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Mercury from mineral deposits and potential environmental impact

Article  in  Environmental Geology · January 2003

DOI: 10.1007/s00254-002-0629-5

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 Original article

Mercury from mineral deposits

and potential environmental impact
James J. Rytuba

of the world’s production has come from just five mercury

Abstract Mercury deposits are globally distributed mineral belts. With the increasing recognition of envi-
in 26 mercury mineral belts. Three types of mercury ronmental problems associated with the use and release of
deposits occur in these belts: silica–carbonate, mercury from industrial and mining processes, production
hot-spring, and Almaden. Mercury is also produced from mercury deposits has steadily decreased since the
as a by-product from several types of gold–silver early 1980s. As a result of lower demand and prices, most
and massive sulfide deposits, which account for 5% of the largest mercury deposits are closed or continue to
of the world’s production. Other types of mineral have limited production. However, mercury continues to
deposits can be enriched in mercury and mercury be produced as a by-product from other ore deposit types,
phases present are dependent on deposit type. principally from several types of gold–silver and massive
During processing of mercury ores, secondary sulfide deposits. With the continuing effort to limit the
mercury phases form and accumulate in mine release of mercury to the global atmospheric mercury pool
wastes. These phases are more soluble than cinna- and aquatic environments, by-product mercury produc-
bar, the primary ore mineral, and cause mercury tion from several ore deposit types that are enriched in
deposits to impact the environment more so than mercury is likely to increase in the future. This by-product
other types of ore deposits enriched in mercury. source of mercury is likely to become increasingly im-
Release and transport of mercury from mine wastes portant as the production from primary mercury deposits
occur primarily as mercury-enriched particles and continues to decrease.
colloids. Production from mercury deposits has This paper reviews the distribution, production, and
decreased because of environmental concerns, mercury speciation of ore deposit types that contain sig-
but by-product production from other mercury- nificant mercury concentration and discusses the relative
enriched mineral deposits remains important. importance of these deposits for producing by-product
mercury. The geochemical processes that contribute to
Keywords Environmental impact Æ Mercury Æ environmental problems associated with mercury deposits
Mining is reviewed and used to evaluate the potential environ-
mental impact of mercury-enriched ores for which more
limited information is available. Several authors have
reviewed the environmental impact of mercury introduced
Introduction during the amalgamation process in the recovery of gold
and silver, most recently by Hylander (2001). Although
Mercury has primarily been produced from mercury- both placer and lode gold deposits are a significant
bearing ores in which mercury is the primary and often source of mercury to the environment, this paper
only ore metal constituent. The total world production of focuses on ore deposits in which mercury is a natural
20 million flasks (a flask equals 34.474 kg) of mercury has component and has not been introduced during ore
largely come from such deposits and nearly three quarters processing.

Received: 29 October 2001 / Accepted: 6 May 2002 Mercury deposits and mineral belts
Published online: 2 August 2002
ª Springer-Verlag 2002 Mercury deposits are globally distributed in several mer-
cury mineral belts that are composed of mercury deposits,
occurrences, and areas of altered country rock that contain
J.J. Rytuba elevated concentrations of mercury (Fig. 1). Within each
US Geological Survey, 345 Middlefield Road,
Menlo Park, CA 94025, USA mineral belt the mercury deposits are co-genetic and
E-mail: jrytuba@usgs.gov reflect similar tectonic and volcanic processes that
Tel.: +1-650-3295418 contributed to the concentration of mercury. For example,
Fax: +1-650-3295373 the California Coast Range mercury mineral belt formed

326 Environmental Geology (2003) 43:326–338 DOI 10.1007/s00254-002-0629-5

 Fig. 1
The distribution of mercury mineral belts with significant mercury production (in red) occur in a relatively few areas of the globe. Three-fourths of the global mercury production has
come from five mercury mineral belts (listed in decreasing mercury production): Almaden, Idrija, Amiata (1), Huancavelica (2), and the California Coast Range (3), which contains the
New Almaden and New Idria deposits. Modified from Bailey and others (1973)

