JOURNALOF

GEOCHEMICAL
EXPLORATION
ELSEVIER Journal of GeochemicalExploration58 (1997) 217-222

The mercury problem in the Amazon due to gold extraction

R.C. V i l l a s B 6 a s 1
CETEM - - Centro de Tecnologia Mineral, Rua 4, Quadra D, Cidade Unit ersitdria, llha do Fund~o+ CEP 21941-590, Rio de Janeiro,
Brazil

Received 1 October 1996:accepted I November 1996

Abstract

~[he environmental impacts caused by the use of mercury (Hg), as a gold (Au) amalgam, in gold extraction in three
geographical areas located in the Brazilian wetlands (Pocon~) and the Amazon (Alta Floresta and Itaituba), are reviewed and
solutions proposed.

tG'vwords: Amazon;gold; amalgam; mercury;environment

1. Introduction dure of gold extraction. A recently developed heuris-

Mercury is widely utilised as an amalgam in
processing alluvial gold ores in rainforest areas
(Cramer, 1990; Veiga et al., 1991; Priester and
Hentscher, 1992). It's use is not just a question of
legislation, law enforcement and social pressures
exerted upon the utilizers (Barreto, 1993) but rather a
question of survival for the garimpeiros (small scale
miners).
Environmental problems related to the presence of
rrercury in the biosphere, whether in liquid, ionic or
w~pour form in Brazil are already well documented
(tzarid et al., 1992; Cfimara, 1993; Hamelmann and
Monte, 1994; Villas B6as, 1995). The possibility in
Brazil of a chemical "time bomb" effect (Stigliani,
1991; Lacerda and Salomons, 1992), requires proac-
tire assessment and management of the entire proce-
Tel.: + 55(21)260 2837. E-m all:
VILLASBOAS@CETEM.GOV.BR
tic system (Veiga and Meech. 1995) for assessing
environmental risks associated with mercury (Hg)
use in gold (Au) extraction operations, allows a
preliminary diagnosis of the problem.
2. Background to the problem
No alternative exists for Hg amalgamation in gold
extraction from alluvial ores. Processes like cyani-
dization, a problem in itself: oil or wax agglomera-
tion; halide extraction; and others, are neither com-
petitive economically nor suitable for the types of
operations and managerial skills usually employed
with secondary ore deposits.
Elemental mercury is very toxic when inhaled
(U.S.D.L., 1978; Jaffe et al., 1983). In addition,
methylation, of mercury also causes serious environ-
mental problems with Hg utilization. Several factors
govern the formation of methyl-mercury (CH3Hg +)
(Fergusson. 1990), including temperature, mercury

0{75-6742/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved.

