The Science of the Total Environment 168 (1995) 63-69

Mercury in environmental and biological samples from a

gold mining area in the Amazon region of Brazil

Dulcideia Palheta, Andrew Taylor* b

a Trace Elements Laboratory, Robens Institute of Health and Safeiy, Universiry of Surrey, Guildford, Surrey GU.2 5XH, UK
bDepartmertt of Clinical Biochemtim, St. Lukes Hospital, Guildford, Surrey GUI 3NT UK

Received 2 September 1994; accepted 1 November 1994

Abstract

A massiveincreasein gold mining in the Amazon region of Brazil has led to an enormousdischargeof metallic
mercury into the aquatic ecosystem.To investigatethe dispersion,total and inorganic mercury concentrationswere
measuredin water, fish and animal tissues,and in blood, urine and hair from membersof the local populations.
Mercury concentrationsin river water, sedimentsand fishwere high comparedwith thoseof non-contaminatedareas.
Cattle and pigskept in the area and with accessto the contaminatedrivers had concentrationsof mercury of 0.1-1.28
pg/g and 11.7-15.7 pg/l in hair and blood, respectively.These resultsare approximately twice those measuredin
specimensfrom control animals.Mean mercury concentrationsin blood, urine and hair of residentswere increased
at 11.4pg/l, 22.8 pg/l and 4.3 pg/g, respectively,and the urine mercury of workersfrom the gold mining siteswere
up to 155 pg/l. The resultsdemonstratewidespreadcontamination of the environment by mercury with transfer of
the metal to fish and animalsusedfor food, and into the inhabitantsof the region. Further investigationsfor possible
adversehealth effects need to be undertaken.

Keywords: Mercury; Gold mining; Amazon region; Blood; Hair; Urine

1. Introduction has a long biological half-life and accumulates

through the food chain as was demonstrated in
Methylmercury is highly toxic to the central the Minamata Bay incident where waste mercury
nervous system and to the developing fetus [l]. It discharged into sea water was methylated and
concentrated into fish 5000-50 OOO-fold [2,3]. In-
dividuals who ate the fish had symptoms of
dysarthria, ataxia and tunnel vision and there
*Corresponding author, Trace Elements Laboratory,
Robens Institute of Health and Safety, University of Surrey, were increased rates of miscarriage and fetal mal-
Guildford, Surrey GU2 5XH, UK. formations among pregnant women. Toxicity

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64 D. Palheta, A. Taylor / The Science of the Total Environment I68 (1995) 63-69

caused by exposure to elemental mercury with
damage to the peripheral and central nervous
systems, the kidney and the fetus, has long been
recognised [4,5].
In the last 10 years there has been a large
increase in gold mining activity in the Amazon
region of Brazil [6,7]. Extraction of alluvial gold
requires the use of metallic mercury to form an
amalgam of gold and mercury, and amounts in
excess of 100 tonnes/year are employed in Brazil.
The amalgam is subsequently heated with release
of mercury vapour into the air. There is aIso
discharge of enormous amounts of mercury into
the Amazonian aquatic ecosystem with an imme-
diate risk to the environment and to fish. Domes-
tic and farm animals who drink river water are
also exposed to increased amounts of mercury.
Humans in these areas will be exposed to the

ATLANTIC OCEAN

Fig. 1. Diagramatic plan of the Gurupi gold field, Para, Brazil with water mercury concentrations represented by the size of the
oatterned blocks
 D. Palheta, A. Taylor / The Science of the Total Enuironment 168 (1995) 63-69 65

Table 1 the Gurupi, Piria and Macaco Rivers, and drinking

Samples collected for measurement of mercury water from the village of Cachoeira were col-
Source Specimen n Specimen n Specimen n lected into containers with 0.2 ml KBrO, (0.1
M)-KBr (1% m/v) and 0.2 ml HCl per 20 ml
Water River 8 Tap 1 water. Specimens were kept at 4C until analysis.
Fish 7 diferent 38
species Fish. Species regularly used as food were caught
Pig Blood 13 Hair 15 in the rivers or bought from markets, their local
Sheep Blood 6 Hair 6 names were Piaba, Tucunare, Cachorrinho de
Cattle Blood 10 Hair 10 Padre, Acara, Traira, Pacu and Mandii. The
Human Blood 23 Hair 35 Urine 25
specimens were later identified by the Natural
History Museum, London as Characidae, Cichlu
metal in an occupational setting and/or via con- sp., Cemicichla sp., Geophagus sp., Hophias mal-
sumption of locally produced fish and meat. To abtzricus, c.f. Myleus sp. and Pimelodus sp., respec-
determine the actual dispersion of mercury and tively. Portions of edible tissues were removed for
possible health risks associated with gold extrac- analysis and stored at -20C.
tion, one area has been investigated with the Domestic animals. Specimens of hair and blood
measurement of total and inorganic mercury in were collected from pigs, sheep and cattle which
water, fish and animal tissues, and in blood, urine grazed alongside and drank water from the Gu-
and hair from members of the local populations. rupi and Piria Rivers. A further series of speci-
mens were obtained from animals at the Para
2. Materials and methods Agricultural College, not within the Gurupi area.
Human specimens.Blood, urine and hair were
2.1. Collection of specimens obtained from villagers who live alongside the
Specimens were collected at sites within the Gurupi River, from residents of Cachoeira and
Gurupi gold field in the northeast of the Brazilian from garimpeiros - the men who work at the
state of Para (Fig. 1). The village of Cachoeira gold fields. All blood, urine and hair specimens
was selected as a base since it is an important were kept at 4C until analysis.
market and gold trading centre within the area. The numbers of specimens collected for analy-
Water. Samples of river water from sites along sis are given in Table 1.