Environmental Geology (2003) 43:326–338

Original article

327
 Original article

along a plate boundary as the boundary changed from a type deposits, and this deposit type is well developed in the
convergent to a transform boundary. An increase in the California Coast Range mercury mineral belt (Fig. 2)
regional thermal anomaly associated with this tectonic where two of the largest deposits of this type are localized,
transition started in the Miocene and resulted in the de- New Almaden and New Idria. Silica-carbonate type de-
velopment of silica–carbonate-type mercury deposits early posits are associated with serpentinite that has been al-
in the evolution of the thermal anomaly, and hot-spring- tered to an assemblage of silicate and carbonate minerals.
type mercury deposits during its waning phase (Rytuba The serpentinite was commonly emplaced along fault
1996). Fifty-one mercury deposits that have individually zones where its relative impermeability serves to localize
produced more than 1,000 flasks of mercury are distrib- carbon dioxide-rich fluids from which the mercury de-
uted along the 400-km length of this mineral belt. Al- posits formed. The mercury ores are hosted in silica–car-
though there are two distinct types of mercury deposits in bonate-altered serpentinite and adjacent sedimentary
the mineral belt, the deposits are genetically related to the rocks.
same regional tectonic and volcanic processes associated Hot-spring-type mercury deposits occur in most of the
with development of a transform plate boundary. world’s mercury mineral belts and these deposits comprise
The mercury deposits adjacent to the Mediterranean Basin most of the deposits in the Great Basin belt including
are not all co-genetic (Fig. 1), but rather consist of mer- McDermitt, the largest of this type (Fig. 2). This deposit
cury belts that are small in aerial extent, and are formed at type can be spatially associated with silica–carbonate type
different times and in different geologic settings. The most deposits where it may overprint the earlier formed silica–
important of these is the Almaden mercury mineral belt in carbonate mercury ores. Hot-spring-type deposits formed
central Spain where over one-third of the world’s mercury in near-surface environments where meteoric-dominated
has been produced (Saupé 1990). This mineral belt con- geothermal systems developed in and adjacent to inter-
sists of 11 mercury deposits located within a small area mediate to felsic volcanic centers (Cox and Singer 1986;
with dimensions of 10·20 km. The mercury ore bodies Rytuba 1996). Mercury ores are hosted in hot-spring sinter
have extremely high grades, up to several weight percent and associated sedimentary and volcanic rocks that have
mercury, mostly as cinnabar, but elemental mercury is been silicified and altered to a clay alteration assemblage.
present in all the deposits and is an important ore mineral Many of the hot-spring-type mercury deposits are geo-
in the Las Cuevas deposit. logically young and thermal fluids are often associated
In North America there are ten mercury mineral belts with these deposits, some of which are still actively
(Fig. 2). The California Coast Range and Great Basin depositing mercury and iron sulfides.
mercury mineral belts have accounted for more than Cinnabar is the main ore mineral in each of the three
three-fourths of the mercury production in North Ameri- mercury deposit types with only a few exceptions. These
ca. Mercury continues to be produced in the California exceptions include elemental mercury as the primary ore
and Great Basin belts as a by-product from gold–silver in some Almaden-type and silica–carbonate-type deposits;
deposits genetically associated with some of the mercury mercury sulfates and chlorides predominating in some
deposits, and from sediment-hosted gold deposits. In silica–carbonate deposits; and corderoite (Hg3S2Cl2), sch-
North America, only the mercury mineral belts in Mexico wartzite [(HgCuFe)12Sb4S13], and livingstonite (HgSb4S7)
continue to produce mercury from mercury deposits. as the dominant mercury minerals in some hot-spring-
Mexico also produces mercury from the reprocessing of type deposits.
precious metal mine tailings where mercury was used in
the amalgamation process to recover gold and silver, such Mineral deposits enriched in mercury
as in the Zacatecas area. The presence of anomalous concentrations of mercury in
many types of mineral deposits has long been recognized
and used in the geochemical exploration for these ores (Rose
Mercury deposit types and others 1979). Mercury geochemical dispersion patterns
Three types of mercury deposits can occur in mercury in sediments, soils, and air have been successfully used to
mineral belts: Almaden type, silica–carbonate type, and find mineral deposits, including several types of large gold
hot-spring type. The Almaden-type primarily occurs in the and base metal deposits (McCarthy 1972; Sillitoe 1995). In
Almaden mercury mineral belt in central Spain (Fig. 1), some of these mineral deposits, the mercury content has
and only a small number of Almaden-type deposits occur been sufficiently high to permit recovery of mercury as a by-
outside this belt. These deposits are primarily localized in product (Table 1). The mineral deposit types discussed in
Silurian quartzite adjacent to submarine mafic craters b
(Hernandez 1985). One of these deposits, Las Cuevas, is
localized within a submarine caldera and some of the Fig. 2
smaller deposits are localized in mafic dikes that are as- Distribution of mercury mineral belts in North America. Production
of mercury from silica–carbonate type mercury deposits has
sociated with these mafic volcanic centers (Rytuba and accounted for more than half of the 4 million flasks of total
others 1988). These deposits are representative of the Al- production from North America. Two of the largest deposits of this
maden type of mercury deposit (Cox and Singer 1986). type, New Almaden (A) and New Idria (B), occur in the California
Silica-carbonate type deposits are more widely distributed Coast Range mercury mineral belt. Hot-spring-type mercury deposits,
in the world’s mercury mineral belts. In North America, such as McDermitt (C) are the most common deposit type in the other
mercury mineral belts. Mercury occurrence (yellow) represents a
the largest production has come from the silica–carbonate single mercury deposit

