barbosa et al. 2001; Drake et al. 2001;
Farhana et al. 2005; Suzuki 1997).
Mercury is emitted into the atmosphere from a
number of natural and anthropogenic sources. It
can then be deposited in the vicinity of the
emission source(s) or subjected to long-range
atmospheric transport followed by deposition in
ecosystems remote from the source(s).In contrast
to most of the other heavy metals, Hg and many
of its compounds behave exceptionally in the
environment due to their volatility and capacity
for methylation. Long-range atmospheric trans-
port of Hg, its transformation to more toxic
methylmercury compounds and the bioaccumu-
lation of these compounds in the aquatic food
chain have motivated intensive research on Hg
within the framework of a pollutant of global
concern (Bergan & Rodhe 2001; Betts 2001;
Ebinghaus et al. 1999; Jackson 1997; Lamborg
et al. 2002; Lindqvist et al. 1991; Pyle & Mather
2003; Schroeder et al. 1998).
The global emissions of Hg are approximately
6000–7500 ton year–1, 50–75% of which are due
to anthropogenic activities (Nriagu 1989; Mason
et al. 1994; Pirrone et al. 2001). Most of the Hg in
the atmosphere is in the form of elementary
mercury vapor (Hg
). Due to its high volatility,
low solubility and chemical stability, Hg
can re-
main in the atmosphere for as long as 1–2 years,
thereby enabling its dispersion and transport over
large distances, regionally and even glob-
ally(Bergan & Rodhe 2001; Bullock & Brehme
2002; Lin & Penkonen 1999; Liu et al. 2002; Sei-
gneur et al. 2003; Schroeder & Muntle 1998).
The global Hg cycle is also influenced by emis-
sions from mining or heavily contaminated indus-
trial areas (Drake et al. 2001; Gillis & Miller 2000a;
Wallschläger et al. 2002). Thus, its geochemical
and environmental characterization in these areas
is not only of interest on a local scale, but also on a
global one. For this reason, it is of great impor-
tance to establish the type and degree of Hg
123
Environ Geochem Health (2006) 28:529–540
contamination of the soil, the residence time in the
soil under different meteorological conditions and
the scale of the flow of Hg into the atmosphere per
unit area of soil surface. This flow of Hg from the
soil to the atmosphere can be measured by using
flow chambers and by analyzing Hg in situ (Carpi
& Lindberg 1998; Gillis & Miller 2000a, b; Lee
et al. 2003; Poissant et al. 2004; Wallschläger et al.
2002; Wängberg et al. 2003).
The Hg flux (soil-air) is related to the total
gaseous Hg (TGM) concentration in the air, the
concentration and species of Hg in the soil, the
temperature and moisture content of the soil and
solar radiation. (Boudala et al. 2000; Carpi &
Lindberg 1997; Engle & Gustin 2002; Gillis &
Miller 2000a; Gustin et al. 1997, 1998; Lindberg
et al. 1995; Lindberg & Stratton 1998; Rasmussen
et al. 1998). Some studies have also reported
widely varying flux rates, which have generally
been attributed to the different soils on which the
chamber is placed and also to large measurement
errors based on different flow rates in the flow
chambers and on the exposure of the flux cham-
ber to variable ambient winds (Gillis & Miller
2000b; Wallschläger et al. 1999).
In some tropical areas (Tanzania, Brazil, Ven-
ezuela, Bolivia, Colombia, Ecuador, Indonesia,
etc.) small-scale miners use Hg (amalgamation
techniques) in the gold (Au) extraction process,
thereby causing Hg contamination of the envi-
ronment. Many reports have been published on
the environmental contamination caused by Au
mining in Brazil and other mining areas (Fostier
et al. 2000; Kambey et al. 2001; Malm et al. 1998).
The soil surfaces of mining sites may emit
several hundred tons of Hg per annum and, con-
sequently, may play a significant role in the global
Hg cycle by contributing to background fluxes of
Hg
in the atmosphere. Nearly 40,000 people are
in one way or another involved in gold mining in
the Guayana region of Venezuela; most are small-
scale miners, including illegal migrants from
neighboring countries. The mining of a stream
placer or a gold quartz vein has one important
process in common – both use Hg for the Au-
amalgamation. This process results in the annual
discharge of 40–50 ton of Hg into local ecosys-
tems (Nico & Taphorn 1994; Shrestra & Ruı́z
1989). Many miners, some local residents and
Environ Geochem Health (2006) 28:529–540
indigenous people may already be suffering from
Hg poisoning, but the effects of Hg that has en-
tered local food chains may have more severe
effects on wildlife, especially piscivorus mammals.
The study reported here was conductedin Bolivar
State (Guayana, Venezuela), between the mining
towns of El Peru and El Callao, in the Cuyunı́
river basin. The aim was to make ‘‘in situ’’ esti-
mates of the scale of Hg emission into the air
from the polluted soil of the mining sites using a
flux chamber connected to a portable mercury
analyzer as well as to gain an understanding of the
possible relationship between the Hg flux and soil
and environment parameters.
Materials and methods