Table 2
Measurement of total mercury in blood, tissues and urine

Hg added Hg found Reproducibility

( /-G/l) ( /G/l) (CV%o)
Blood
Endogenous - 5.2 5.4
Inorganic mercury (+ 100) 105.8 102 3.0
Methylmercury (+100) 116.8 110 5.6
Urine
Endogenous - 3.7 13.0
Inorganic mercury (+50) 51.6 96 3.1
Methylmercury (+50) 45.5 91 7.1
Tissue homogenate
Endogenous - 11.2 - 7.2
Inorganic mercury (+ 100) 104.9 94.9 11.4
Methylmercury (+ 100) 103.2 94.6 11.0
Accuracy and precision (number of replicates = 10).
66 D. Palheta, A. Taylor / The Science of the Total Environment 168 (1995) 63-69

Table 3
Speciation of inorganic and organic mercury in urine

Hg added Hg found Recovery Reproducibility

( /-G/l) ( cLg/l) (%o) (CV%o)
Endogenous - 2.8 - 9.5
Inorganic mercury (+50) 54.0 102.5 3.3
Methylmercury (+50) 4.2 2.5 4.7
Measurement of inorganic mercury. Accuracy and precision (number of replicates = 10)

2.2. Determination of mercury experiments are shown in Table 2 and demon-

Tissue samples were homogenised for analysis
[8], hair was dissolved in 40% m/v NaOH [9] and
blood was examined without pre-treatment [lo].
Concentrations of mercury were measured by
cold-vapour atomic absorption spectrometry. To-
tal mercury was measured using a stannous chlo-
ride-cadmium chloride solution as the reductant.
When a stannous chloride solution was used, only
the inorganic mercury was determined [9].
Urine and water samples were digested at room
temperature with KIMnO,-H,SO,, for the mea-
surement of total mercury using stannous chlo-
ride as the reductant. A second analysis, without
digestion, yielded the inorganic mercury concen-
trations [ 111.
These procedures were evaluated using speci-
mens spiked with mercuric chloride or meth-
ylmercury. Recoveries of added mercury, and pre-
cision were determined for all sample types.
3. Results
3.1. Accuracy and precision of the analytical
procedures
The results for the recovery and reproducibility
strate that the procedure measured mercury ac-
curately and with good precision. The protocol to
differentiate between inorganic and organic mer-
cury species was also demonstrated to be effective
(Table 3).
3.2. Mercury concentrations in water and biological
samples
Water mercury concentrations are shown in
Fig. 1. River water collected around the gold
mining areas contained up to 800 rig/l mercury
compared with < 200 rig/l in the drinking water
and in river water upstream from the mining
operations. The highest concentrations were in a
lake which drained the mining area and in the
River Gurupi close to the areas where the mining
activity was at its most intense. Concentrations
fell as tributaries and other sources caused the
river to increase greatly in size, with an effective
dilution of the mercury.
Total mercury concentrations in the fish speci-
mens are given in Table 4. Higher levels occured
in carnivorous compared with plant eating species.
The proportion of organic mercury in the samples
varied from 87 to 100%.