328 Environmental Geology (2003) 43:326–338

 Original article

this study are those defined in Cox and Singer (1986), Bliss types: volcanogenic massive sulfide (VMS), sedimentary
(1992), and Mosier and Page (1988). Significant by-product exhalative (sedex), hot-spring gold–silver, Comstock epi-
mercury has been produced from the following deposit thermal gold–silver vein, quartz–alunite gold (high sulfi-

Environmental Geology (2003) 43:326–338 329

 Original article
Table 1
Mineral deposits enriched in Mineral deposit type
mercury and mercury phases
Mineral deposits that have produced
present
by-product mercury
Volcanogenic massive sulfide
Sedimentary exhalitive (sedex) deposits
Polymetallic base metal
Hot-spring gold
Comstock gold–silver
High sulfidation gold–silver
Sediment-hosted gold
Antimony–mercury
No by-product mercury production
Antimony
MVT
Volcanogenic manganese
Basaltic copper
Volcanogenic uranium
Bedded barite
Low sulfide gold–quartz vein
Porphyry copper
dation gold–silver), sediment-hosted gold, antimony–mer-
cury, and polymetallic replacement and vein deposits. The
largest by-product production has and continues to come
from VMS and sedex deposits, especially those deposits that
are enriched in zinc. The 27 major massive sulfide and 62
sedex deposits and mineral belts in the world are more
numerous and widely distributed than the mercury deposit
mineral belts (Fig. 3). Total mercury production from some
of the more mercury-enriched VMS deposits, such as Bol-
iden and others deposits in the Skellefte district, Sweden,
and sedex deposits, such as Balmat, New York, (Fig. 3) has
been comparable to that from moderate size mercury de-
posits of the hot-spring and silica–carbonate type. Although
simple and disseminated antimony deposits typically have
not produced by-product mercury, several antimony de-
posits in Tajikistan, the largest being Dhizhikrut, have and
continue to produce mercury as a by-product. A new hydro-
metallurgic processing of antimony–mercury concentrates
at the Isfara plant, Tajikistan, generates both electrolytic
antimony and mercury.
Other mineral deposit types contain elevated concentra-
tions of mercury, greater than 10 lg/g, but, to date, these
have not been a significant source of by-product mercury
(Table 1). These deposit types include Mississippi Valley
type (MVT), volcanogenic manganese, basaltic copper,
volcanogenic uranium; simple antimony, porphyry cop-
per, low-sulfide-gold-quartz, and bedded barite deposits.
Among these deposits, the highest mercury concentration
occurs in disseminated and simple antimony deposits and
the Tajik antimony deposit. However, all of these deposit
types can potentially contain sufficient mercury to be of
environmental concern during the processing of ores and
disposal of mine wastes.
The geologic and geochemical processes that form a par-
ticular type of mineral deposit also concentrate mercury in
phases that are specific to that mineral deposit type. As a
result, the mercury-containing phases present in ores