Study site
The study site (Cuyuni river basin; Fig. 1) is lo-
cated in Bolivar State, Venezuela, which covers
an area of approximately 36,000 km2. Several
gold mines are located in this area, mainly around
El Callao city, and Hg has been used for decades
here in the extraction, preparation and recovery
stages of the Au operations. Gold is recovered
through its amalgamation with Hg onto a copper
plate followed by burning of the amalgam. These
processes result in the direct release of Hg into
the atmosphere. Inefficient recovery processes
also mean that significant amounts of Hg are
transferred to tailing waste and surface waters.
The Cuyuni river basin geologically belongs to
the Precambrian Shield of Guayana. The geologic
formation ‘‘El Callao’’ consists of a greenstone
belt, the oldest of the region, which contains
amphibolites, quartz-veins and many of the
known auriferous deposits. The principal constit-
uents of these deposits are stockworks of quartz-
veins, which vary in width from centimeters up to
1 m, with Au contents of up to 100–200 mg kg–1.
The annual average temperature is 26.3
C, and
the annual average precipitation ranges from 1300
to 2000 mm, corresponding to five dry months and
seven humid ones, respectively. The soils com-
prise stony loam, 0.5–1 m in depth. Rock outcrops
occur in some places. In general, the soils are very
acidic with good drainage and low natural fertility.
They are classified as haplustox (humic laterite).
531
There are approximately 500 Au mills dis-
tributed throughout the Cuyuni river basin;
these are located in diverse zones, such as Hoja
de Lata, Atlántida, Bizkaitarra-km 88 and El
Bochinche and, especially, in the zone of El
Callao. The El Callao zone has been one of the
most important auriferous production sites in
Venezuela, with more than 230 mining sites
(quartz-vein ores and placers) of auriferous
pyrite and native gold (Rodriguez 1986). At the
time of this article, approximately 110 mills are
distributed throughout different sectors of El
Callao, such as La Ramona, Peru, New Mexico,
Nacupay and El Choco. Some 200 ha of the soils
of these mill sites have been heavily contami-
nated, with the concentrations of Hg in these
soils ranging between 0.5 and 500 mg kg–1.
The principal Hg form is Hg
–around 95% of
the total Hg measured (Contreras, personal
communication). This high contamination
extends – albeit to a lesser degree – to the
squares and parks in nearby El Callao City.
All measurements were made in the El Callao
zone. It was chosen as the site for measuring the
Hg flux from the soil to the atmosphere because
(1) the area has been under a relatively higher
population/environmental pressure due to the
presence of many mills; (2) mining activities in
which Hg has been used to extract Au have been
going on for hundreds years. The measurements
were conducted from May 16 to May 31, 2004 in
11 selected mining sites and in Bolivar Square of
El Callao City (Table 1). The sampling codes
used are given in Table 1.
Mercury analysis
A Zeeman atomic absorption spectrometer
(ZAAS) manufactured by Lumex (St. Petersburg,
Russia) was used in this study. The operation of
the RA-15 + analyzer is based on differential
Zeeman atomic absorption spectrometry using a
high frequency modulation of light polarization
(ZAAS-HFM) for the Hg determination. The
instrument collects samples at a mass-flow con-
trolled flow rate of 20 L m–1 and the concentra-
tion can be read directly in the Zeeman AAS.
The analytical method used is based on that of
Sholupov et al. (2004).
123
532
Fig. 1 Location of study
site
Mercury analyses of the soil samples were
performed using the Milestone Instruments (So-
risole, Italy) Hg analyzer (model DMA-80). The
analytical accuracy was checked with certified
reference materials: W-1 rock (U.S. Geological
Survey), San Joaquin Soil and Montana Soil (U.S.
National Institute of Standards and Technology
and National Research Council of Canada); the
precision was assessed by performing the analysis
ten times for a simple soil sample. The relative
standard deviation (RSD) was < 5%.
Flux chamber measurements
We used a 20·60·20-cm Plexiglas chamber
(height · length · width) to obtain flow
123
Environ Geochem Health (2006) 28:529–540
measurements, which corresponds to a covered
surface area of 0.12 m2, a volume of 0.24 dm3 and
a flow rate of 20 L m–1. The inlet and outlet
heights were 5 and 16 cm, respectively. Plexiglas
was chosen as the construction material (Walls-
chläger et al. 1999) because it is inert, transparent
and a hard plastic, which permits the transmission
of natural solar visible radiation.
A blank measurement for the chamber was
performed by sealing off the bottom of the
chamber and passing the ambient air through it to
determine whether or not the chamber material
itself accumulates or releases mercury. We mea-
sured chamber blank fluxes in the field by
attaching a Plexiglas plate to the bottom of the
chamber (Wasllschläger et al., 1999). These flux
Environ Geochem Health (2006) 28:529–540 533