Table 4
Total and organic mercury concentrations in fish
--- -
Species No. of Total mercury Organic
samples ( /G/g) mercury (%)

Characidae 4 0.19 87
Cichla sp. 3 0.11 91
Crenicichla sp. 8 0.21 94
Geophagus sp. 2 0.03 90
Hoplias malabaricus 13 0.61 95
cf Myleus sp 2 0.04 100
Pimelodus biochii 6 0.18 98
 D. Palheta, A. Taylor / The Science of the Total Environment 168 (1995) 63-69 67

Control animals
Exposed animals Control animals 2.0

1.o

NS

Fig. 3. Concentrations of mercury (pg/g) in hair samples

from pigs, cattle and sheep raised in the Gurupi gold field
(exposed) and the Para Agricultural College (control). NS, no
significant difference between results from the two groups.

there was no exposure to mercury. These differ-

Pigs Cattle
Fig. 2. Concentrations of mercury
from pigs, cattle and sheep raised
(exposed) and the Para Agricultural
cance between results from the two
not significant.
Sheep
(@g/l) in blood samples
in the Gurupi gold field
College (control). Signifi-
groups: *, P < 0.001; NS,
ences were statistically significant for the cattle.
Blood, urine and hair mercury concentrations
in garimpeiros, residents of Cachoeiro and those
living along the Gurupi River are given in Table
5.

4. Discussion
Total mercury levels in blood and hair from
domestic farm animals are shown in Figs. 2 and Uncontaminated freshwater mercury concen-
3. Higher concentrations are evident in specimens trations are < 10 rig/l. Thus, the concentrations
from pigs compared with cattle and sheep, but for determined in the Gurupi and Piria Rivers con-
all animals the levels were higher than in similar firm significant contamination from the gold re-
species living in the agricultural college where covery procedures. All the mercury in the water

Table 5
Mercury concentrations in human subjects

Sample Group Range Number

of results of results
-
Blood Garimpeiros 2.0-29.3 10
(/G/O Villagers 2.7-9.6 3
River dwellers 1.0-64.7 10
(Reference range) 1.7-9.9
Urine Garimpeiros 1.0-155 20
(M/l) Villagers 1.0-2.5 5
(Reference range) 0.1-6.9
Hair Garimpeiros 0.4-32.0 20
@pm) Villagers 0.8-4.6 5
River dwellers 0.2-15.0 10
(Reference range) <2
Reference range from Minoia et al. [14] and Taylor (151.
68 D. Palheta, A. Taylor /The
specimens was in the organic form. These in-
creased levels were obtained during the rainy
season when the rivers were exceptionally full and
expansive (several hundred metres wide). Even
higher concentrations might be anticipated at
other times of the year. Levels of up to 600 rig/l
were determined in Minamata Bay while else-
where in the Amazonian region, river waters have
been found with mercury concentrations as high
as 8.6 pg/l [6]. The Brazilian National Council
for the Environment has set a safety limit of 200
g/l, a level which was clearly breached during
the period of this study. Thus, water used for
drinking, agricultural and recreational purposes
represents a hazard to the inhabitants of this
area.
Previous measurements of mercury in fish mus-
cle of specimens from uncontaminated rivers were
N 0.06 pg/g. The higher concentrations in some
of the fish reported here demonstrate the accu-
mulation of mercury from the water, possibly via
smaller aquatic organisms. The major proportion
of the mercury in fish was in the organic form
indicating probable methylation of the discharged
mercury.
Domestic animals foraging, grazing and
drinking around the contaminated rivers also ac-
cumulated mercury, some to much higher concen-
trations than in unexposed controls. High levels
in hair are more usually derived from external
contamination where airborne mercury is in-
creased. Mercury in blood reflects recent and
current exposure to mercury and as a conse-
quence of the foraging and scavenging lifestyle of
the pigs these animals accumulated more mer-
cury, both the test and control groups, than did
the sheep and cattle. The cattle grazing around
the river had significantly increased blood mer-
cury concentrations compared with the controls.
Some of the pigs also had very high (> 50 pg/l)
blood mercury levels, but the group data were not
significantly different from the controls. However,
the exposed animals were much younger (< 1
year of age) than the controls and would have
accumulated less mercury from usual dietary
sources. The results indicate that mercury accu-
mulated in at least some of the domestic animals
and would provide a further source to humans if
Science of the Total Environment 168 (1995) 63-69
used as foodstuffs. Additional measurements in
meat and milk should be undertaken to de-
termine the realistic hazard from these products.
The human subjects included in this study were
exposed to several different sources of mercury;
amalgam ation and heating processes
(garimpeiros), further gold refining activities
within the villages, eating of contaminated fish
and meat and intake of contaminated river water.
Our results confirm that occupationally and non-
occupationally exposed subjects accumulate mer-
cury, and in discussions with the sampling team
some individuals described symptoms which were
consistent with mercury toxicity.
Despite the widespread publicity which has at-
tended this topic [12] there are few published
reports of the concentrations of mercury in hu-
man subjects living or working in these regions
[13]. The results from this study clearly indicate
that widespread environmental contamination
with mercury exists and that further monitoring
of environmental, animal and human specimens is
necessary.
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