ARTICLE IN PRESS

Environmental Research 109 (2009) 355367

Contents lists available at ScienceDirect

Environmental Research
journal homepage: www.elsevier.com/locate/envres

Human exposure to mercury in the vicinity of chlor-alkali plant

Darija Gibicar a, Milena Horvat a,, Martina Logar a, Vesna Fajon a, Ingrid Falnoga a, Romano Ferrara b,
Enrica Lanzillotta b, Claudia Ceccarini b, Barbara Mazzolai c, Bruce Denby d, Jozef Pacyna d,e
a

Jozef Stefan Institute, Department of Environmental Sciences, Jamova cesta 39, 1000 Ljubljana, Slovenia
Institute of Biosics Area della Ricerca, Pisa, Italy
Scuola Superiore SantAnna, CRIM Laboratory, Pisa, Italy
d
Norwegian Institute for Air Research, PO Box 100, No-2027 Kjeller, Norway
e
Faculty of Chemistry, Gdansk University of Technology, 11/12 G. Narutowicza Str., 80-952 Gdansk, Poland
b
c

a r t i c l e in fo

abstract

Article history:
Received 23 July 2008
Received in revised form
1 January 2009
Accepted 23 January 2009
Available online 14 March 2009

The main objectives of our study were to estimate the impact of a mercury cell chlor-alkali (MCCA)
complex in Rosignano Solvay (Tuscany, Italy) on the local environment and to assess mercury exposure
of inhabitants living near the plant. Measurement campaigns of atmospheric Hg near the MCCA plant
showed that the impact of the emitted Hg from the industry on the terrestrial environment is restricted
to a close surrounding area. Total gaseous mercury concentrations in ambient air of inhabited area
around the MCCA plant were in the range of 8.08.7 ng/m3 in summer and 2.84.2 ng/m3 in winter.
Peaks of up to 100 ng/m3 were observed at particular meteorological conditions. Background levels of
2 ng/m3 were reached within a radius of 3 km from the plant. Reactive gaseous mercury emissions from
the plant constituted around 4.2% of total gaseous mercury and total particulate mercury emission
constituted around 1.0% of total gaseous mercury emitted. Analysis of local vegetables and soil samples
showed relatively low concentrations of total mercury (30.12919 mg Hg/kg DW in the soil; o0.05111
mg Hg/kg DW in vegetables) and methylmercury (0.023.88 mg Hg/kg DW in the soil; 0.031.18 mg Hg/kg
DW in vegetables). Locally caught marine sh and fresh marine sh from the local market had
concentrations of total Hg from 0.049 to 2.48 mg Hg/g FW, of which 37100% were in the form of
methylmercury. 19% of analysed sh exceeded 1.0 mg Hg/g FW level, which is a limit set by the European
Union law on Hg concentrations in edible marine species for tuna, swordsh and shark, while 39% of
analysed sh exceeded the limit of 0.5 mg Hg/g FW set for all other edible marine species. Risk
assessment performed by calculating ratio of probable daily intake (PDI) and provisional tolerable daily
intake (PTDI) for mercury species for various exposure pathways showed no risks to human health for
elemental and inorganic mercury, except for some individuals with higher number of amalgam llings,
while PDI/PTDI ratio for methylmercury and total mercury exceeded the toxicologically tolerable value
due to the potential consumption of contaminated marine sh.
& 2009 Elsevier Inc. All rights reserved.

Keywords:
Chlor-alkali plant
Human exposure
Mercury
Methylmercury
Selenium
Vegetable
Fish
Air

0. Introduction
Mercury is a naturally occurring element in the Earths crust.
Over geological time, it has been distributed throughout the
environment by natural processes, such as volcanic activity, res,
movement of rivers, lakes, and streams, oceanic up-welling, and
biological processes. Since the advent of humans, and particularly
since the industrial revolution of the late 18th and 19th centuries,
anthropogenic sources have become a signicant contributor to
the environmental distribution of mercury and its compounds
(WHO, 2003). Major human sources of mercury involve coal
combustion in power plants, the production of caustic soda with
the use of the Hg cell process, and cement production (Pacyna

 Corresponding author. Fax:+386 1 5885346.

E-mail address: milena.horvat@ijs.si (M. Horvat).

0013-9351/$ - see front matter & 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.envres.2009.01.008

et al., 2006). Although the mercury cell chlor-alkali (MCCA)

technique is in many places being replaced by alternative
techniques, it is still the most commonly used in Europe. More
recent estimates report emissions from the chlor-alkali industry to
be responsible for about 17% or 40.4 ton/yr of anthropogenic total
mercury emissions (Pacyna et al., 2006).
In Tuscany, Italy, mercury is present in the environment as a
product of natural and anthropogenic sources. The cinnabar (HgS)
deposits of Mt. Amiata are a major source of Hg in the central part
of Tuscany. Mercury mining and smelting activities in this area
were present as early as the Etruscan period (8th1st centuries
B.C.) and ceased in 1980. In this area high mercury levels were
found in soil, vegetation, air (Bargagli et al., 1987; Barghigiani and
Bauleo, 1992; Ferrara et al., 1992), farm produce (Barghigiani and
Ristori, 1994) and sh (Barghigiani et al., 1991; Barghigiani and De
Ranieri, 1992; Rossi et al., 1993; Barghigiani et al., 2000; Scerbo
et al., 2005). Additional sources of mercury contamination in this

ARTICLE IN PRESS
356

D. Gibicar et al. / Environmental Research 109 (2009) 355367

region are geothermal power plants (Bargagli and Barghigiani,

1991) that mobilise natural mercury in the central part of the
region. Moreover two MCCA plants are located in Tuscany causing
additional mercury pollution. One is Europes largest MCCA plant
located on the coast near Livorno in Rosignano Solvay that
discharges waste directly in the Tyrrhenian Sea, and the other one
is located in a small village Saline di Volterra, which discharges
waste into the S. Marta, a canal owing into the river Cecina
(Scerbo et al., 2005).
The chlor-alkali complex in Rosignano Solvay has been in
operation since 1940. Its impact on the surrounding environment
has been studied by several investigators since 1970 (Renzoni
et al., 1973; Baldi and Bargagli, 1984; Baldi and DAmato, 1986;
Ferrara et al., 1989, 1992, 2001; Maserti and Ferrara, 1991). Maserti
and Ferrara (1991) reported that before 1973, a yearly discharge of
Hg from the MCCA plant into the coastal seawater was between
12,500 and 14,500 kg. In 19751976, after the waste treatment
facilities were installed (Baldi and DAmato, 1986), the reported
discharge was 350750 kg Hg/yr. In 2001 the discharge of Hg was
estimated at 400500 kg Hg/yr (Ferrara et al., 2001). Once
discharged Hg enters in the aquatic ecosystems, part of the
inorganic mercury (I-Hg) can be microbially converted into
methylmercury (MeHg) and taken up by aquatic organisms. Fish
accumulate mercury directly from food and the surrounding
water (Rainbow, 1985). They can bioconcentrate large amounts of
this metal and seafood is considered the single largest source of
methylmercury in humans (Clarkson, 1997).
The main objectives of our study were to assess the impact of
mercury emission from the MCCA plant in Rosignano Solvay on
the local environment. We determined Hg species in the atmosphere of the village surrounding the MCCA plant, the deposition
of Hg from the plant, levels of total mercury (THg) and
methylmercury in the soil and in the locally grown vegetables.
The results were compared with the levels of Hg from the rural
reference area, situated 20 km south from the plant (village
Donoratico). Additionally we determined levels of total and
methylmercury in various sh caught from the Rosignano Solvay
area, Castiglion della Pescaia and vicinity of Elba Island and sh
bought at the local market. Finally we performed a robust exposure
assessment for inhabitants living near the MCCA plant and
compared it with the exposure for inhabitants of the reference area.
In order to evaluate whether there is an increased risk of adverse
health effects from elemental, inorganic, methylmercury and total
mercury exposure, simple risk assessment was performed by
estimating probable daily intakes (PDI) of elemental Hg, inorganic,
methylmercury and total mercury and comparing them with the
provisional tolerably daily intakes (PTDI) of mercury.
The study was carried out in the years 20022004 within the
European Union funded project named EMECAP (European
Mercury Emissions from Chlor Alkali Plants).

1. Methods
1.1. Study location
The village Rosignano Solvay is situated in Tuscany along the Tyrrhenian coast,
500 m from the shore-line, about 20 km south of Livorno (Fig. 1). The plant has
been in operation since 1940 (Maserti and Ferrara, 1991). The chlorine production
in the Solvay chlor-alkali plant nowadays is around 120,000 ton/yr (Euro Chlor,
2005). The village Donoratico, located 20 km south of Rosignano Solvay, was
selected as the most suitable reference area. It has no industrial plants in the
immediate vicinity with a similar life style of inhabitants as in Rosignano.
1.2. Atmospheric mercury and modelling of Hg deposition
Four seasonal measurement campaigns were carried out during winter and
summer in years 2002 and 2003 in order to determine the following parameters:

total gaseous mercury (TGM) concentration, reactive gaseous mercury (RGM)