enriched in mercury are dependent on the type of mineral
330 Environmental Geology (2003) 43:326–338
Mercury phase and speciation
Hg solid solution in sphalerite (ZnS)
Hg solid solution in sphalerite (ZnS)
and cinnabar (rarely)
Hg solid solution in sphalerite (ZnS) and cinnabar
Cinnabar, Hgo, corderoite (Hg3S2Cl2)
Cinnabar, corderoite
Cinnabar
Cinnabar, Hg in pyrite, As–Sb sulfides
Cinnabar
Hg solid solution in Sb sulfides, cinnabar
Hg solid solution in ZnS
Hg adsorbed on Fe–Mn oxides
Hg–Cu amalgam
Cinnabar
Cinnabar
Hg in sulfosalts, Au–Ag amalgam
Cinnabar
deposit (Table 1). Mercury is not evenly distributed
throughout these mineral deposits, but is enriched in parts
of the deposit and commonly concentrated in a particular
mineral phase. In VMS deposits, mercury primarily is
present in solid solution within sphalerite (ZnS), which
can contain up to 41.1 wt% mercury in its structure
(Tauson and Abramovich 1980). The most mercury en-
riched VMS deposits occur in the Skellefte district, Sweden
(Fig. 3) where over 85 deposits are present and commonly
have ores containing from 10 to 340 lg/g of mercury
(Allen and others 1997). Because mercury minerals are
generally not present in VMS deposits, the high mercury
content of these ores has often been overlooked. In other
mineral deposit types that contain sphalerite, such as
sedex and polymetallic replacement and vein deposits,
mercury is also typically present in solid solution within
sphalerite and only rarely as cinnabar (four polymetallic
replacement deposits; Singer and others 1997). As a result
of the close association of mercury with sphalerite in these
deposit types, the mercury content of these sulfide ores is a
function of the amount and mercury enrichment of
sphalerite present. Schwartz (1997) has summarized the
mercury content of zinc-rich ores and concluded that
sedex deposits have the highest mercury content ranging
from 27 to 1,198 lg/g mercury. The mean concentration of
92 VMS deposits is 32 lg/g, but the mercury content is
strongly dependent on the age of deposit with Proterozoic
age deposits having the highest mean mercury content of
196 lg/g (Schwartz 1997). Mercury is not equally distrib-
uted within the zinc-rich ores, but is selectively enriched in
sphalerite deposited during distinct episodes in the
ore-forming process. For example, in the Red Dog, Alaska,
sedex deposit, the mercury content in sphalerite deposited
early in the paragenetic sequence averages several tens of
lg/g whereas late-stage sphalerite averages about 1,000 lg/g
(Kelley and others 2000). Thus, the mercury content of
sulfide concentrates from a particular deposit may vary
considerably as various parts of the deposit are mined. In
 Fig. 3
Distribution of the global volcanogenic massive sulfide (VMS) and sedimentary exhalitive (sedex) mineral belts and recently formed submarine sulfide deposits that are enriched in
mercury (noted by Hg) or have produced by-product mercury (modified from Barrie and Hannington 2000; Sangster 1990)