Table 1 Summary of Hg fluxes, Hg content and some properties of the soil samples
Soil Hg flux Average Hgflux Range of Hg flux Hg soil Organic pH Sand Silt Clay
sample at 1 p.m. between 6 a.m. (lg m–2h–1) content matter (%) (%) (%) (%)
(lg m–2h–1) and 8 p.m (lg g–1)
(lg m–2h–1)

SJ1 407.50±1.50 239.2±146 50.5–420.1 29.2 2.5 7.7 68 18 14

SJ2 288±1.40 129.6±100.7 20–288 15 1.7 7.6 76 13 11
SJ3 240.50±1.20 97.5±84.7 16.9–240.5 11.7 1.3 7.6 84 7 9
SJ4 180.60±1.40 87.8±78.5 11.0–221 8 1.1 7.7 86 7 7
JH1 320.90±1.10 182.3±117.5 12.8–330 49.2 4.4 7.4 14 24 62
JH2 264.30±1.0 105.7±94.7 9.6–264.3 29 1.3 7.7 20 50 30
JH3 208±1.80 63.5±60,43 7.7–208 12.5 1.3 7.7 40 44 16
NC1 212.03±2.10 99.6±73.78 13.5–212 11 2.2 6.7 24 57 19
NC2 120.80±1.40 53.6±44.3 6.2–120.8 6 1.7 6.6 18 60 12
LR1 99.23±1.60 33.7±31.31 0.65–99 5 3.1 6.2 18 28 54
LR2 44.03±2.0 16.2±14.6 1.80–44 2 2.8 6.1 14 60 26
Square EC 15.92±1.80 9.1±5.5 1.31–15.9 0.5 4.1 6.7 55 29 16

SJ (1–4), Mills of the San Jose area located in the town of El Peru; JH (1–4), mills of Josefa Herrera area at El Peru town;
NC (1–2) = mills of the Nacupay area near El Callao City; LR (1–2), mills of Alejandria at the town of La Ramonan; Square
EC, Bolivar Square in El Callao City

blanks ranged from 2.8±3.1 to 4.5±3.4 ng m–2 h–1,
which constituted less than 0.1% of the average
Hg fluxes measured. Based on these results, we
concluded that blank measurements would not
significantly influence the soil flux measurements.
However, the ambient TGM concentration did
vary during the periods in which the blank mea-
surements were taken, even though the chamber
was elevated to around 100 cm in order to reduce
the intrusion of near-surface air with high TGM
concentrations. The blank measurements were
also affected by changes in solar radiation and
temperature. Consequently, we carried out blank
measurements before each soil flux measurement.
Solar radiation measurements
Solar radiation was measured using a radiometer
Li-Cor model LI 1000 Datalogger (Lincoln, Nb.),
and the temperature was measured with a ther-
mometer from Premium Instruments (Chicago,
Ill.).
Soil characterization
Organic matter in the soil was analyzed by the
dichromate oxidation method, particle size dis-
tribution (sand, silt, clay) was analyzed using the
Robinson pipette method and pH was determined
potentiometrically in a soil paste saturated with
water (Soil Conservation Service 1972).
Results and discussion
To illustrate the dependence of Hg soil content
on Hg flux, the correlation between Hg flux at
1 p.m and the associated soil Hg concentrations is
shown in Fig. 2. While the regression coefficient is
good and significant, it may have had higher
statistical significance if the soil samples of the JH
mill sites (Table 1), with their higher Hg contents,
were omitted. Mercury fluxes lower than ex-
pected in these soils may reflect the differences
among them with respect to some of the soil
characteristics, mainly texture (Table 1) and
perhaps porosity and compactness. Based on
these results, the Hg
emission from the JH soils
(argillaceous) is more difficult than that from
sandy soils, probably due to a higher Hg
physical
sorption capacity of clay soil than sandy soil.
Mechanical disturbance of Hg
droplets, which
improves the Hg
emission process due to the
breaking of the thin oxidation layer on the
droplet surface, may also be more likely in sandy
soils.
Mercury emissions increased during the day-
time as surface processes evolved, such as

123
534 Environ Geochem Health (2006) 28:529–540

Flux Hg at 1 pm (µgm -2h-1)
Fig. 2 Correlation between flux Hg at 1 p.m. and Hg
content in soil
500 y = 6.516x + 103.01 increasing incident light and soil surface temper-
R2 = 0.637 ** ature, both of which facilitate the release of Hg
400 into atmosphere. Environmental parameters such
as air temperature, solar radiation, wind turbu-
300 lence and precipitation (Carpi & Lindberg 1997;
Gustin et al. 1998; Lindberg et al. 1999; Poissant
200 et al. 1999) have all been demonstrated to influ-
ence the emission of Hg from the soil.
100 Figure 3 illustrates the solar radiation-en-
hanced Hg flux and shows how large fluctuations
0 in Hg flux occur with small changes in soil tem-
0 10 20 30 40 50 60
perature and large changes in light, thereby
Soil Hg (µg g-1)
indicating the great importance of solar radiation
in influencing Hg emissions. When the sun was
intermittently hidden by clouds, Hg emissions

Fig. 3 Mercury flux, soil a 500 2500

temperature and solar
radiation at soil sites SJ 1
(a) and JH 1 (b) 400 2000

Solar Radiation (W)

Hg Flux (µgm-2h-1)
Soil temp (°C/5)

300 1500

200 1000

100 500

0 0
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Time (hour)

b 400 2500

2000
300
Solar Radiation (W)
Hg Flux (µgm-2h-1)
Soil temp (°C/5)

1500
200
1000

100
500

0 0
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Time (hour)
Hg Flux
Soil temperature
Solar radiation