concentration, total particulate mercury (TPM) concentration, Hg ux from soil
and Hg content in rain. Nine sampling stations were selected in the village of
Rosignano Solvay around the chlor-alkali plant, taking into account where citizens
live, and 1 sampling station in the reference area.
Total gaseous mercury (TGM) refers to gaseous elemental mercury (GEM) and
small contributions from other gaseous mercury species (less than 1%) that also
may be trapped by the sampler and detected as Hg0. Daily trend of TGM
concentrations has been determined by an automated Gardis-3 analyser
(Ekoservis, Lithuania) using the double amalgamation technique followed by cold
vapour atomic absorption spectrometry (CV AAS). Detailed procedure and
comparison of results in measurements between GARDIS, TEKRAN and the LIDAR
set-up were described by Wangberg et al. (2003), conrming a high degree of
analytical quality for mercury measurements in air.
RGM is operationally dened gaseous mercury fraction present in ambient air.
It is believed that RGM mostly consists of mercury dichloride (HgCl2), but other
divalent mercury species are also conceivable. Mist chamber, containing a KCl/HCl
solution has been used to trap RGM. The solution was then analysed by SnCl2
reduction and CVAFS (Wangberg et al., 2003).
Daily average concentrations of TPM at two stations have been determined by
quartz bre lter traps. The details of the method have been described previously
by Wangberg et al. (2003).
The deposition of mercury near the source has been evaluated on the base of
mercury concentration in rain samples. Hg ux from soil has been determined by
ux chamber technique, a detailed procedure was described elsewhere (Xiao et al.,
1991; Kim and Lindberg, 1995; Wangberg et al., 2003).
The Atmospheric Pollution Model (TAPM) from CSIRO in Australia was used
for meteorological calculations and an off-line dispersion chemistry model
EPISODE has been adapted to include a mercurychlorine chemistry scheme in
modelling process and to calculate deposition and concentration elds of GEM,
RGM and TPM. A mercury/chlorine/ozone chemistry scheme was developed to
describe chemistry in the plume as well as in the factory itself. For the local scale
modelling the development and testing of a suitable dispersion modelling system
to describe local scale mercury dispersion and chemistry was performed. The
model was validated against observed concentration and emission data, collected
during the measurement campaigns. The dispersion and deposition of mercury
emitted from the MCCA plant was simulated for the year 2002 and local
concentration and deposition elds were calculated. Detailed modelling description was described elsewhere (Denby and Pacyna, 2004).

1.3. Sampling of soil, vegetables and sh

Soil samples were collected during October of 2001 and 2002 and July 2002
from 15 gardens in the Rosignano Solvay area (Fig. 2) and the Donoratico area as
the control station (4 sampling points). Surface soil samples were transferred to
plastic bags and stored in a freezer. Homogenisation was done by gentle mixing
using a glass stick. Dry weight was determined in separate aliquots by heating to
constant weight at 105 1C.
From the same sampling points vegetable samples (celery, salad, fennel,
tomato, beet, basil, radish, parsley, aubergines, garlic, onion, bean, celery, gourd,
potato) were collected during October of 2001 and 2002 and July 2002. Collected
vegetable samples were rinsed with tap water, air-dried and transferred to plastic
bags and stored deep-frozen. Prior to homogenisation in agate mortar vegetable
samples were freeze-dried. Before and after freeze-drying the weight was recorded
in order to be able to express the data on both fresh (as consumed) and dry weight
bases.
Nineteen sh and 1 crab were collected offshore Rosignano Solvay, Castiglion
della Pescaia and the Island of Elba and 6 sh were bought in the Piombino
market. Fish were collected in October 2001 and April 2002. Sampling locations
are shown in Fig. 1 and Table 4. Samples belonged to species Trachinus araneus
(striped weever), Trigla lucerna (tub gurnard), Scorpaena notata (scorpion sh),
Serranus scriba (painted comber, perch), Uranoscopus scaber (stragazer),
Conger conger (conger eel), Lichia amia (leer sh, jack), Pomatomus saltatrix
(bluesh) and Eriphia verrucosa (crab). Samples were stored in a freezer below
20 1C. Prior the analysis sh samples were slightly thawed, the skin removed and
sh muscle carefully removed and homogenized. Fresh muscle samples were
analysed.

1.4. Analytical methods for determination of Hg species and total selenium in air, soil,
vegetables and sh
Various analytical methods were used which are described elsewhere.
A summary of the analytical methods is presented in Table 1. The accuracy of
the results was checked by the use of certied reference materials for total and
methylmercury determination for each batch of the samples. We used NIST SRM
2976 (Mussel homogenate, assigned values: 61.073.5 ng THg/g, 27.772.0 ng
MeHg/g), NIST SRM 2977 (Mussel tissue, assigned value: 97105 ng THg/g), NRCC
DOLT-2 (Dogsh liver, assigned values: 199071000 ng THg/g, 693753 ng MeHg/g)

ARTICLE IN PRESS
D. Gibicar et al. / Environmental Research 109 (2009) 355367

357

Fig. 1. Map of Tuscany (Italy) with marked sampling locations: the Rosignano Solvay mercury cell chlor-alkali plant in red square, reference station (Donoratico) in yellow
triangle, blue circles indicating origin of analysed sh. The distance between Riosignanio and Donoratico is about 20 km. For interpretation of the references to colour in this
gure legend, the reader is referred to the web version of this article.

and NRCC TORT 2 (Lobster Hepatopancreas, assigned value: 270760 ng THg/g) to

control the analytical accuracy for Hg determination in sh; IAEA 405 (Estuarine
sediment, assigned values: 770850 ng THg/g, 5.4970.05 ng MeHg/g) to control
the analytical accuracy for Hg determination in soil samples, IAEA 336 (Lichen,
assigned value: 167233 ng THg/g) and IAEA 140 (Fucus; sea plant homogenate,
assigned values: 3244 ng THg/g, 0.62670.107 ng MeHg/g) to control the analytical accuracy for Hg determination in vegetable samples. The mean levels of total
and methylmercury in NIST 2976 (63.175.1 ng THg/g, N 25; 27.072.0 ng
MeHg/g, N 4), NIST 2977 (10377 ng THg/g, N 5), DOLT-2 (18167160 ng THg/g,
N 3; 650718 ng MeHg/g, N 3), TORT 2 (273 ng THg/g, N 1), IAEA 405
(800711 ng THg/g, N 3; 5.2270.10 ng MeHg/g, N 5), IAEA 336 (19175 ng
THg/g, N 3), IAEA 140 (33.470.6 ng THg/g, N 3, 0.6070.05 ng MeHg/g,
N 3), were well within their range given for the assigned values.

1.5. Exposure assessment

To determine possible exposure to mercury by various pathways, such as
inhalation and consumption of contaminated food, probable daily intake values
were calculated for the general adult population. The equation used for calculating
total daily exposure dose was
PDItotal PDIinhalation PDIingestion
PDIingestion mg=kg body weight=day food intakeg=day
 I- or MeHg concentrationmg=gaverage body weightkg
PDIinhalation mg=kg body weight=day daily respiratory volume m3
0

3

 Hg concentrationng=m   10

average body weight kg

Average daily sh intake was obtained from the European Food Safety Authority
(EFSA, 2004), where 32 g/day of sh for Italy is reported. Average body weight for
an adult Italian is estimated at 70 kg (EFSA, 2004). We estimated an average daily
vegetable intake to be around 300 g. Measured concentrations of mercury in air,
sh and vegetables as sources of Hg were considered and taken from Table 2. For
Hg in drinking water, amalgam llings and food other than sh and vegetables,
average daily Hg intakes reported by WHO (2003) were included. Daily respiratory
volume of 20 m3 was considered.
Estimated PDI values were considered against the provisional tolerable daily
intake (PTDI) to evaluate whether there is an increased risk of adverse health
effects from elemental Hg, inorganic Hg, methylmercury and total mercury

exposure. A comparison of the two parameters was achieved by determining the

ratio of the PDI to the PTDI, expressed as a percentage (PDI/PTDI  100%). Values
approaching or exceeding 100% identify those exposure scenarios where the
toxicological reference value may be exceeded and that require more careful
evaluation.
1.6. Statistical analysis
Standard descriptive statistics were produced for the various variables and
strata, with use of the medians and/or geometric means for most variables.
STATGRAPHIC Plus for Windows Version 4.0 and SPSS 12.0.1 for Windows were
used as software. One-way ANOVA for sample comparison was used and
MannWhitneys test and KruskalWallis test at 95.0% condence level for post
hoc testing. To investigate associations between the attributes, Spearmans rank
correlations and Pearsons correlations on log transformed data were used.

2. Results
2.1. Levels of atmospheric mercury in Rosignano Solvay and
modelling of its distribution and deposition
TGM concentrations in Rosignano Solvay were in the range of
8.08.7 ng/m3 in summer and 2.84.2 ng/m3 in winter, although
peaks of up to 100 ng/m3 were observed in particular meteorological conditions (Table 2). At the reference station TGM
concentrations ranged between 1.5 and 5.5 ng/m3 (Table 2).
Reactive gaseous mercury (HgII) concentrations measured in
Rosignano Solvay, most likely mercury chloride homologues
(277691 pg/m3), were higher compared to the reference station
in Donoratico (87326 pg/m3).
Concentrations of mercury associated with particulate matter
(TPM) ranged from 25 to 70 pg/m3 in Rosignano Solvay while in
the control station the range was 1326 pg/m3. Rain samples from

ARTICLE IN PRESS
358

D. Gibicar et al. / Environmental Research 109 (2009) 355367

Fig. 2. Sampling stations around the mercury cell chlor-alkali plant in Rosignano Solvay. The position of the chlor-alkali plant is circled with the red line. Red square
indicates the cell of the plant. For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.

Rosignano Solvay contained 615 ng Hg/L and from Donoratico

4.65.5 ng Hg/L. Measurements of mercury degassing rate from
soil around the chlor-alkali plant was estimated to be 045 ng/m2/h.
Mercury degassing rate from soil in reference station was lower and
ranged 02.5 ng/m2/h (Table 2).
The dispersion and deposition of mercury emitted from the
MCCA plant were simulated for the year 2002. The results are
shown in Fig. 3, where TGM concentrations and deposition of
TGM as a function of distance from the plant are shown.
Heightened concentrations of TGM were found only in the region
close to the plant and background levels of 2 ng/m3 were reached
within 3 km of the plant.
Emissions of mercury from the plant were estimated to be
around 285 kg/yr (Gronlund et al., 2005). Our results show that
around 4.2% of total emitted Hg was present in the form of HgII,
and only around 1.0% in the form of TPM, while most of the
emitted mercury was in its elemental form Hg0. Only 14% (or
6.8 kg/yr) of total emitted Hg were deposited within 5 km from
the plant. The remaining 86% were dispersed and transported
away from the area, showing its characteristics of a global
pollutant. It is known that mercury may travel as far as 2500 km
in just 72 h and estimates of airborne residence time range from
6 days to 6 years (US EPA, 2001), before the mercury is
redeposited in air or water by rainfall or other climatological
conditions.