PII S0375-6742(96)00075-1
218 R.C. Villas Bgms/ Journal of Geochemical Exploration 58 (1997) 217-222
and bacteria concentrations, pH, type of soil, type of
sediment, sulfide concentration, and redox condi-
tions, as well as seasonal variations. Methylation
occurs under both aerobic and anaerobic aquatic
conditions, although the later are favoured (Jensen
and Jernelov, 1969; Cheng Yan et al., 1994). Maxi-
mum methylation occurs in the E h range from +0.1
to - 0 . 2 V, being CH 3Hg + more stable in neutral to
acid and (CH3)zHg (dimethyl-Hg) in basic condi-
tions (Fergusson, 1990). Methylation is not an exclu-
sive property of tropical environments but occurs in
all climates (Parks et al., 1984).
The influence of sulphide ion on methylation of
Hg depends on redox conditions. If anaerobic condi-
tions prevail, HgS (low solubility) removes much of
the Hg from being methylated. If aerobic conditions
prevail (Rogers, 1977) the S 2 ion may be oxidized
to SO 2 freeing Hg ions for methylation.
Methyl-mercury accounts for about 0.1 to 1.5% of
the total mercury in sediments and around 2% of the
total in sea water (Mason and Morel, 1993); in fish,
it is greater than 80% of the total mercury. This is
the most serious aspect of the presence of Hg in fish
which are a basic food of people living in the many
scattered, small villages in fiver basins in Brazil. The
concentration of mercury in the hair and urine of
these people shows that local populations relying on
fish as their main food have been much more af-
fected by mercury than the garimpeiros. The latter
eat more beef than fish (Rodrigues et al., 1994).
The complex chemistry of mercury in the envi-
ronment is always of concern to those devoted to the
study of mercury (Renuca, 1993). The transfer of Hg
from air into water, and vice-versa, is governed by
Henry's Law, being of the order of H ~ 0.3, dimen-
sionless for metallic vapor Hg °, and O r g - H g - O r g
(e.g. Hg(CH3)2), and of the order of H ~ 10 -4, or
lower, dimensionless, for the Inorg-Hg-lnorg and
O r g - H g - I n o r g species (Brosset, 1987).
Besides mercury, the dispersion of particulate ma-
terial by earth moving operations also contributes to
the deleterious effects on biota. The physical impacts
on the environment from mining activities also in-
volve release of Hg rich particulate matter into rivers,
lakes, oceans and the air. Mercury seems to be
associated with the fine sediments due to the pres-
ence of iron-aluminate-hydroxides. There is rela-
tively little published data available on these physi-
cal dispersion processes and results for the Brazilian
Amazon.
The presence of hydrated iron oxides and organic
matter acts as an efficient natural regulator of Hg
methylation and bio-availability in aquatic systems,
even when the fight redox conditions exist for mer-
cury ionization (Silva, 1994). Contaminants can be
partitioned between water, sediment, particulate mat-
ter, and organisms (Duursma, 1994). Partition coeffi-
cients (Kd's) can be determined and are useful for
calculating the percentage distribution between, for
example, dissolved and particulate matter, the diffu-
sion of contaminants into the bottom sediment, and
their accumulation in biota. By determining Hg con-
centrations in sediments and organisms, the concen-
trations in the water compartment can thus be pre-
dicted. Partition coefficients have not been deter-
mined in the Amazon region for logistical reasons.
Estuaries can be sources or sinks of " m e r c u r y "
depending on the stage of pollution. A newly con-
taminated tropical estuary will be a sink for a very
long period, although equilibrium between input and
output may be reached sooner than in temperate
climates. The estuary may afterwards become a
source with very long turnover times of up to 1000
years (Duursma, 1994) and thus become a "time
bomb".
3. Sampling areas
Three sampling areas were selected in the Ama-
zon rain forest: the wetlands village of Pocon6 and
surroundings (Lat. 16°16'S and Long, 56°37'W); the
village of Alta Floresta and surroundings (Lat. 9°52'S
and Long. 56°05'W); and the village of Itaituba and
surroundings (Lat. 4°16'S and Long. 55°59'W).
The rational behind the selection of these areas is
one of "increasing degree of difficulty in mercury
assessment in the environment". In other words,
Pocon~ is a well settled town, founded in colonial
times, with well established landowners and cattle
raising farms. The landowners, having discovered
gold on their property, began operations to recover
the gold. These operations do not involve alluvial
work and the release of mercury is mainly in the
amalgamation step and firing. On the other hand,
Alta Floresta is a recently established real estate
 R.C Villas B~as/ Journal of Geochemical Exploration 58 (1997) 217-222
development, 10 to 15 years old, based on creating a
living infrastructure in the Brazilian interior. How-
ever, due to the occurrence of alluvial gold, a mass
movement of garimpeiros in the area occurred and
problems arose related to the release of mercury and
particulates into rivers. Finally, Itaituba is a huge
county which is larger than some European countries
and where river dredging for gold exploitation oc-
curs over the entire geographical area.
4. Collection of mercury released during ore pro-
cessing
Data (Table 1) was obtained in several field oper-
ations, before remedial action were proposed and, by
consent, adopted.
The release of mercury to the environment may
be grouped into three mayor classes:
4. i. First release o f Hg
The first release of Hg is just after the concentra-
tion step when mercury might be added to the over-
all mass of ore as it passes through the " c o b r a -
f u m a n d o " (literally means the " s m o k i n g - s n a k e " and
is a riffled wood channel which removes gold parti-
cles as sediment is passed over it in a water flow), or
after mercury has been added to the amalgamation
concentrate. In both cases a " p o o l " is set-up in such
a way that the discharged material is held-up at the
pool site. Refer to Table 1, " T a i l i n g s " , for the range
of concentrations before introducing optimization
measures.
Table 1
Mercury concentrations in several compartments in the sampling area
Area Mercury. a
Background (ppm) SedimentsCn/B~ b
Pocon6 ~ 0.10 1.5 to 24
A. Floresta ~ 0.07 1.5 to 48
Rk, Rato ~ 0.15 1.5 to 24
From the several field samples of CETEM.
b Cn/B. accounts for the ratio between the concentration of Hg in the minus 74 p~m fraction, Co, and B°, the background value of Hg in the
same fraction.
219
4.2. Second release o f Hg
The second release of Hg can occur at the firing
phase of the amalgam when it is volatilized. Two
methods are used: closed and open volatilization.
Our goal was to show how closed firing could be as
attractive economically as open firing from the oper-
ator's point of view and also how less dangerous it is
because of the use of sealed retorts. Refer to Table 1,
" A i r " , presenting the average concentrations found
in the villages indicated.
4.3. Third release o f rig
The third release of Hg can occur at the gold
shops where gold is bought from the " g a r i m p e i r o s " .
Fume hoods have now been introduced in such a
way that vapour emissions to the inside and outside
environment are minimized. Refer to Table 1, " G o l d
shops".
5. Solutions to the above problems
Problems with mercury release in small scale,
secondary gold ore processing do not occur solely in
the Brazilian wetlands and in the Amazon Basin, but
are widespread in the Pacific Rim, Latin America,
and Africa, which together are responsible for the
production of thousands of tonnes of gold per year.
The conception, design and implementation of ade-
quate methods for mercury utilization, monitoring
and release mitigation are required in all of these
areas.
Air (v~g/m ~) Gold shops (~zg/m ~) Au/Hg Tailings (ppm)
0.14-1.68 ~ 100 I : 1.5 1-25
up to 5.8 up to 40.6 1 : 1.47 5-134
up to 6.65 )9.89 N.A. 47
220 R.C. Villas B~as / Journal of Geochemical Exploration 58 (1997) 217-222