123
Environ Geochem Health (2006) 28:529–540 535

a 500 behind the clouds, Hg emissions increased shar-

y = 0.1058x - 4.2413
ply, again despite only a small change in the soil
R2 = 0.575 ***
400 temperature.
Flux Hg (µgm-2h-1)

It has been reported that solar radiation en-

300
hances the Hg flux on a short time scale (minutes)
200 through the direct transfer of the photoenergy to
Hg, and also over longer time periods (hours) by
100 increasing the soil temperature (Zhang et al.
2001). Gustin et al. (1999, 2003) suggested that
0
0 500 1000 1500 2000 2500 light-enhanced volatilization could be caused by
Solar Radiation (W) the desorption of Hg
or by a photochemical
reaction with a Hg species. In our case where the
b 500 y = 7.5209x - 168.07 major species of Hg in polluted soil is Hg
,
R2 = 0.284 ***
the simple release of Hg
vapor is probably the
400
Flux Hg (µgm-2h-1)

dominant process occurring with incident light in

300 the field.
Our results indicate that Hg emission is more
200
highly dependent on solar radiation than on soil
100 temperature (Fig. 4). This in turn suggests that
Hg is emitted from a shallow surface layer of soil
0 where light penetration is possible. Our data
15 25 35 45 55
Soil temperature (°C) suggest that solar radiation may be the dominant
factor affecting Hg emission.
Fig. 4 Correlation between the Hg flux and solar radia-
The relationship between Hg
emission and
tion (a) or soil temperature (b)
soil temperature can be further examined using
the Arrhenius equation; this approach can be
y = -10.337x + 44.424 used to quantify the general dependence of the
16
R2 = 0.381 Hg
emission process on temperature:
Ln Hg Flux (ngm-2h-1)

Ea
12 lnðHgfluxÞ ¼ þ constant
RTs

where Ea is the apparent activation energy for

8 Hg
emission, R is the gas constant
(1.9872 kcal mol–1) and Ts is the soil temperature
in K.
4 The natural logarithm of the Hg flux is plotted
3.1 3.2 3.3 3.4 3.5
against inverse temperature in Fig. 5. The best fit
Inverse of the soil temperature (103 K-1)
– Ea of 20.4 kcal mol–1 – is higher than the Hg

Fig. 5 Natural logarithm of the Hg flux over soil and the liquid heat of vaporization of 14.5 kcal mol–1 at
inverse of the soil temperature (1.0–0.5 cm ) – the 20
C (Lide 1993). Therefore, if we consider all of
Arrhenius plot
the soils studied, our measured Ea values are
greater than the heat of vaporization of existing
also changed correspondingly (1 p.m. in Fig 3a or Hg
. This supports the hypothesis of a physical
11 a.m. and 2 p.m. in Fig 3b) with changes in the desorption process of Hg
on the soil components
solar radiation. Emissions dropped rapidly at (minerals and organic matter) prior to the Hg

both soil sites immediately following shading vaporization.
from the sun despite only a gradual decline in soil The apparent activation energy for Hg
emis-
temperature. When the sun re-appeared from sion at the SJ, JH, NC and LR soil sites and at the

123
536 Environ Geochem Health (2006) 28:529–540

Table 2 Soil Hg flux at several unpolluted sites

Site Method Hg (ng m–2 h–1) Reference

Background forest soils, Sweden Chamber flux 2–2.5 Xiao et al. (1991)
Background soils, Sweden Modeling 0.3 Schlüteret et al. (1995)
Boreal forest floor, Sweden Chamber flux 1–4 Lindberg et al. (1998)
Unpolluted soils Chamber flux 2–7 Carpi & Lindberg (1998)
Open field soils, Tennessee 12–45
Grassland, Quebec Chamber flux 1–8.3 Poissant & Casimir (1998)
Soils in Nevada Chamber flux 2.4–2.5 Wallschläger & others (1999)
Apple orchard, University of Connecticut Chamber flux 0.31–12.98 Gillis & Miller (2000a)
Shaded forest soil, Michigan Chamber flux 1.4 Zhang et al. (2001)
Quaternary volcanic rock, flowery 8.22–18.4
peak, NV and Quaternary basalt, long Valley Chamber flux 0–20 Engle & Gustin (2002)
Caldera, California
Soils, Nova Scotia Chamber flux –1.4–4.3 Boudala et al. (2000)
Agricultural soils Micrometeorological 9–67 Cobos et al. (2002)
No contaminated soils in NW USA Modeling 0–2.3 Bash et al. (2004)
and SW Canada
Background throughout, Nevada 2
Substrate near altered geologic units Chamber flux 15.5 Nacht & Gustin (2004)
Unpolluted soils in Lara State Venezuela Chamber flux 2 –10 In this work