2.2. Total and methylmercury in soil from Rosignano Solvay

Soil gathered from 15 gardens located around the MCCA plant
in Rosignano Solvay showed relatively low concentrations of total
and methylmercury (Table 2). Concentrations of THg ranged
between 30.1 and 2919 mg/kg DW (Fig. 4) and were similar to
concentrations found by Maserti and Ferrara in 1991 on the same
area.
Average concentrations of THg and MeHg in soil from the
Rosignano Solvay area were slightly higher (but not statistically
signicant at the 95.0% condence level) than concentrations
found in the reference area (Table 2). Total mercury in soil was
elevated (2920 mg/kg DW) only at one station of Rosignano Solvay
area, which was situated near the chlor-alkali plant in the western
direction. None of the analysed soil samples exceeded the Soil
Guideline Value for inorganic mercury contamination set by
Department for Environment, Food and Rural Affairs (DEFRA,
2002) (8 mg/kg DW) or Canadian Soil Quality Guideline for
agricultural soils (6.6 mg/kg) or the UK soil guideline value for
inorganic Hg for allotments (8 mg/kg). Mean concentrations of
THg and MeHg were only slightly higher in soil samples collected
in autumn than those collected in summer, but the difference
was not statistically signicant at 95% condence level. Mean
MeHg/THg ratio in soil collected in autumn (0.61%) was higher
than the mean MeHg/THg ratio in soil collected in summer

ARTICLE IN PRESS
D. Gibicar et al. / Environmental Research 109 (2009) 355367

359

Table 1
Summary of analytical methods used for the analysis of total Hg, MeHg and selenium.
Sample, analyte

Air, Hg0
Air, Hg

II

Air, Hg(p)
Hg degassing rate
from soil
Soil, total Hg
Vegetable, total Hg
Fish, total Hg
Vegetable, soil, MeHg

Fish, MeHg

Fish, HgII and MeHg

Vegetable, Se

Methods
Pretreatment/extraction/digestion

Detection

Limit of detection

Reference

Amalgamation on gold trap

AAS Gardis-3

0.1 ng/m3

Mist chamber-adsorption on KCl/HCl solution-reduction

with SnCl2-amalgamation on gold trap
Quartz bre ltre traps-reduction by pyrolysis

AFS

5 pg/m

AAS

5 pg/m3

Flux chamber-amalgamation on gold trap

AAS Gardis-3

0.1 ng/m3

Acid digestion with HNO3 and H2SO4 in closed Teon vialsreduction with SnCl2-amalgamation on gold trap
Acid digestion with HNO3 in closed Teon vials-reduction
with SnCl2-amalgamation on gold trap
Acid digestion with HNO3 in closed Teon vials-reduction
with SnCl2-amalgamation on gold trap
Acidication with HCl-extraction of MeHgCl into CH2Cl2back extraction of MeHgCl into water phase by evaporation of
CH2Cl2-ethylation of ionic Hg species-room temperature
adsorption on Tenax
Acid leaching with KBr/H2SO4-extraction of MeHgBr into
toluene- clean-up with aqueous solution of cysteinere-extraction of MeHg into benzene
Alkaline dissolution with KOH/methanol-aqueous phase
ethylation room temperature adsorption on Tenax
Irradiation in TRIGA Mark II reactor at a ux of 2  1010 n/mm2/s

CV AAS

0.05 ng/g

Wangberg et al.
(2003)
Wangberg et al.
(2003)
Wangberg et al.
(2003)
Wangberg et al.
(2003)
Horvat et al. (1991)

CV AAS

0.05 ng/g

Horvat et al. (1991)

CV AAS

0.05 ng/g

Horvat et al. (1991)

Isothermal gas
chromatography,
pyrolysis, CV AFS

0.01 ng/g

Horvat et al. (1993)

Liang et al.
(1994a, b)

GC ECD

0.5 ng/g

Horvat et al. (1988,

1990, 1994)

CV AFS

30 pg/g for MeHg and

80 pg/g for Hg2+
10 ng/g

Logar et al. (1999)

Liang et al. (1994b)
Byrne and
Kosta (1974)

NAA, Gamma
spectrometry

Table 2
Summary statistics for concentrations of TGM, RGM and TPM in air, and for concentrations of THg, MeHg (expressed as Hg) and MeHg/THg ratios and Se concentrations
in soil, vegetables and rain samples from Rosignano Solvay and the reference area.
Rosignano solvay
Mean7Std. dev. (n)

Reference area (Donoratico)

Median

MinMax

Mean7Std. dev. (n)

Median

MinMax

Air
TGM (ng/m3)
Winter
Summer
RGM (pg/m3)
TPM (pg/m3)

2.84.2
8.08.7 (100)
277691
2570

87326
1326

Rain
THg (ng/L)

615

4.65.5

Soil
THg (mg/kg DW)
MeHg (mg/kg DW)
MeHg/THg (%)
Degassing rate (ng Hg/m2/h)

Vegetables
THg
(mg/kg DW)
(mg/kg FW)

MeHg
(mg/kg DW)
(mg/kg FW)
MeHg /THg (%)

1.55.5

2047480 (36)
0.6670.68 (36)
0.6370.45 (36)

84.5
0.43
0.51

30.12919
0.023.88
0.011.76
045

1257113 (6)
0.3670.32 (6)
0.6370.95 (6)

112
0.34
0.28

30.4341
0.030.88
0.012.54
02.5

19.5720.5 (94)
3.4674.78 (94)

16.2
1.45

o0.05111
o0.0124.0

13.2713.2 (21)
3.0073.94 (21)

9.92
2.12

0.2254.7
0.0317.1

0.2770.21 (94)
0.0570.06 (94)
10.8721.1 (94)

0.20
0.02
1.87

0.031.18
0.0020.348
0.0987.0

0.2170.15 (21)
0.0570.06 (21)
7.10712.7 (21)

0.15
0.02
1.63

0.090.72
0.010.29
0.3153.5

17.9713.4
4.374.3

11.6
2.7

o1058.2
o0.522.8

14.4711.5 (21)
2.3472.13 (21)

8.80
1.86

o1047.6
0.009.98

Se
(mg/kg DW)
(mg/kg FW)

ARTICLE IN PRESS
360

D. Gibicar et al. / Environmental Research 109 (2009) 355367

Fig. 3. Concentration elds of: (a) average annual Hg0 concentrations in air, expressed in ng/m3, (b) average mercury deposition rates, expressed in ng/m2/h. Concentration
elds were calculated for the year 2002. The red square shows the position of the cell of the MCCA plant. For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.

(0.25%). MeHg/THg ratios in soil are probably related primarily to

the combined soil environmental conditions such as soil organic
matter nature, microbial activity, pH and THg concentration that
affect demethylation (Remy et al., 2006). The MeHg/THg ratio in
soil samples from Rosignano Solvay was relatively low (median
0.51%) and was slightly higher (but not statistically signicant at
95% condence level) than the MeHg/THg ratio in soil from the
reference area (median 0.28%) (Table 2).

2.3. Total mercury, methylmercury and selenium content in

vegetables from Rosignano Solvay and Donoratico area
We analysed vegetables grown in 15 gardens located around
the MCCA plant and compared them to concentrations in
vegetables grown at the reference site. In general vegetables
contained relatively low concentrations of total and methylmercury (Tables 2 and 3). Cabbage, salad, tomato, beet and basil from
the Rosignano Solvay area showed slightly higher concentrations
of THg and MeHg compared to the reference area, but the
difference was not statistically signicant at the 95% condence
level. Mean THg and MeHg concentrations in analysed vegetables
differed signicantly between the vegetable species (THg:
F 4.36, p 0.0000; MeHg: F 2.43, p 0.0038). The highest
THg concentrations expressed on a dry weight basis were found in
basil, beet, celery, parsley and mint (Table 3).
The MeHg/THg ratio in vegetables varied statistically signicant at the 95% condence level between the vegetable species
(F 5.24, p 0.0000) and between the sampling locations
around the MCCA plant (F 1.82, p 0.0327), but not between
the Rosignano Solvay area and the reference area. The highest
MeHg/THg ratio was observed in aubergine, bean, garlic, gourd,
onion and tomato. In general, taking into account all vegetable
species, a positive Spearmans rank correlation was found
between MeHg and THg (R2 0.4368, p 0.0001) and between
THg and MeHg/THg ratio (R2 0.7826, p 0.0000).

Mercury and selenium co-accumulation in 1:1 formation in

humans could be an important Hg detoxication process (Kosta
et al., 1975; Byrne et al., 1995; Falnoga et al., 2000) and the lack of
selenium in the body can deteriorate the antioxidative role of
selenoproteins, such as glutathione peroxidase, formate dehydrogenase and selenophosphate synthase. The Se deciency in
human diet is more common than its toxicity, because many
regions have low levels of soil selenium. Some countries
supplement agricultural fertilizers with selenium. Vegetables
from Rosignano Solvay and the reference area contained relatively
low levels of selenium, which ranged from o10 to 58.2 mg/kg DW
or o0.5 to 22.8 mg/kg FW. No statistically signicant differences
between the sampling stations or between the species were
found. The highest selenium concentrations were found in basil,
onion and salad (Table 3). Selenium in vegetables was not
associated with the content of THg or MeHg/THg ratio in the
plants. However weak positive association between log(Se) and
log(MeHg) was observed (R2 0.2229, p 0.0484).
Assuming daily consumption of 300 g of locally grown
vegetable, the daily intake of selenium would range from 0.15 to
6.84 mg. Intake of selenium by vegetables in this region is poor.
The recommendations of US National Academy of Sciences set
daily intake of selenium in the range of 50200 mg as safe and
adequate (McLaughlin et al., 1999; Reilly, 1996).