Environmental Geology (2003) 43:326–338

Original article

331
 Original article
parts of some gold-rich VMS deposits, such as Eskay
Creek, Canada (Fig. 3; Roth and others 2000), mercury is
also present as cinnabar, and more rarely as an amalgam
with gold and silver as in the most mercury-rich deposit in
the Skellefte district, Langsele, in Sweden (Nysten 1986).
Mercury is commonly a trace constituent in several types
of gold–silver deposits. In both hot-spring and quartz–
alunite (high sulfidation) gold–silver deposits, mercury
can be present in mercury phases that are similar to those
present in hot-spring-type mercury deposits, primarily
cinnabar, elemental mercury, and corderoite (Table 1).
However, as in VMS and sedex deposits, mercury is not
equally distributed throughout the gold ores, but is con-
centrated in parts of deposits. For example, at the Crofoot/
Lewis hot-spring-type gold deposit, Nevada, distinct
mercury phases (cinnabar and corderoite) were present
only in the most mercury-enriched part of the deposit and
significant by-product mercury was produced when this
part of the ore deposit was mined. The mercury content
was much lower (0.1–219 lg/g) in the remainder of the
deposit, such that distinct phases of mercury were not
discernable (Ebert and others 1996). In sediment-hosted
gold deposits, such as in the Carlin gold belt, Nevada,
mercury is typically present as a trace constituent aver-
aging 20 lg/g and locally as high as 640 lg/g (Li and
Peters 1999). Distinct mercury-bearing phases are present
and can include cinnabar, pyrite-enriched mercury, and
arsenic and antimony sulfides in which mercury is present
in solid solution.
In ore deposit types that have not produced by-product
mercury, a variety of mercury-bearing phases can be
present and in some of these deposits mercury is present
in solid solution in sulfide ore minerals (Table 1). More
commonly, mercury is distributed throughout the ore
body and not concentrated in a distinct mineral phase. In
antimony deposits, mercury can be present as cinnabar
and in solid solution within the antimony sulfide stibnite.
In the oxidized parts of these ores, cinnabar and corderoite
form as discrete phases within antimony oxides such as
stibiconite and valentinite. In MVT deposits, mercury can
be present in zinc-rich ores where it is present in solid
solution in sphalerite. In manganese deposits, discrete
phases of mercury have rarely been reported (two deposits,
Singer and others 1997) and it is likely that mercury is
sorbed onto iron and manganese oxides. Mercury is
known to form inner sphere complexes with these phases.
In basaltic copper deposits, such as in the Lake Superior
basaltic copper deposits, Michigan, mercury is present as
an amalgam in copper where concentrations range up to
20 lg/g in ores and several hundred lg/g in mine tailings
from stamp mills (Kerfoot and others 2000). Mercury–
gold–silver amalgams have also been reported from
Comstock and hot-spring-type gold deposits as well as low
sulfide gold quartz deposits. In both volcanogenic uranium
and bedded barite deposits, cinnabar is the dominant
mercury mineral present. Porphyry–copper systems typi-
cally do not have elevated mercury contents and only three
porphyry copper deposit are reported to contain cinnabar
(Dizon, Philippines, Andacolla, Chile, Tsagaan-Suvarga,
332 Environmental Geology (2003) 43:326–338
Mongolia; Singer and others 1997). In the Sulphurets,
Canada, porphyry copper contains an unusual association
of mercury with gold–silver telluride phases. The associ-
ation of quartz–alunite-type gold deposits with porphyry
systems indicates that the more volatile mercury species
are depleted in the high temperature porphyry part of the
system and are concentrated in the superjacent, lower
temperature quartz–alunite gold deposits.
Environmental impacts
of mercury-enriched ore deposits
The release of mercury to the environment from mineral
deposits enriched in mercury can impact humans and
biota through direct and indirect pathways. Direct path-
ways include ingestion of tailings and soils contaminated
with mercury and respiration of mercury vapor and
enriched particles. Ingestion is primarily a concern for
children that display pica activity. Indirect pathways that
impact humans are more important and include con-
sumption of fish and, more rarely, edible plants that have
been contaminated with methylmercury that has formed
from biochemical transformation of mercury released
from a mineral deposit.
Mercury may be released from ore deposits in several
ways. Mercury-mineralized areas emit mercury to the
atmosphere that may significantly contribute to the
atmospheric pool of mercury, or be regionally re-deposited
(Gustin and others 2002). Mine wastes and contaminated
soils are a potential source of particulate mercury and
soluble ionic mercury species that can be transported from
the mineralized site and converted to methylmercury in
downstream aquatic environments. At mercury-enriched
ore deposits developed by underground working, acid
mine drainage may be an important source of mercury and
methylmercury. Finally, various ore-processing methods,
such as roasting and smelting of ores, may release mercury
species to the atmosphere.
Studies of mercury emissions to the atmosphere from
mineralized areas have focused on primary mercury
deposits (Ferrara and others 1998) and associated
geothermal areas; consequently, little is known about
emissions from other ore deposit types that are enriched in
mercury. Ferrara and others (1991) have shown that in the
Amiata mercury mineral belt, Italy (Fig. 1), soil degassing
is the main source of mercury release to the atmosphere.
In other large mercury mineralized areas, such as the
New Idria district in California (Fig. 2), most of the
mercury emissions to the atmosphere (up to 90%) come
from mineralized locations with slightly elevated mercury
content (up to 5 lg/g; Coolbaugh and others 2002). About
a tenth of the total emissions comes from mine wastes and
mining-disturbed areas with high mercury content (Gustin
and others 2001). Gustin and others (2001, 2002) have
estimated that emissions from the Great Basin mercury
belt and associated mineralized areas in Nevada are about
a third of the total mercury released by coal-fired power