Table 3 Comparison of differences measured soil Hg fluxes in polluted sites

Site Method Hg (ng m–2 h–1) Reference

Chlor-alkali sludge Laboratory chamber + activated 120,000–170,000 Lindberg & Turner (1977)
charcoal
Polluted mining soils (Almaden) Laboratory chamber + activated 130–330 Lindberg et al. (1979)
charcoal
Old roasted cinnabar banks (Almaden) Chamber flux 80,000–110,000 Ferrara et al. (1997)
Soils amended with municipal Chamber flux 170–700 Carpi & Lindberg (1997)
sewage sludge
Soil unit - mining districts Ivanhoe Chamber flux 0–27,600 Engle et al. (2001)
Municipal landfill in Korea Modeling 3.99–1,011 Kim et al. (2001)
Mine waste, Peavine peak, Nevada Chamber flux 16.27–84.47 Engle & Gustin (2002)
Contaminated floodplains in Germany Chamber flux 43 Wallschläger et al. (2002)
Mining districts: Chamber flux 3,122–5,066 Gustin et al. (2002)
Knoxville – McLaughlin,
Knoxville reed mine 4,666
Carson River, Nevada 116,778–203,000
Idria, Aurora 115,828
New Idria mine 18,959
Knoxville mining district 105–12,214
New Idria mining district 6–9,600
Ivanhoe mining district Chamber flux 97–59,100 Gustin et al. (2003)
Carson River superfind 0–11,500
Sulphur Banks superfund site 188–9,499
Soils around plant chlor-alkali Chamber flux 1,950–13,700 Wängberg et al. (2003)
Soils around plant chlor-alkali Chamber flux 1–13 Southworth et al. (2004)

EC Square soil site (15.5, 22.9, 23.1, 22.5 and
21.1 kcal mol–1, respectively) coincides well with
other published soil Hg
activation energies
(Boudala et al. 2000; Carpi & Lindberg 1997;
Gustin et al. 2003; Xiao et al. 1991).
However, at the SJ soil site, the Ea value
(15.5 kcal mol–1) is close to activation energy of
elemental Hg, which implies that the volatiliza-
tion of Hg mainly occurs as result of vaporization
of the Hg
.

123
Environ Geochem Health (2006) 28:529–540 537

The differences between the Ea values calcu- even in the Hg global cycle, although it is not an
lated for several soil sites may be due to any important source of atmospheric Hg in relation to
number of differences in the soil characteristics, other anthropogenic sources (approx. 4000 ton;
such as Hg speciation, Hg
sorption mechanisms Mason et al. 1994).
in soil particles, among others, and to differences
in the depths at which the soil temperatures were
Conclusions
measured, since the surface probe was inserted at
around 0.5–1 cm below the soil surface. The
The Hg flux measurements from the polluted soils
apparent activation energy will be higher in those
(gold mining and milling sites) in the El Callao
soils in which the temperature measurements are
area are approximately fivefold higher than the
deeper, since the Hg vaporization process mainly
reported world background Hg fluxes. In agree-
occurs in the soil surface.
ment with other reported data, we found the Hg
For comparison purposes, Hg emissions from
flux to be strongly correlated with solar radiation
substrates not considered to be naturally en-
at a soil site exposed to direct sunlight. We ob-
riched in Hg ( < 0.1 lg g–1; Gustin et al. 2000)
served large differences in Hg flux between
range from 0 to approximately 15 ng m–2 h–1
cloudy and sunny hours in the same day.
(Engle et al. 2001). Our results (Table 1) are five
The apparent activation energy for mercury
orders of magnitude higher than both these
emission indicates that the volatilization of mer-
world background levels (Table 2) and regional
cury occurred primarily as a result of the vapori-
background levels (Lara region, Venezuela; 2–
zation of elemental mercury (Hg
) from the soil.
10 ng m–2 h–1). If we compare the values with
The differences between the Ea values and the
those from some of the polluted sites (Table 3),
calculated and measured Hg fluxes, respectively,
we find that only the chloroalkali plant sites and
at different soil sites may be due to differences in
some polymetallic ore mining districts show a
the soil characteristics.
similar degree of Hg emission (>100,000 ng m–
2 –1 Our results show that heavily polluted Hg soils
h ). However, there is a significant difference:
can be important source areas of Hg emission to
the substrate Hg concentration at our polluted
the atmosphere and might contribute significantly
Hg-Au mining sites is very low in relation to that
to the regional – or even global – Hg cycle.
at mining sites with cinnabar as the source of Hg
Moreover, such a large amount of Hg in air is a
(Gustin et al. 2003). The Ea of Hg vaporization
threat to ecosystems and to human health.
is of course very low for Hg
liquid relative to
HgS; moreover, mercury size distribution, sorp- Acknowledgments Funding for this study was provided
tion in soil components, etc. can cause some by the FONACIT (Venezuela), Proyect S1-2000000760,
variation in Ea values. IRNASA-CSIC (Spain) and Faculty of Agronomy, Uni-
versity Central of Venezuela. We also would like to thank
There are also significant differences in the
Mr. José Alejandrı́a (Company MINVECA) and Dr. Ar-
degree of Hg emission between the SJ and JH soil mando John Madero (CVG-TECMIN) for their logistic
sites, which can be due to differences in the tex- support.
ture (Table 1): SJ soils with higher Hg emission
are sandy soils, whereas JH soils with lower Hg
emission are clay soils. References
When we considered only the exposed surface
of the El Callao mining soils (approx. 200 ha), we Barbosa, A. C, Jardim, W, Dorea, J. G, Fosberg, B, & Sousa,
J. (2001). Hair mercury speciation as a function of
estimated a total Hg flux during the diurnal hours
gender, age and body mass index in inhabitants of the
on the order of 400 g h–1. This level of Hg emis- Negro River basin, Amazon, Brazil. Archives of Envi-
sion is of the same order of magnitude as the ronmental Contamination and Toxicology, 40, 439–444.
emissions from the Almadén mine or from a large Bash, J. O., Miller, D. R., Meyer, T. H., & Bresnahan, P.
A. (2004). Northeast United States and Southeast
coal-fired power plant (Ferrara et al. 1997). This
Canada natural mercury emissions estimated with a
level of Hg emission (around 3 ton year–1) may surface emission model. Atmospheric Environment,
be significant at the local or regional levels, or 38, 5683–5692.