2.4. Mercury concentrations in local sh

The concentrations of total Hg in 26 analysed sh samples
varied from 0.049 to 2.48 mg/kg of which 37100% were found in
the form of methylmercury (Table 4). The highest mercury content
was found in sh from the local market in Piombino. Five of the
26 analysed samples (or 19%) exceeded 1.0 mg/kg FW level, which
is a limit set by the European Union law on Hg concentrations in
edible marine species for tuna, swordsh and shark. Ten of the
26 analysed samples (or 39%) exceeded the limit set for all other

ARTICLE IN PRESS
D. Gibicar et al. / Environmental Research 109 (2009) 355367

361

Fig. 4. Mean mercury concentrations of total mercury (mg/kg DW) in soil samples from 15 sampling points around the MCCA plant in Rosignano Solvay and from the
reference area (village Donoratico).

Table 3
Mercury, methylmercury (expressed as Hg) and selenium in vegetables from Rosignano Solvay and Donoratico, expressed as mg/kg of dry weight and fresh weight.
Vegetable

THg

MeHg

(mg/kg DW)

(mg/kg FW)

Cabbage
R. Solv. (8)a
Donoratico (3)

24.2710.9b
12.27 8.3

Salad
R. Solv. (15)
Donoratico (3)

Fennel
R. Solv. (9)
Donoratico (0)

Tomato
R. Solv. (17)
Donoratico (4)

MeHg/THg

(mg/kg DW)

(mg/kg FW)

3.872.2
2.171.3

0.1570.13
0.1670.09

0.0270.01
0.0370.01

26.5717.6
10.874.6

2.271.9
1.170.6

0.2570.12
0.1570.01

18.1716.0

1.271.0

3.878.8
0.4470.27

Se
(mg/kg DW)

(mg/kg FW)

0.670.4
1.670.8

13.679.9
12.074.8

2.771.6
2.371.2

0.0270.02
0.0170.00

2.072.4
1.570.7

20.4710.9
23.6721.3

2.872.4
2.572.3

0.3370.18

0.0270.01

2.772.0

0.470.8
0.0470.02

0.1270.07
0.1070.02

0.0170.01
0.0170.00

14.6721.3
21.1723.0

12.076.7
11.475.5

1.270.6
1.070.5

Beet
R. Solv. (8)
Donoratico (5)

44.2735.2
17.776.6

3.774.2
2.671.1

0.3170.17
0.1770.05

0.0270.02
0.0370.01

2.875.7
1.170.5

o10
8.473.2

udl
1.270.5

Basil
R. Solv. (12)
Donoratico (4)

32.5717.7
24.3721.4

9.875.5
6.976.9

0.4070.28
0.3070.11

0.1370.09
0.0970.04

1.470.8
2.071.4

23.5718.6
12.077.9

7.376.7
3.171.0

Mint
R. Solv. (1)
Donoratico (0)

47.9

0.23

0.11

0.5

11.1

5.6

Parsley
R. Solv. (5)
Donoratico (2)

26.376.7
28.0717.1

9.872.9
9.374.2

0.3470.34
0.6170.16

0.1270.10
0.2270.10

1.371.2
2.972.3

13.674.7
21.9714.9

5.774.0
7.373.9

Garlic
R. Solv. (2)
Donoratico (0)

1.7;1.9

0.6; 0.8

0.39;0.46

0.16; 0.17

20.7; 26.8

o10; 11.3

udl;4.0

24.0

ARTICLE IN PRESS
D. Gibicar et al. / Environmental Research 109 (2009) 355367

362

Table 3 (continued )
Vegetable

THg

MeHg

MeHg/THg

(mg/kg DW)

(mg/kg FW)

(mg/kg DW)

(mg/kg FW)

Onion
R. Solv. (4)
Donoratico (0)

3.774.8

0.570.7

0.4570.49

0.0670.05

Bean
R. Solv. (4)
Donoratico (0)

0.870.5

0.270.1

0.1770.06

0.0470.02

Se
(mg/kg DW)

(mg/kg FW)

36.8737.0

29.3724.7

3.873.0

34.6731.7

15.277.0

4.373.1

Radish
R. Solv. (1)
Donoratico (0)

19.9

8.0

0.36

0.15

1.83

3.51

14.0

Celery
R. Solv. (2)
Donoratico (0)

21.5; 26.9

3.3; 7.9

0.37; 0.67

0.06; 0.20

1.7; 2.5

o10; 24.1

udl; 7.1

Potato
R. Solv. (1)
Donoratico (0)

1.5

0.3

0.16

0.03

10.6

20.5

4.2

Aubergine
R. Solv. (3)
Donoratico (0)

0.770.5

0.170.1

0.2670.12

0.0470.03

52.5735.9

19.2711.9

2.371.2

Gourd
R. Solv. (1)
Donoratico (0)

0.3

0.04

0.20

0.03

67.9

10.7

1.4

Plum
R. Solv. (1)
Donoratico (0)

0.6

0.1

0.11

0.02

19.5

o10

udl

a
b

Rosignano Solvay (number of samples).

Average7Std. dev.

edible marine species, which is 0.5 mg/kg FW. In the study of

Storelli et al. (2005) around 20% of analysed samples of striped
mullet caught from the Ionian and Adriatic Seas exceeded the EU
law limit for mercury in seafood.

By summing intake of elemental Hg from two sources: ambient

Hg coming from the MCCA plant (up to 50% PTDI) and Hg inhaled
from evaporating amalgam llings (up to 125% PTDI according to
WHO (2003), the tolerable intake of Hg0 of 4 mg/day can be
exceeded (following worst case scenario for up to 175% of PTDI,
Table 5).

2.5. Exposure assessment

2.5.1. Exposure to mercury vapour in Rosignano Solvay
Exposure to elemental mercury by the general population and
in occupational settings is primarily through inhaling mercury
vapours. Considering measured concentrations of TGM in air
(Table 2), daily intake of inhaled atmospheric Hg in Rosignano
Solvay was estimated at 0.062.0 mg/day of which 0.051.6 mg/day
is retained in the body. For the reference area, intake of Hg from
ambient air has been estimated at 0.030.11 mg/day (Table 5).
Although the elemental Hg intake is estimated to be up to
18 times higher in Rosignano Solvay than in the reference area,
this intake is still relatively low and constitutes maximum up to
50% of tolerable intake 4 mg/day (WHO, 2003). Dental amalgam
for example is a much more signicant source of Hg0 exposure.
Estimates of daily intake from amalgam restorations range from 1
to 27 mg/day (ATSDR, 1999) with the majority of dental amalgam
holders being exposed to less than 5 mg mercury/day (WHO,
2003). Of course there is a considerable variation in Hg intake
from dental amalgam between individuals, primarily due to the
number of amalgams present, gum chewing habits and bruxism.

2.5.2. Estimated dietary exposure to inorganic mercury

We estimated dietary exposure to I-Hg from consumption
of sh with concentrations of total mercury in the range of
0.0492.48 mg/kg of which up to 62.8% were in the form of
inorganic mercury. If we assume average consumption of 32 g
of marine sh per day as reported by the EFSAs journal (2004),
the daily intake consists of up to 22.9 mg (Table 5) or 16.4% of PTDI
set by WHO (2003). Daily intake of inorganic mercury from
consumption of locally grown vegetables was estimated at up to
7.1 mg for Rosignano Solvay and up to 5.0 mg for the reference area
Donoratico, if consumption of 300 g of vegetable per day was
assumed (Table 5).
Considering intakes of inorganic Hg from other possible
sources, such as drinking water and food other than sh and
vegetables taken from the literature (IPCS, 1991; WHO, 2003), the
total PDI for I-Hg for an average person (70 kg body weight) in
Rosignano Solvay ranges from 0.052 to 0.481 mg/kg body weight/
day or 324% of tolerable intake of 2 mg/kg body weight/day for
I-Hg set by the WHO (2003). The intake of inorganic mercury

ARTICLE IN PRESS
D. Gibicar et al. / Environmental Research 109 (2009) 355367

363

Table 4
Total and methylmercury (expressed as Hg) in muscles of marine organisms, determined by CV AAS, GC-ECD and CV AFS.
Fish species

Trachinus lineolatus
Trigla lucerna
Scorpaena Notata
Scorpaena Notata
Trigla lucerna
Serranus scriba
Uranoscopus scaber
Conger conger
Lichia amia
Pomatomus saltatrix
Eriphia Verrucosa
Scorpaena Notata
Scorpaena Notata
Trachinus lineolatus
Trigla lucerna
Scorpaena Notata
Uranoscopus scaber
Serranus scriba
Conger conger
Seriola dumerili
Trachinus lineolatus
Trigla lucerna
Trigla lucerna
Serranus scriba
Uranoscopus scaber
Conger conger

Striped weever
Tub gurnard
Scorpion sh
Scorpion sh
Tub gurnard
Painted comber
Stargazer
Conger eel
Leersh; jack
Blue sh
Crab
Scorpion sh
Scorpion sh
Striped weever
Tub gurnard
Scorpion sh
Stargaze
Painted comber
Conger eel
Amberjack
Striped weever
Tub gurnard
Tub gurnard
Painted comber
Stargaze
Conger eel

Weight (g)

Sampling location

THg (mg/kg)

MeHg expressed
as Hg (mg/kg)

MeHg/THg (%)

140
120
95
105
75
90
135
100
145
110
120
95
105
340
400
100
460
90
530
200
160
130
70
95
135
100