plants in the US. In these mineralized areas, a significant
amount of mercury can be concentrated in the foliar
portion of plants because plants uptake mercury primarily
through their leaves (Gustin and others 2001). Levels of
mercury up to 9.8 lg/g occur in Pinus and Cytisus growing
in mercury-contaminated soils in the Amiata mercury
mineral belt (Ferrara and others 1991). Inorganic mercury
species predominate in mercury-enriched plants that have
grown in contaminated soils in the southwest Alaska
mercury mineral belt (Bailey and Gray 1997). The leaf
parts contain the highest mercury concentration, up to
970 ng/g, and stems the lowest, 210 ng/g (Bailey and
others 2002). Methylmercury concentrations in leaves can
be significant, up to 11 ng/g, and is species dependent,
with highest values in willow and lowest in alder (Bailey
and others 2002).
Mercury mine wastes consist of several types of material
with varying mercury content and speciation that reflect the
type of mercury ore deposit and processing method used.
Mercury mine sites are typically small in aerial extent and
consist of a furnace and a condensing system. The ores have
been mined by both underground and open pit methods and
were commonly processed in a rotary furnace or retort that
heated mercury sulfide above its stability temperature.
Elemental mercury vapor was released along with sulfur
dioxide and other stack gases and dust, and this vapor was
vented into a condensing system. Condensing systems
consisted of a series of U-shaped pipes in which the mercury
vapor was cooled. Liquid mercury was collected in a water-
cooled basin at the base of each U of the condensing column.
Mercury-enriched dust was also collected in a cyclone prior
to entering the condenser, but considerable dust, termed
condenser soot, collected on the inside surfaces of the
condenser. This material was periodically removed and
reprocessed, or discarded along with the mine tailings,
commonly termed calcines.
Secondary mercury minerals formed from the mercury-
enriched vapor within the furnace or retort, and in the
condensing systems (Kim and others 2000). These min-
erals are very fine grained (micrometer and nanometer
particles) and formed on surfaces of rock fragments within
the furnace (or retort), as well as in the soot within the
condensing system. The speciation of these secondary
mercury phases is distinct from those present in the
primary mercury ores, and typically more soluble.
Metacinnabar, the high-temperature polymorph of mer-
cury sulfide, is the dominant secondary mercury mineral
in calcines derived from silica–carbonate-type mercury
deposits because, during the roasting process, impurities
introduced into the mercury sulfide crystal structure
impede its reversion back to cinnabar upon cooling to
ambient conditions (Kim and others 1998). In calcines
derived from hot-spring-type deposits where chloride is
enriched, secondary mercury phases consist of mercury
chloride minerals, such as corderoite, in addition to
metacinnabar and mercury sulfates and oxides (Kim and
others 2000). In addition to these secondary minerals,
some primary mercury minerals remain in the calcine
because of encapsulation within silicate and carbonate
Original article
minerals. The concentration of mercury in calcines ranges
from 10 to 800 lg/g, with higher concentrations occurring
in calcines generated by retorts, which are inherently more
inefficient than rotary furnaces. The highest concentration
of mercury in mine wastes, up to several weight per cent,
occurs in condenser soot and cyclone dust that has not
been reprocessed. The mercury species in these wastes can
include elemental mercury, metacinnabar, and mercury
sulfates and chlorides (Kim and others 2000). Other mer-
cury mine wastes include waste rock and low-grade ore
with mercury concentrations that range from 100 to
1,500 lg/g, and mercury phases similar to that present in
the primary ore. Mercury retorts and furnace operations
released significant mercury vapor and dust that accu-
mulated in soils, with concentrations of up to 30 lg/g
mercury occurring in surface soils. At very long-lived
mines, such as Almaden, Spain, mercury concentrations in
soil can be as high as several hundred lg/g . The speciation
of mercury in these soils is likely to be similar to that
found in condenser soot. Soil profiles developed on
serpentinite and clastic sedimentary rocks indicate that
mercury species deposited on the soil surface by stack