123
538
Bergan, T, & Rodhe, H. (2001). Oxidation of elemental
mercury in the atmosphere; constraints imposed by
global scale modelling. Journal of Atmospheric
Chemistry, 40, 191–212.
Betts, K. S. (2001). Arctic may be naturally generating
reactive gaseous mercury. Environmental Science and
Technology, 434A–435A.
Boudala, F. S., Folkins, I., Beauchamp, S, Tordon, R,
Neima, J, & Johnson, B. (2000). Mercury flux mea-
surements over air and water in Kejimkujik National
Park, Nova Scotia. Water, Air and Soil Pollution, 122,
183–202.
Bullock, O. R, & Brehme, K. A (2002). Atmospheric
mercury simulation using CMAQ model: Formulation
description and analysis of wet deposition results.
Atmospheric Environment, 36, 3135–2146.
Carpi, A, & Lindberg, S. E. (1997). Sunlight-mediated
emission of elemental mercury from soil amended
with municipal sewage sludge. Environmental Science
and Technology, 31, 2085–2091.
Carpi, A., & Lindberg, S. E. (1998). Application of a
Teflon dynamic flux chamber for quantifying soil
mercury fluxes: tests and results over background
soils. Atmospheric Environment, 32, 873–882.
Cobos, D., Baker, J., & Natera, E. (2002). Conditional
sampling for measuring mercury vapor fluxes. Atmo-
spheric Environment, 36, 4309–4321.
Contreras, F., Romero, A., Adams, M., Garcia-Sanchez,
A., & Santos, F. (2005). Efecto de la aplicación
de arcillas adsorbentes y caliza en la inmovilizacion de
Mercurio en suelos del Estado Bolivar. In: Actas
del XVII Congreso Venezolano de la Ciencia del
Suelo.
Drake, P. L., Rojas, M., Reh, C. M., Charles, A. M., &
Jenkins, F. M. (2001). Occupational exposure to air-
borne mercury during gold mining operations near El
Callao, Venezuela. International Archives of Envi-
ronmental Health, 74, 206–212.
Ebinghaus, R., Tripathi, R. M., Wallschlager, D., &
Lindberg, S. E. (1999). Natural and anthropogenic
mercury sources and their impact on the air-surface
exchange of mercury on regional and global scales.
In: R. Ebinghaus, R. Turner, L. de Lacerda, O.
Vasiliev, & W. Solomons (eds.), Mercury contami-
nated sites. Springer, Berlin Heidelberg New York,
pp 1–50.
Engle, M, Gustin, M., & Zhang, H. (2001). Quantifying
natural source mercury missions from the Ivanhoe
mining district, north-central Nevada, USA. Atmo-
spheric Environment, 35, 3987–3997.
Engle, M. A., & Gustin, M. S., (2002). Scaling of atmo-
spheric mercury emissions from three naturally en-
riched areas: Flowery Peak, Nevada; Peavine Peak,
Nevada; and Long Valley Caldera, California. The
Science of the Total Environment, 290, 91–104.
Farhana, Z., Shamim, R., Soghra, H., & Rizwan, K. (2005).
Low dose mercury toxicity, human health. Environ-
mental Toxicology and Pharmacology, 20 351–360.
Ferrara, R., Maserti, B., Anderson, M., Hender, H.,
Ragnarson, P., & Svanderg, S. (1997). Mercury
degassing rate from mineralised areas in the Medi-
123
Environ Geochem Health (2006) 28:529–540
terranean basin. Water, Air and Soil Pollution, 93,
59–66.
Fostier, A. H., Forti, M. C., Guimarães, J. R., Melfi, A. J.,
Boulet, R., Espirito Santo, C. M., & Krug, F. J. (2000).
Mercury fluxes in a natural forested Amazonian
catchment (Serra do Navio, Amapá State, Brazil).
Science of the Total Environment, 260, 201–211.
Gillis, A., & Miller, D. R. (2000a). Some local environ-
mental effects on mercury emission and absortion at a
soil surface. Science of the Total Environment, 260,
191–200.
Gillis, A., & Miller, D. R. (2000b). Some potential errors
in the measurement of mercury gas exchange at the
soil surface using a dynamic flux chamber. Science of
the Total Environment, 260, 181–189.
Gustin, M., Taylor, G., & Maxey, R. (1997). Effect of
temperature and air movement on the flux of ele-
mental mercury from substrate to the atmosphere.
Journal of Geophysical Research, 102, 3891–3898.
Gustin M., Rasmussen P., & Biester H. (1998). Mecha-
nisms influencing the volatile loss of mercury from
soil. Symposium volume Air and Waste Management
Association meeting September (1998). Measurement
of Air Toxics and Related Air Pollutants, 224–235.
Gustin, M., Lindberg, S. E., & Marsik, F. et al. (1999).
Nevada Storms proyect: measurement of mercury
emissions from naturally enriched surfaces. Journal of