1.5 km in front of Punta di Castinglioncello

1 mile km in front of Punta di Castinglioncello
5.6 miles in front of the port Vada and Cecina
5.6 miles in front of the port Vada and Cecina
5.6 miles in front of the port Vada and Cecina
5.6 miles in front of the port Vada and Cecina
5.6 miles in front of the port Vada and Cecina
5.6 miles in front of the port Vada and Cecina
1.5 miles in front of the fosso bianco di Vada
1.5 miles in front of the fosso bianco di Vada
1.5 miles in front of the fosso bianco di Vada
Castiglion della Pescaia
Castiglion della Pescaia
Vicinity of Island Elba
Vicinity of Island Elba
Vicinity of Island Elba
Vicinity of Island Elba
Vicinity of Island Elba
Vicinity of Island Elba
Vicinity of Island Elba
Market in Piombino
Market in Piombino
Market in Piombino
Market in Piombino
Market in Piombino
Market in Piombino

0.185
0.218
1.20
0.260
0.049
1.55
0.133
0.424
0.170
0.454
0.508
0.429
0.502
0.855
0.129
0.115
1.08
0.680
0.352
0.301
2.48
0.251
0.534
0.860
1.98
0.570

0.185
0.122
0.727
0.129
0.022
0.834
0.071
0.202
0.107
0.290
0.292
0.372
0.415
0.605
0.093
0.095
0.401
0.680
0.239
0.184
2.38
0.234
0.519
0.845
1.90
0.547

100
56.0
60.4
49.4
45.5
54.0
53.4
47.6
63.0
63.9
57.4
86.7
82.7
70.7
72.1
82.5
37.2
100
68.0
60.9
95.9
93.2
97.2
98.3
96.0
96.0

Rosignano Solvay seems to be similar as in the reference area

Donoratico.
An important source of I-Hg that has not been included in the
PDI estimation is consumption of mushrooms, which is very
frequent in Italy. A variety of mushroom species have been shown
to contain elevated levels of mercury (Bressa et al., 1988; Kalac
et al., 1991). The extent of bioaccumulation of mercury seems to
be species-dependent (Kalac et al., 1991); the edible mushroom
Pleurotus ostreatus has been found to bioaccumulate up to
140 times the concentration in the soil (Bressa et al., 1988).
There are also a number of other possible pathways for nonoccupational exposure to inorganic forms of mercury. These
include playing on or in contaminated surface soils; playing with
liquid mercury from broken electrical switches, thermometers,
barometers, blood pressure monitors, etc. Exposure from drinking
water is usually minor (WHO, 2003).

2.5.3. Estimated exposure to methylmercury

In 2003 the Joint WHO/FAO Expert Committee on Food
Additives (JECFA) recommended a provisional tolerable weekly
intake (PTWI) for methylmercury of 1.6 mg/kg body weight/week
(equivalent to 0.23 mg methylmercury/kg body weight/day (PTDI))
in order to sufciently protect the developing foetus (WHO, 2003).
The RfD for MeHg set by the US EPA (2001) is even lower,
0.1 mg methylmercury/kg body weight day.
In Rosignano Solvay, the intake of methylmercury has been
estimated at 0.7076.26 mg/day from consumption of local marine
sh and only up to 0.10 mg/day from consumption of locally grown
vegetables (Table 5). An average adult person in Rosignano Solvay
(70 kg) consuming on average 32 g sh from the local market
consumes and retains up to 1.089 mg MeHg/kg body weight/day.
The calculated PDI/PTDI ratio for MeHg ranges up to 474% and
exceeds the toxicologically tolerable value set by JEFCA (2003).
The elevated safety limit from consumption of marine sh from
Adriatic and Ionian Seas was observed also by Storelli et al. (2005).

Fish are an important source of proteins, vitamin D, selenium,

long-chain n-3 fatty acids eicosapentaenoic acid (EPA), docosapentaenoic acid (DPA) and docosahexaenoic acid (DHA). Since
some sh contain elevated MeHg concentrations and other
harmful substances, such as polychlorinated biphenyls and
dioxins, many countries already advise that susceptible population strata should avoid consummation of certain type of sh.
Methylmercury in sh is primarily bound to the amino acids in
sh muscle; thus, skinning, trimming and cooking do not
signicantly reduce MeHg concentrations (Kris-Etherton et al.,
2002).

2.5.4. Total mercury exposure in Rosignano Solvay

The PTDI for total mercury has been estimated by JEFCA (2003)
at 0.71 mg/kg body weight/day (equivalent to 5 mg/kg body weight/
week). In Rosignano Solvay the PDI for total mercury for an
average 70-kg adult has been estimated at 0.0751.389 mg/
kg body weight/day, which is similar to the intake in the reference
area (0.0751.332 mg/kg body weight/day). According to our estimations (Table 5), the PDI/PTDI ratio for total mercury inhaled and
ingested from various sources (air, amalgam, sh, vegetables,
drinking water and food other than vegetables and sh) ranged
from 11% to 196% in Rosignano Solvay and 11188% in the
reference area.
Estimated PDI/PTDI ratios for total mercury in Rosignano
Solvay were: up to 4% from inhalation of ambient air, up to 14%
from ingesting local vegetables and up to 160% from consuming
local marine sh. Estimated PDI/PTDI ratios for total mercury in
Donoratico as the reference area were: up to 0.3% from inhalation
of ambient air, up to 10% from ingesting local vegetables and up to
160% from consuming local marine sh.
According to EFSAs report from 2004, the average estimated
daily intake of total mercury in Italy is 8.6 mg/day or 0.123 mg/kg
body weight/day for an average 70-kg adult, which corresponds to
17.2% of the PTDI. EFSAs estimation is based on lower Hg

ARTICLE IN PRESS
D. Gibicar et al. / Environmental Research 109 (2009) 355367

364

Table 5
Estimated range of daily intakes of inorganic mercury, elemental mercury, methylmercury and total mercury in mg for inhabitants of Rosignano Solvay and the reference
area.
Medium

Probable daily intake (PDI) in mg/day

Hg vapour

Inorganic Hg

MeHg

Total Hg

Aira
Rosignano Solvay
Reference area

0.062.0a
0.030.11

0b
0

0b
0

0.062.00
0.030.11

Local vegetablesc
Rosignano Solvay
Reference area

0
0

0.007.10
0.015.04

0.000.10
0.000.09

0.007.20
0.015.13

Fishd
Amalgame
Drinking waterf
Other foodg

0
0.05.0
0
0

0.0022.9
0
0.05
3.6

0.7076.16
0
0
0

1.5779.36
0.05.0
0.05
3.6

Total
Rosignano Solvay
Reference area

0.067.00
0.035.11

3.6533.66
3.6631.61

0.7076.26
0.7076.26

5.2897.2
5.2693.3

Total PDI in mg/kg bw/dayh

Rosignano Solvay
Reference area

0.0010.100
0.0000.073

0.0520.481
0.0520.452

0.0101.089
0.0101.089

0.0751.39
0.0751.33

Provisional tolerable daily intake (PTDI)

PDI/PTDI (%)
Rosignano Solvay (%)
Reference area (%)

4 mg/dayi

2 mg/kg bw/dayi

0.23 mg/kg bw/dayj

0.71 mg/kg bw/dayj

2175
1128

324
323

4474
4474

11196
11188

Daily intakes from sources of Hg, such as dental amalgam, drinking water and food other than sh and vegetables were taken from the literature.
a
Assumes a daily respiratory volume of 20 m3, and air concentration of 2.8100 ng/m3 for Rosignano Solvay and 1.55.5 ng/m3 for Donoratico.
b
For the purposes of comparison, it is assumed that the atmospheric concentrations of species of mercury other than mercury vapour are negligible.
c
Assumes a daily intake of 300 g of vegetables with concentration of total Hg 0.0124 ng/g FW and MeHg 0.0020.348 ng/g FW for Rosignano Solvay and concentration
of total Hg 0.0317.1 ng/g FW and MeHg 0.0010.29 ng/g FW for Donoratico. Concentration of inorganic Hg is calculated as (conc. of total Hgconc. of MeHg).
d
Assumes a daily intake of 32 g of sh with concentration of 0.0222.38 mg MeHg/g FW and 0.0492.48 mg total Hg/g FW. Concentration of inorganic Hg is calculated as
(conc. of total Hgconc. of MeHg) and ranges from 0.000.716 mg I-Hg/g FW.
e
Assumes a daily intake of 1.25 mg from dental amalgam, reported by WHO (2003). Daily intake of up to 27 mg from dental amalgam has been reported by ATSDR
(1999).
f
Assumes a daily intake of 0.05 mg of inorganic Hg (IPCS, 1991; WHO, 2003).
g
Assumes a daily intake of 3.6 mg of inorganic Hg (IPCS, 1991; WHO, 2003).
h
Assumes an average body weight of 70 kg.
i
PTDI according to WHO (2003).
j
PTDI according to JEFCA (2003).

concentrations in sh and molluscs (0.070.45 mg/g) which were

gathered from available data from 1997. The average intake of
total mercury by an adult in the Member States of EFSAs
report is estimated at 5.53 mg/day or 0.079 mg/kg body weight/
day for an average 70-kg adult. The EFSAs data show that for a
food item like sh the variation of mean consumption in different
countries across Europe is very high and the variation in food
consumption could result in exposures that vary by a factor
of 10.