50
The solutions to the problem were divided into I
two categories: (1) the existing problem; and (2)
[Hgl* 40
future avoidance of the problem. To tackle both
30
requires involvement of the local communities (Un- (ppm)
ions, Rotary's, County Officials, the public etc.) to 20
have any chance of success, i.e., the solutions are to
10
be established by consent! Hoffmann (1994) has
described the project goals achieved with participa- 0
@ .~0 100 150 21M
tion of the local people.
Accredited analytical procedures were used
Time (rain)
(Wilken, 1991) to sample the soil, water, air. Results
were then discussed in several meetings with local Fig. 1. Mercury concentration in the residue ([Hg]*) versus time
community involvement and societal commitments of electrolysis (Sobral and Santos. 1995).
were reached in other to mitigate the problems asso-
ciated with Hg releases. These commitments were:
(1) closed circuit utilization of mercury in the con-
centration/amalgamation steps; (2) burning of the rine that in a aqueous media results in hypochlorite.
amalgam in retorts in the field, and use of fume Such a process may be viewed as an electrolytic
hoods in gold dealers' shops; and (3) confinement of segregation process, because small amounts of NaCI
processed material in specially build settling ponds. are intermixed with the resulting residue ( " o r e " ) in
These measures were taken both for the present an aqueous pulp that is electrolyzed. The general
problems and proposed to avoid future problems. For reactions may be written as:
the present problems, remediation measures were Hg + 2 C 1 0 - + 4C1 + 2 H 2 0
also taken regarding mercury fixation a n d / o r recov-
ery as below. CI 2 + HgCI 4- + 4 O H (1)
and
5.1. Immobilization of Hg
2Au + 7NaCI + NaCIO~ + 3 H 2 0
Mercury can be fixed by sulphur in polysulphites. 2 NaAuCI 4 + 6NaOH (2)
This method, however, which can be utilized for the
the dissolved gold being electrowon jointly with
inactivation of Hg in solid masses, has been criti-
mercury.
cized on the grounds of the equilibrium constants for
The data in Fig. 1 has been recorded by CETEM.
the several H g - S bonds. No field tests were con-
Mercury recovery from railings was conducted by
ducted. However, laboratory testing was performed
installing an electrooxidation pilot demonstration unit
utilizing polysulphite solutions, obtained from a mix-
in which up to 92% Hg recovery was achieved for a
ture of sulphur flowers and soda ash, i.e., commer-
6 h electrolysis time, in a 100 g / L NaCl solution,
cial grade sulphur and sodium hydroxide. The re-
with an average energy consumption of 177 k W h / t ,
sults, in terms of the actual degree of fixation are
at pH 6-7, from tailings containing 6.8 m g / k g of
still pending because of difficulty in analyzing HgS
Hg, producing a final solid material with 0.5 m g / k g
below 1 ppm (Wilken, 1991).
of Hg. The dissolution of mercury may be viewed as:
5.2. RecoL,ery of rig 2 NaOC1 + Hg ° + 4 HC1
-~ 2 N a - + HgCI]- + 2 H 2 0 + C12
Whenever possible, mercury has to be recovered.
One method tested by CETEM is that of electro- and mercury being deposited as elemental mercury.
oxidation (Veiga et al., 1991; Sobral and Santos, A series of pilot plant runs are being conducted in
1995). Its main feature is generation of hypochlorite the location of Rio do Rato in order to decrease the
ions by oxidation of chloride ions to elemental chlo- energy consumption of the electro-oxidation process.
 R. C. Villas B~as / Journal of Geochemk~l Exploration 58 (1997) 217 222
6. Conclusions
Fhe following conclusions were arrived at:
1. Avoiding the use of mercury at the gravimetric
separation stage is possible without diminishing
gold recovery.
2. Introduction of retorts in the amalgamation pro-
cess improved it and was well accepted by the
garimpeiros (small scale miners).
3. Instaling of fume hoods in gold shops proved to
be very efficient in decreasing the overall mer-
cury content in the air.
4, Confinement of processed material in ponds origi-
nating from the amalgamation stage, was adopted.
5, Recovery of mercury, via electro-oxidation seems
to be a clean alternative in small-scale operations.
6. Projects as described in this article are as success-
ful as long as solutions depend on consent, since
in remote regions laws are impossible to enforce.
Acknowledgements
The Conselho Nacional de Desenvolvimento
Cientffico e Tecnol6gico, CNPq/Brasil is thanked
for partial financial support of this project in the
Amazon region. The manuscript benefited greatly
from the comments and suggestions of two anony-
mous referees and of Dr. Rod Allan who very pa-
tiently translated the original article into readable
English.
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