Geophysical Research, 104 D17, 21831–21844.
Gustin, M. S., Lindberg, S. E., Austin, K., Coolbaugh, M.,
Vetter, A., & Zhang, H. (2000). Assessing the con-
tribution of natural sources to regional atmospheric
mercury budgets. Science of the Total Environment,
259, 61–72.
Gustin, M. S., Biester, H., & Kim, C. S. (2002). Investi-
gation of the light-enhanced emission of mercury from
naturally enriched substrates. Atmospheric Environ-
ment, 36, 3241–3254.
Gustin, M. S., Coolbaugh, M. F., Engle, M. A., & Fitzgerald,
B. C. et al. (2003). Atmospheric mercury emissions
from mine wastes and surrounding geologically en-
riched terrains. Environmental Geology, 43, 339–351.
Jackson, T. A. (1997). Long-range atmospheric transport of
mercury to ecosystems, and the anthropogenic emis-
sions a critical review and evaluation of the published
evidence. Environmental Reviews, 5, 99–120.
Kambey, J., Farrell, A., & Bendell-Young, L. (2001).
Influence of illegal gold mining on mercury levels in
fish of North Sulawesís Minahasa Peninsula, (Indo-
nesia). Environmental Pollution, 114, 299–302.
Kim, K.Y, Kim, M.Y, & Lee, G. (2001). The soil-air ex-
change characteristic of total gaseous mercury from a
large-scale municipal landfill area. Atmospheric
Environment, 35, 3475–3493.
Lamborg, C. H, Fitzgerald, W. F, O‘Donnell, J., & Torg-
erson, T. (2002). A non-steady-state compartmental
model of global-scale mercury biogeochemistry with
interhemispheric atmospheric gradients. Geochimica
et Cosmochimica Acta, 66, 1105–1118.
Lee, Y. H., Wangberg, I., & Munthe, J. (2003). Sampling
and analysis of gas-phase methylmercury in ambient
air. Science of the Total Environment, 304, 107–113.
Environ Geochem Health (2006) 28:529–540
Lide D. R. (Ed.). (1993). CRC handbook of chemistry and
physics. CRC Press, Boca Raton.
Lin, C. J., & Pehkomen, S. O. (1999). The chemistry of
atmospheric mercury: A review. Atmospheric Envi-
ronment, 33, 2067–2079.
Lindberg, S. E., Jackson, D. R., Huckabee, J. W., Janzen,
S. A., Levin, M. J., & Lund, J. R. (1979). Atmospheric
emission and plant uptake of mercury from agricul-
tural soils near the Almadén mercury mine. Journal of
Environmental Quality, 8, 572–578.
Lindberg, S. E., & Turner, R. R. (1977). Mercury emis-
sions from chlorine-production solid waste deposits.
Nature, 268, 133–136.
Lindberg, S. E, Kim, Y., Meyers, T., & Owens, J. (1995). A
micrometeorological gradient approach for quantify-
ing air/surface exchange of mercury vapour: tests over
contaminated soils. Environmental Science Technol-
nology, 29, 126–135.
Lindberg, S. E, Hanson, P. J, Meyers, T. P, & Kim, K. M.
(1998). Air/Surface Exchange of mercury vapor over
forest: the need for a reassessment of continental
biogenic emissions. Atmospheric Environment, 32,
895–908.
Lindberg, S. E., & Stratton, W. J. (1998). Atmospheric
mercury speciation: Concentration and behavior of
reactive gaseous mercury in ambient air. Environ-
mental Science Technology, 32, 49–57.
Lindberg, S. E., Zhang, H., & Gustin, M. et al. (1999).
Increase in mercury emissions from desert soils in
response to rainfall irrigation. Journal of Geophysical
Research, 104(D17), 21879–21888.
Lindqvist, O., Johansson, K., & Aastrup, M. et al. (1991).
Mercury in the Swedish environment – recent re-
search on causes, consequences and corrective meth-
ods. Water, Air and Soil Pollution, 55, 1–262.
Liu, S., Nadim, F., & Perkins, C. et al. (2002). Atmospheric
mercury monitoring survey in Beijing, China. Che-
mosphere, 48, 97–107.
Malm, O., De Freitas, M., Hissnauer, P., Rodrı́guez, W., &
Neves Pinto, F. (1998). Use of ephiphite plants as
biomonitors to map atmospheric mercury in a gold
trade center city, Amazon, Brazil. Science of the Total
Environment 213, 57–64.
Mason R., Fitzgerald W., Morel F. (1994). The biogeo-
chemical cycling of elemental mercury: Anthropo-
genic influences. Geochimica et Cosmochimica Acta,
58(15), 3191–3198.
Nacht, D. M., & Gustin, M. S. (2004). Mercury emissions
from background and altered geologic units through-
out Nevada. Water, Air and Soil Pollution, 151, 179–
193.
Nico, L. G., & Taphorn, D. C. (1994). Mercury in fish from
gold-mining regions in the upper Cuyuni river system,
Venezuela. Fresenius Environmental Bulletin, 3, 287–