3. Discussion
MCCA plants produce chlorine, thus the emission plume may
contain a mixture of Hg0, Cl2 and HgCl2. The main sources of
gaseous Hg in the caustic-chlorine industry are ventilation air
outlets from cell rooms, H2 gas outlets, Hg evasion from waste
water and solid wastes. Emission of mercury from the MCCA plant

in Rosignano Solvay was measured by differential absorption

LIDAR (DIAL) technique in 2003 by Gronlund et al. (2005). They
estimated the emission of Hg from the plant to be around
2054 g/h, which was similar to the earlier measurements made
in 1990 (around 43 g/h) by Ferrara et al. (1992). The measured ux
depends on ambient temperature and wind speed, since these
parameters affect the temperature of the cells and the re-emission
processes from contaminated soil around the cell and from spills
distributed in the cell house structures (Gronlund et al., 2005;
Bennett et al., 2006).
Concentrations of ambient air measured in Rosignano Solvay in
2002 were relatively low: 8.08.7 ng/m3 in summer and
2.84.2 ng/m3 in winter, although at particular meteorological
conditions concentrations of up to 100 ng/m3 were observed.
Background mercury levels (2 ng/m3) were reached already 3 km
from the MCCA plant. In Poland for example, 1800 m from the cell
of the MCCA plant in Tarnow, mean measured TGM concentration
in ambient air were 16 ng/m3 (Jarosinska et al., 2006).

ARTICLE IN PRESS
D. Gibicar et al. / Environmental Research 109 (2009) 355367

We found most of the mercury in the atmosphere around the

MCCA plant in Rosignano Solvay in its elemental form, which
circulates in the atmosphere and can be widely dispersed and
transported over thousands of kilometres affecting soils and
aquatic environments in remote areas. We observed only around
4.2% of total emitted Hg present in the form of HgII, which is in
contrast to Hg0 easily deposited to ground and vegetation by
precipitation or dry deposition. Only around 1.0% of total Hg was
present in the form of TPM. The deposition of emitted Hg depends
on the amount of HgII and TPM emitted, rather than the total
mercury emitted. The results of modelling of emitted Hg showed
that only 14% (or 6.8 kg/yr) of total emitted Hg were deposited
within 5 km from the plant, while the remaining 86% were
dispersed and transported away from the area, showing its
characteristics of a global pollutant.
As mercury cycles between atmosphere, pedosphere and
hydrosphere, undergoes many complex chemical and physical
transformations such as biotic and abiotic methylation or
Hg0 oxidation which may increase toxicity and bioavailability of the
metal (Lindqvist et al., 1991; Stein et al., 1996). Mercury deposited
to soil is affected by various chemical and biological transformation processes such as Hg0 oxidation, HgII reduction or methylation, depending on several soil parameters (pH, temperature, soil
humic substances content, the nature of organic matter and its
quantity, etc.) (Weber, 1993; Remy et al., 2006; Wang et al., 2003).
Methylation and demethylation processes involve activity of SO4reducing bacteria, methanogens, photoreduction (Costa and
Liss, 2000) and other abiotic processes in soil. If Hg0 is dry
deposited to soil, it has the potential to be converted to reactive
Hg and sequestered in the soil. If HgII is dry deposited to
soils, it has the potential to be reduced and re-emitted through
volatilization. The chemistry of either oxidation or reduction may
prevail. In case of prevailing oxidation, a larger metal retention
may occur after some time, since it is the reduced species
that returns to the atmosphere through volatilization and not
the oxidized one. Since atmospheric levels of mercury measured
in Rosignano Solvay were only twothree times higher than
those measured at the reference station, as expected also
surface soil from the Rosignano Solvay area contained relatively
low levels of total mercury (30.12919 mg/kg DW) and methylmercury (0.023.88 mg/kg DW). Similar concentrations of THg in
soil from the same area were found also by Maserti and Ferrara in
1991.
Assimilation through plants plays a major role in the entry of
mercury into terrestrial food chains (Barghigiani and Ristori, 1994;
WHO, 1989). The assimilation of mercury by plants does not
depend only on its concentration in soil, but also on the ratio of
soil and air mercury contamination, on bio-chemical conditions of
soil and on meteorological conditions. Vascular plants accumulate
Hg (a) through the roots from soil as ionic Hg or dissolved gaseous
Hg (DGM); (b) through the stomata from the atmosphere,
particularly as Hg0; (c) through foliar adsorption of divalent,
reactive gaseous mercury and particulate Hg (Shaw and Panigrahi,
1986; Lindberg et al., 1992; Bishop et al., 1998). Plants also emit
mercury vapour from leaves (Ericksen et al., 2003). Vegetation can
thus act as a source or a sink of atmospheric Hg. Data from
monitoring forested ecosystems indicates that dry deposition to
forest canopies is a signicant removal process for both atmospheric Hg0 and MeHg species (Lindberg et al., 1991; Iverfeldt, 1991;
Hultberg et al., 1994; Munthe et al., 1995). The assimilation from soil
by roots depends on soil type, content of humic acid, microbiological
activity, pH and redox potential. The assimilation through leaves
depends on type of plant, air contamination and atmospheric aerosol
deposition. Bryophytes and lichens have no roots and assimilate
mercury only from air and water and can be used as active
biomonitors (Fernandez et al., 2002; Bargagli and Barghigiani, 1991;

365

Bargagli et al., 1987; Maserti and Ferrara, 1991). Mercury assimilation

by some vascular plants is considered to be negligible, whereas
others bioconcentrate mercury (e.g., Pinus sp., About et al., 2001).
These plants have been used under experimental conditions for
decontamination of polluted soils. It is known that certain species,
such as carrots, lettuce and mushroom in particular, are likely to
assimilate more mercury than others growing at the same location.
In our study the highest concentrations of mercury (expressed on a
dry weigh) were observed in basil, beet, celery, parsley, and mint.
Vegetables grown in the area around the MCCA plant in Rosignano
Solvay contained slightly higher levels of total and methylmercury
compared to the vegetables grown 20 km south, but the difference
was not statistically signicant and the number of samples was
relatively low.
Another contribution to the mercury pollution by the MCCA
plant in Rosignano Solvay is the mercury discharged through an
efuent channel into adjacent coastal seawater. Ferrara et al.
(2001) estimated the release of mercury in the coastal seawater
through a discharge ditch of the MCCA plant in Rosignano Solvay
to be about 400500 kg/yr at the present chlorine production.
They also estimated that from the 1950s to 1973 1214 ton/yr of
mercury owed into the sea through a discharge ditch, which
were incorporated into the surrounding sediments. Once in the
aquatic ecosystem, part of the inorganic mercury can be microbially converted into methylmercury and taken up by aquatic
organisms. It is known that sh accumulate mercury directly from
food and from the surrounding water (Rainbow, 1985) and can
bioconcentrate large amounts of this metal. Methylmercury
concentration in sh depends on the feeding habits of the sh,
mercury concentrations in tissues of its prey, the shs age and
position in the food chain. The highest concentrations are found in
large and old predatory sh, such as sharks, swordsh, tuna and
pike. Mediterranean Sea constitutes beside the anthropogenic
input the richest natural reserve of Hg. Deep environment of the
Mediterranean Sea, the high temperature and the absence of solar
radiation favour a high methylation rate (Bacci, 1989) resulting in
bioconcentration in predator species and biomagnication
through the benthic food chains. Many studies have described
elevated levels of mercury in marine organisms from the
Mediterranean Sea (Renzoni and Baldi, 1975; Hornung et al.,
1993; Storelli et al., 2002, 2005, 2007).
The elevated Hg content in marine sh observed during our
study cannot be directly associated with the emissions of Hg from
the MCCA plant in Rosignano Solvay, since many other (natural
and anthropogenic) sources of Hg in the Mediterranean exist.
However, for freshwater sh, an assumption is made that an
increase in local deposition leads to a linear increase in mercury
levels in local freshwater sh. Fish and sediments collected in
rivers or canals downstream the MCCA plants contain higher
Hg levels compared to the samples collected upstream (Scerbo
et al., 2005; Raldua et al., 2007). Moreover, histopathological
analysis showed that sh downstream the MCCA plants have
signicantly higher prevalence of liver pathologies (Raldua et al.,
2007).
We performed simple exposure and risk assessment for
elemental, inorganic, methyl and total mercury, drawn on
measurements conducted for this study, as well as on measurements and intake estimates drawn from the literature. We
concluded that following worst case scenario, people living near
the MCCA plant in Rosignano Solvay inhale up to 2.0 mg Hg0/day
from the ambient air (or 50% of the PTDI according to WHO
(2003), while people living in the reference area Donoratico inhale
up to 0.11 mg Hg0/day. Dental amalgam is a much more signicant
source of exposure to elemental mercury, whose contribution can
exceed the provisional tolerable intake of 4 mg/day. Estimates of
daily intake from amalgam restorations range from 1 to 27 mg/day

ARTICLE IN PRESS
366

D. Gibicar et al. / Environmental Research 109 (2009) 355367

(ATSDR, 1999) with the majority of dental amalgam holders being

exposed to less than 5 mg mercury/day (WHO, 2003). Of course
there is a considerable variation in Hg intake from dental
amalgam between individuals, primarily due to the number of
amalgams present, gum chewing habits and bruxism. By summing intake of elemental Hg from two sources: ambient Hg
coming from the MCCA plant (up to 50% PTDI) and Hg inhaled
from evaporating amalgam llings (up to 125% PTDI according to
WHO (2003), the tolerable intake of Hg0 of 4 mg/day can be
exceeded (following worst case scenario for up to 175% of PTDI,
Table 5).
Estimated exposure to inorganic mercury by ingestion of local
vegetables, sh and other food in inhabitants of Rosignano Solvay
was similar as in the reference population (up to 33.66 mg/day or
24% of PTDI) and showed no unacceptable risks to human health.
In contrary, estimated exposure to methylmercury seems to pose
an elevated risk of possible adverse effects of methylmercury
exposure, since marine sh from this area contain elevated levels
of methylmercury. Considering average consumption of 32 g of
sh per day, the PDI/PTDI ratio can be easily exceeded (up to
474%). Our estimated daily intakes of mercury relay on average
daily intake values and as such underestimate intakes in the case
of higher consumption rates. Diets vary considerably among
individuals in the study population, so the variation in food
consumption could result in exposures that vary by a factor of 10.
Human health risk assessment for mercury emitted from the
MCCA plants has been performed also by the organisation
representing chlorine industry named Euro Chlor (2003), based
upon the data from the immediate vicinity of mercury-based
plants operating according to current Best Available Technology
under the terms of the Integrated Pollution Prevention and
Control (IPPC) Directive 96/61/EC. Their results of worst case
scenario for human health risk assessment for inorganic and
elemental mercury, calculated from the DI/TDI ratio (daily Hg
intake (DI) 3.12 mg/kg body weight/day; tolerable daily intake
(TDI) 4 mg/kg body weight/day), showed no unacceptable risks
to human health. For the aquatic compartment and the sediments
the predicted exposure concentrations/predicted no-effect concentrations (PEC/PNEC) ratios were less than one, showing no
unacceptable risk. The PEC/PNEC ratios for the terrestrial
compartment varied from less then one for soil organisms to
more than one for terrestrial predators. For inorganic and organic
mercury worst case scenario of risk assessment for the marine
environment in the North Sea (OSPAR) area, including various
ecotoxicology studies, showed DI/TDI ratio higher than one for sea
birds as aquatic predators (Euro Chlor, 1999). It was concluded
that mercury is a persistent, toxic and bioaccumulable chemical.
Its potential for secondary poisoning (food-chain biomagnication) and for long-range transport, makes it a high priority
chemical for emission control. However, due to its natural
occurrence, mercury will remain ubiquitous in the environment.

4. Conclusions
The aim of our study was to provide analysis of potential
mercury risks in an area near a mercury cell chlor-alkali plant in
Rosignano Solvay in Italy. The main conclusion is that the impact
of the mercury cell chlor-alkali plant in Rosignano Solvay on the
local terrestrial environment is restricted only to the close
surrounding area. Only 14% of emitted gaseous Hg from the
mercury cell chlor-alkali plant is deposited within 5 km from the
source. The remaining 86% are dispersed and transported away
from that area increasing the atmospheric pool of mercury.
Exposure assessment performed by calculating ratios of probable
daily intake and provisional tolerable daily intake of mercury for

various exposure pathways showed no unacceptable risks to

human health for elemental and inorganic mercury, except for
individuals with higher number of amalgam llings. In contrary,
the PDI/PTDI ratio for methylmercury and total mercury exceeded
the toxicologically tolerable value due to the potential consumption of local marine sh. Exceeded PDI/PTDI ratio for methylmercury and total mercury from consumption of contaminated sh is
not directly associated with the emissions of mercury from the
MCCA plant in Rosignano Solvay, but is a product of anthropogenic
and natural sources of Hg present in the Mediterranean. We
conclude that any exceeded tolerable daily intake values are due
to other sources of mercury, rather than the mercury cell chloralkali plant.

Acknowledgments
This work was supported by the 5FP EU project EMECAP
(European Mercury Emission from Chlor-Alkali Plants, QLK4-CT2000-00489), the Ministry of Education, Science and Sport of the
R Slovenia (Programme P1-0143) and by nancial support by the
young researchers programme. Part of the programme was also
co-nanced by the Centre of Excellence for Environmental
Technologies funded by the EU structural funds and the IAEA
CRP 13250/RD. The authors wish to thank Ana Nusa Prosenc for
help with Hg and Se analysis by neutron activation analysis.
References
About, J.R., Fernandez, J.A., Carballeira, A., 2001. Sampling optimization, at site
scale, in contamination monitoring with moss, pine and oak. Environ. Pollut.
115, 313316.
ATSDR, 1999. Toxicological Prole for Mercury. Agency for Toxic Substances and
Disease Registry, US Department of Health and Human Services, Public Health
Service, Atlanta, GA.
Bacci, E., 1989. Mercury in the Mediterranean. Mar. Pollut. Bull. 20, 5963.
Baldi, F., Bargagli, R., 1984. Mercury pollution in marine sediment near a chloralkali plant: distribution and availability of the metal. Sci. Total Environ. 39,
1526.
Baldi, F., DAmato, M.L., 1986. Mercury pollution in marine sediment cores near
cinnabar deposits and a chlor-alkali plant. Sci. Total Environ. 57, 111120.
Bargagli, R., Iosco, F.P., Barghigiani, C., 1987. Assessment of mercury dispersal in an
abandoned mining area by soil and lichens analysis. Water Air Soil Pollut. 36,
219225.
Bargagli, R., Barghigiani, C., 1991. Lichen biomonitoring of mercury emission and
deposition in mining, geothermal and volcanic areas of Italy. Environ. Monit.
Assess. 16, 265275.
Barghigiani, C., Bauleo, R., 1992. Mining area environmental mercury assessment
using Abies alba. Bull. Environ. Contam. Toxicol. 49, 3136.
Barghigiani, C., Ristori, T., Biagi, F., De Ranieri, S., 2000. Size related mercury
accumulations in edible marine species from an area of the northern
Tyrrhenian Sea. Water Air Soil Pollut. 124, 169176.
Barghigiani, C., De Ranieri, S., 1992. Mercury content in different size classes of
important edible species of the northern Tyrrhenian Sea. Mar. Pollut. Bull. 24,
114116.
Barghigiani, C., Pellegrini, D., DUlivo, A., De Ranieri, S., 1991. Mercury assessment
and its relation to selenium levels in edible species of the northern Tyrrhenian
Sea. Mar. Pollut. Bull. 22, 406409.
Barghigiani, C., Ristori, T., 1994. Mercury levels in land products of Mt. Amiata
(Tuscany, Italy). Arch. Environ. Contam. Toxicol. 26, 329334.
Bennett, M., Edner, H., Gronlund, R., Sjoholmb, M., Svanberg, S., Ferrara, R., 2006.
Joint application of Doppler Lidar and differential absorption lidar to estimate
the atomic mercury ux from a chlor-alkali plant. Atmos. Environ. 40,
664673.
Bishop, K.H., Lee, Y.-H., Munthe, J., Dambrine, E., 1998. Xylem sap as a pathway for
total mercury and methylmercury transport from soils to tree canopy in the
boreal forest. Biogeochemistry 40, 101113.
Bressa, G., Cima, L., Costa, P., 1988. Bioaccumulation of mercury in the mushroom
Pleurotus ostreatus. Ecotoxicol. Environ. Saf. 16, 8589.
Byrne, A.R., Kosta, L., 1974. Simultaneous neutron-activation determination of
selenium and mercury in biological samples by volatilization. Talanta 21,
10831090.
Byrne, A.R., Skreblin, M., Falnoga, I., Al-Sabti, K., Stegnar, P., Horvat, M., 1995.
Mercury and selenium: perspectives from Idrija. Acta Chim. Slov. 42, 175198.
Clarkson, T.W., 1997. The toxicology of mercury. Crit. Rev. Clin. Lab. Sci. 34,
369440.