292.
Nriagu, J. (1989). A global assessment of natural sources of
atmosphere trace metals. Nature, 338, 47–49.
Pirrone, N., Costa, P., Pacyna, J. M., & Ferrara, R. (2001).
Mercury emissions to the atmosphere from natural
and anthropogenic sources in the Mediterranean
region. Atmospheric Environment, 35, 2997–3006.
539
Poissant, L., & Casimir, A. (1998). Water-air and soil-air
exchange rate of total gaseous mercury measured at
background sites. Arm Environment, 32(5), 883–893.
Poissant, L., Pilote, M., & Casimir, A. (1999). Mercury flux
measurement in a naturally enriched area: correlation
with environmental conditions during the Nevada
study and tests of release if mercury from soils
(STORMS), Journal of Geophysical Research Arm
Environment, 104, 21845–21857.
Poissant, L., Pilote, M., Constant, P., Beauvais, C., Zhang,
H., & Xu, X. (2004). Mercury gas exchanges over
selected bare soil and flooded sites in the bay St.
François wetlands (Québec, Canada). Atmospheric
Environment, 38, 4205–4214.
Pyle, D. M., & Mather, T. A. (2003). The importance of
volcanic emissions for the global atmospheric mer-
cury cycle. Atmospheric Environment, 37, 5115–
5124.
Rasmussen, P., Edwards, G., Kemp, J., Fitzgerald-Hubble,
C., & Schroeder, W. (1998). Towards an improved
natural sources inventory for mercury. In: Met Envi-
ron: Int Symp: Metallur Soc Can Inst Min Metall Pet
(CIM), pp 1–8.
Rodrı́guez, S. (1986). Recursos Minerales de Venezuela.
Boletı́n de Geologı́a, vol 15, no. 25. Ministerio de
Energı́a y Minas, Venezuela.
Schlüter, K., Seip, H., & Alstad, J. (1995). Mercury
translocation in and evaporation from soil: I Soil
lysimeter experiments with 203Hg radiolabelled
compounds. Journal of Soil Contamination, 4, 269–
298.
Schroeder, W. H., Anlauf, K. G., Barrie, L. A., Lu, J. Y., &
Steffen, A. (1998). Arctic springtime depletion of
mercury. Nature, 394, 331–332.
Schroeder, W. H., & Munthe, J. (1998). Atmospheric
mercury: an overview. Atmospheric Environment, 32,
809–822.
Seigneur, C., Lohman, K., Vijayaraghavan, K., & Shia, R.
(2003). Contributions of global and regional sources
to mercury deposition in New York State. Environ-
mental Pollution, 123, 365–373.
Sholupov, S., Pogarev, S., Ryzhov, V., Mashyanov, N., &
Stroganov, V. (2004). Zeeman atomic absortion
spectrometer RA-915 + for direct determination of
mercury in air and complex matrix samples. Fuel
Processing Technology, 85, 473–485.
Shrestra, K., & Ruı́z, X. (1989). A preliminary study of
mercury contamination in the surface soil and river
sediments of the Roscio District, Bolivar State Ven-
ezuela. Science of Total Environment, 79, 233–239.
Soil Conservation Service, (1972). Soil survey laboratory
methods and procedures for collecting soil samples.
USDA, Washington, D.C.
Southworth, G. R, Lindberg, S. E., Zhang, H., & Ans-
combe, F. R. (2004). Fugitive mercury emissions from
a chlor-alkali factory: sources and fluxes to the
atmosphere. Atmospheric Environment,
38, 597–611.
Suzuki, T. (1977). Mercury compounds. In: R. Goyer, &
M. Mehlman (ed.), Toxicology of Trace Elements.
Wiley and Sons, New York, pp 1–41. Wiley and Sons.
123
540
Wallschläger, D., Turner, R., & London, J. et al. (1999).
Factors affecting the measurement of mercury emis-
sions from soils with flux chambers. Journal of Geo-
physical Research, 104, 21859–21871.
Wallschläger, D., Kock, H. H., Schroeder, W., Lindberg, S.
E., Ebinghaus, R., & Rolf-Dieter, W. (2002). Esti-
mating gaseous mercury emission from contaminated
floodplain soils to the atmosphere with simple field
measurement techniques. Water, Air and Soil Pollu-
tion, 135, 39–54.
Wängberg I., Hans, E., & Ferrara, R. et al. (2003).
Atmospheric mercury near a chlor-alkali plant in
123
Environ Geochem Health (2006) 28:529–540
Sweden. Science of the Total Environment, 304,
29–41.
Xiao, Z. F., Munthe, J., Schroeder, W., & Linqvist, O.
(1991). Vertical fluxes of volatile mercury over forest
soil and lake surfaces in Sweden. Tellus, 43B,
267–279.
Zhang, H., Lindberg, S. E., Marsik, F. J., & Keeler, G. J.
(2001). Mercury air/surface exchange kinetics of
background soils of the Tahquamenon river wa-
tershed in the Michigan Upper Peninsula. Water, Air
and Soil Pollution, 126, 151–169.