ARTICLE IN PRESS
D. Gibicar et al. / Environmental Research 109 (2009) 355367

Costa, M., Liss, P., 2000. Photoreduction and evolution of mercury from seawater.
Sci. Total Environ. 261, 125135.
Denby, B., Pacyna, J., 2004. Deliverable D5.4. EMECAP. Final report to the European
Commission, Brussels, Belgium, 2004.
DEFRA, 2002. Soil Guideline Values for Inorganic Mercury Contamination.
Department for Environment, Food and Rural Affairs.
EFSA (European Food Safety Authority), 2004. SCOOP 3.2.11intake of As, Cd, Pb
and Hg. EFSA J. 34, 114 Available at /http://www.mhlw.go.jp/shingi/2004/08/
dl/s0817-2k2.pdfS.
Ericksen, J.A., Gustin, M.S., Schorran, D.E., Johnson, D.W., Lindberg, S.E., Coleman,
J.S., 2003. Accumulation of atmospheric mercury in forest foliage. Atmos.
Environ. 37, 16131622.
Euro chlor mercury risk assessment, Local scenario, an overview, 2003. Available
at:
/http://www.chem.unep.ch/Mercury/2003-ngo-sub/Eurochlor/Euro%
20Chlor%20Hg%20RA%20Local%20Scenario%20Summary.docS.
Euro Chlor, 1999. Euro chlor risk assessment for the marine environment
OSPARCOM RegionNorth Sea, Mercury. Available at: /http://www.
eurochlor.org/HgS.
Euro Chlor, 2005. Chlorine Industry Review 20042005. Euro Chlor, Brussels.
Available at: /http://www.eurochlor.orgS.
Falnoga, I., Tusek-Znidaric, M., Horvat, M., Stegnar, P., 2000. Mercury, selenium, and
cadmiun in human autopsy samples from Idrija residents and mercury mine
workers. Environ. Res. Sect. A 84, 211218.
Fernandez, J.A., Ederra, A., Nunez, E., Martynez-Abaigar, J., Infante, M., Heras, P., et
al., 2002. Biomonitoring of metal deposition in northern Spain by moss
analysis. Sci. Total Environ. 300, 115127.
Ferrara, R., Maserti, B.E., Paterno, P., 1989. Mercury distribution in marine sediment
and its correlation with the Posidonia oceanica prairie in a coastal area affected
by a chlor-alkali complex. Toxicol. Environ. Chem. 22, 131134.
Ferrara, R., Maserti, B.E., Edner, H., Ragnarsson, P., Svanberg, S., Wallinder, E., 1992.
Mercury emissions into the atmosphere from a chlor-alkali complex measured
with the lidar technique. Atmos. Environ. 26A (7), 12531258.
Ferrara, R., Lanzillotta, E., Ceccarini, C., 2001. Dissolved gaseous mercury
concentration and mercury evasional ux from seawater in front of a chloralkali plant. Environ. Technol. 22 (8), 971978.
Gronlund, R., Sjoholm, M., Weibring, P., Edner, H., Svanberg, S., 2005. Elemental
mercury emissions from chlor-alkali plants measured by lidar techniques.
Atmos. Environ. 39, 74747480.
Hornung, H., Krom, M.D., Cohen, Y., Bernhard, N., 1993. Trace metal content in deep
water sharks from the eastern Mediterranean Sea. Mar. Biol. 115, 331338.
Horvat, M., Byrne, A.R., May, K., 1990. A modied method for the determination of
methylmercury by gas chromatography. Talanta 37 (2), 207212.
Horvat, M., Liang, L., Bloom, N.S., 1993. Comparison of distillation with other
current isolation methods for the determination of methylmercury compounds
in low level environmental samples, Part I. Sediment. Anal. Chim. Acta 281,
135152.
Horvat, M., Lupsina, V., Pihlar, B., 1991. Determination of total mercury in coal y
ash by gold amalgamation cols vapour atomic absorption spectrometry. Anal.
Chim. Acta 243, 7179.
Horvat, M., May, K., Stoeppler, M., Byrne, A.R., 1988. Comparative studies of
methylmercury determination in biological and environmental samples. Appl.
Organomet. Chem. 2, 515524.
Horvat, M., Mandic, Liang, L., Bloom, N.S., Padberg, S., Lee, Y.H., Hintelmann, H.,
Benoit, J., 1994. Certication of methylmercury compounds concentration in
marine sediment reference material, IAEA-356. Appl. Organomet. Chem. 8,
533540.
Hultberg, H., Iverfeldt, A., Lee, Y.-H., 1994. Methylmercury inputoutput and
accumulation in forested catchments and critical loads for lakes in southwestern Sweden. In: Watras, C.J., Huckabee, J.W. (Eds.), Mercury Pollution:
Integration and Synthesis. Lewis Publishers, Chelsea, MI, pp. 313322.
IPCS, 1991. Inorganic Mercury. World Health Organization, International Programme on Chemical Safety, Geneva (Environmental Health Criteria 118).
Iverfeldt, A., 1991. Mercury in forest canopy through fall water and its relation to
atmospheric deposition. Water Air Soil Pollut. 56, 553564.
Jarosinska, D., Barregard, L., Biesiada, M., Muszynska-Graca, M., Dabkowska, B.,
Denby, B., Pacyna, J., Fudala, J., Zielonka, U., 2006. Urinary mercury in adults in
Poland living near a chlor-alkali plant. Sci. Total Environ. 368, 335343.
Joint FAO/WHO Expert Committee on Food Additives (JEFCA), World Health
Organization (WHO), 2003. Sixty-rst meeting 1019 June 2003, summary and
conclusions. Available on-line: /ftp://ftp.fao.org/es/esn/jecfa/jecfa61sc.pdfS.
Kalac, P., Burda, J., Staskova, I., 1991. Concentrations of lead, cadmium, mercury,
and copper in mushrooms in the vicinity of a lead smelter. Sci. Total Environ.
105, 109119.
Kim, K.H., Lindberg, S.E., 1995. Design and initial tests of a dynamic enclosure
chamber for measurments of vapour-phase mercury uxes over soils. Sci. Total
Environ. 80, 10591068.
Kosta, L., Byrne, A.R., Zelenko, V., 1975. Correlation between selenium and mercury
in man following exposure to inorganic mercury. Nature 254, 238239.
Kris-Etherton, P.M., Harris, W.S., Appel, L.J., for the Nutrition Committee, 2002. Fish
consumption, sh oil, omega-3 fatty acids, and cardiovascular disease.
Circulation 106, 27472757.

367

Liang, L., Horvat, M., Bloom, N.S., 1994a. An improved speciation method for
mercury by GC/CVAFS after aqueous phase ethylation and room temperature
precollection. Talanta 41 (3), 371379.
Liang, L., Bloom, N.S., Horvat, M., 1994b. Simultaneous determination of mercury
speciation in biological materials by GC/CVAFS after ethylation and roomtemperature precollection. Clin. Chem. 40, 602607.
Lindberg, S.E., Turner, R.R., Meyers, T.P., Taylor Jr., G.E., Schroeder, W.H., 1991.
Atmospheric concentrations and deposition of airborne Hg to Walker branch
watershed. Water Air Soil Pollut. 56, 577594.
Lindberg, S.E., Meyers, T.P., Taylor Jr., G.E., Turner, R.R., Schroeder, W.H., 1992.
Atmospheresurface exchange of mercury in a forest: results of modeling and
gradient approaches. J. Geophys. Res. 97 (D2), 25192528.
Lindqvist, O., Johansson, K., Aastrup, M., Andersson, A., Brinkmark, L., Hovsenius,
G., Hakanson, L., Iverfeldt, A., Meili, M., Timm, B., 1991. Mercury in the Swedish
environment: recent research on causes, consequences and corrective
methods. Water Air Soil Pollut. 55, 1261.
Logar, M., Horvat, M., Falnoga, I., Stibilj, V., 1999. A methodological study of
mercury speciation using Dogsh liver CRM (DOLT-2). Fres. J. Anal. Chem. 366,
452460.
Maserti, B.E., Ferrara, R., 1991. Mercury in plants, soil and atmosphere near a chloralkali complex. Water Air Soil Pollut. 56, 1520.
McLaughlin, M.J., Parker, D.R., Clarke, J.M., 1999. Metals and micronutrientsfood
safety issues. Field Crops Res. 60, 143163.
Munthe, J., Hultberg, H., Iverfeldt, A., 1995. Mechanisms of deposition of
methylmercury and mercury to coniferous forests. Water Air Soil Pollut. 80,
363371.
Pacyna, E.G., Pacyna, J.M., Fudala, J., Strzelecka-Jastrzab, E., Hlawiczka, S., Panasiuk,
D., 2006. Mercury emissions to the atmosphere from anthropogenic sources in
Europe in 2000 and their scenarios until 2020. Sci. Total Environ. 370, 147156.
Rainbow, P.S., 1985. The biology of heavy-metals in the sea. Int. J. Environ. Stud. 25,
195211.
Raldua, D., Dez, S., Bayona, J.M., Barcelo, D., 2007. Mercury levels and liver
pathology in feral sh living in the vicinity of a mercury cell chlor-alkali
factory. Chemosphere 66 (7), 12171225.
Reilly, C., 1996. Selenium in Food and Health. Blackie Academic & Professional,
London, Weinheim, New York, 323pp.
Remy, S., Prudent, P., Probst, J.L., 2006. Mercury speciation in soils of the
industrialised Thur River catchment (Alsace, France). Appl. Geochem. 21 (11),
18551867.
Renzoni, A., Bacci, E., Falciai, L., 1973. Mercury concentration in the water,
sediments and fauna of an area of the Tyrrhenian Coast. Rev. Intern. Oceanogr.
Med. XXXIXXXII, 1745.
Renzoni, A., Baldi, F., 1975. Osservazioni sulla distribuzione di mercurio nella fauna
del Mar Ligure e del Mar Tirreno. Acqua e Aria 8, 597602.
Rossi, A., Pellegrini, D., Belcari, P., Barghigiani, C., 1993. Mercury in Eledone cirrhosa
from the northern Tyrrhenian Sea: contents and relations with life cycle. Mar.
Pollut. Bull. 26, 683686.
Scerbo, R., Ristoria, T., Stefaninia, B., De Ranieri, S., Barghigiani, C., 2005. Mercury
assessment and evaluation of its impact on sh in the Cecina river basin
(Tuscany, Italy). Environ. Pollut. 135, 179186.
Shaw, B.P., Panigrahi, A.K., 1986. Uptake and tissue distribution of mercury in some
plant species collected from a contaminated area in India: its ecological
implications. Arch. Environ. Contam. Toxicol. 15, 439446.
Stein, E.D., Cohen, Y., Winer, A.M., 1996. Environmental distribution and transformation of mercury compounds. Crit. Rev. Environ. Sci. Technol. 26, 143.
Storelli, M.M., Giacominelli-Stufer, R., Marcotrigiano, G.O., 2002. Total and
methylmercury residues in cartilaginous sh from Mediterranean Sea. Mar.
Pollut. Bull. 44, 13541358.
Storelli, M.M., Storelli, A., Giacominelli-Stufer, R., Marcotrigiano, G.O., 2005.
Mercury speciation in the muscle of two commercially important sh, hake
(Merluccius merluccius) and striped mullet (Mullus barbatus) from the
Mediterranean Sea: estimated weekly intake. Food Chem. 89, 295300.
Storelli, M.M., Barone, G., Garofalo, R., Marcotrigiano, G.O., 2007. Metals and
organochlorine compounds in eel (Anguilla anguilla) from the Lesina lagoon,
Adriatic Sea (Italy). Food Chem. 100, 13371341.
US EPA (Environmental Protection Agency), 2001. Available at URL: /http://
www.epa.gov/mercury/exposure.htmS.
Wang, D., Shi, X., Wei, S., 2003. Accumulation and transformation of atmospheric
mercury in soil. Sci. Total Environ. 304, 209214.
Wangberg, I., Edner, H., Ferrara, R., Lanzillotta, E., Munthe, J., Sommar, J., Sjoholm,
M., Svanberg, S., Weibring, P., 2003. Atmospheric mercury near a chlor-alkali
plant in Sweden. Sci. Total Environ. 304, 2941.
Weber, J.H., 1993. Review of possible paths for abiotic methylation of mercury (II)
in the aquatic environment. Chemospere 26, 20632072.
WHO, 1989. Environmental Health Criteria 86: Mercury-Environmental Aspects.
World Health Organisation, Geneva.
WHO, 2003. Concise International Chemical Assessment Document 50. Elemental
Mercury and Inorganic Mercury Compounds: Human Health Aspects. IPCS,
WHO, Geneva, Switzerland.
Xiao, Z.F., Munthe, J., Schroeder, W.H., Lindqvist, O., 1991. Vertical uxes of volatile
mercury over forest soil and lake surfaces in Sweden. Tellus 43B, 267279.