gases have been dissolved and transported downward such
that anomalous mercury values extend to depths of about
50 cm (Rytuba 2002).
In temperate climates where the source of mass loading is
from mercury mine wastes, transport of mercury from
mine sites occurs primarily in the particulate form, and
most of the mercury flux occurs during peak flow events
(Ferrara and others 1991; Whyte and Kirchner 1999). In
arid climates, however, the transport of mercury from
mine sites is limited and watersheds are not usually im-
pacted at distances greater than 1 km from the mine (Gray
and others 1999). Mercury mine wastes deposited adjacent
to streams were removed by flood events, thus providing
renewed space for continuous mine waste disposal during
the life of the mine. The release of mercury from mine
wastes is dependent on particle size because mercury
concentration in calcines increases with decreasing parti-
cle size such that the fine-grained fraction of calcines may
have twice the mercury concentration of the coarsest
fraction (Lowry and others 2001; Shaw and others 2001).
Colloidal transport of mercury from mine wastes is an
important transport mechanism. Laboratory-column
leaching experiments of calcines indicate that mercury-
bearing (>2 lg/g) colloids in the 50–400-nm size range
consist of crystalline alunite–jarosite, hematite, and an
amorphous silica–aluminum phase (Lowry and others
2001; Shaw and others 2001). Mercury is not present as
sorbed species, but as colloidal size particles of cinnabar,
metacinnabar, montroydite, and mercuric chloride (Kim
and others 2001). These fine-grained mine wastes and
mercury-bearing colloids can contaminate stream sedi-
ments and overbank deposits with mercury (up to
1,500 lg/g) for great distances downstream from mine
sites (Gray and others 2000; Rytuba 2000). Downstream
from the Idrija mine in Slovenia (Fig. 1), the world’s sec-
ond-most productive mercury mineral belt, sediments in
the River Soca and in the Gulf of Trieste are contaminated
Environmental Geology (2003) 43:326–338 333
 Original article
with inorganic mercury more than 50 km from the mine
area (Horvat and others 1999). Sediments contaminated
with tailings are a concern because they are a source of
ionic mercury that can become methylated in downstream
aquatic environments. For example, inorganic mercury
phases in mine tailings from the Idrija mine introduced
into Gulf of Trieste contribute to methylation of
mercury in bottom seawater sediments (Horvat and
others 1999).
Mercury and methylmercury in mine drainage
Mine drainage may be an important source of mercury and
methylmercury from mercury-enriched ores that have been
mined primarily by underground mining methods. The
concentration of mercury and methylmercury in mine
drainage is dependent on the type of ore deposit associated
with the drainage, and whether the mine drainage has re-
acted with mine wastes. The reaction of mine drainage with
mine wastes increases the concentration of both mercury
and methylmercury in mine drainage and is an important
process that controls the release and transport of both
mercury species from mine sites (Rytuba 2000). The highest
mercury concentration, up to 300,000 ng/l, occurs in mine
drainage that has reacted with mine wastes from silica–
carbonate-type mercury deposits (Fig. 4 population I) and
exceeds the 12-ng/l USEPA aquatic life criteria. Mercury is
primarily present in the filtered fraction of mine drainage as
particles less than 0.45 lm, indicating that colloids and
dissolved mercury species leached from the mine wastes
predominate in the water. In contrast, mercury concentra-
tions are considerably lower in mine drainage at the point of
discharge from underground mine workings where the
drainage has not reacted with mine wastes (Fig. 4 field II).
The total mercury concentration has a similar range in
values for both silica–carbonate and hot-spring-type
deposit. Mercury can be present as dissolved species and
colloids (particles <0.45 lm), or as a particulate phase with
size greater than 0.45 lm. Mine drainage from low-sulfide–
gold–quartz vein deposits have relatively low concentra-
tions of mercury because of the low concentration of
mercury in this deposit type (Ashley 2002). Mine drainage
from volcanogenic massive sulfide deposits has very low
concentrations of mercury (Fig. 4, field IV) even though the
mercury concentration of these ores is higher than that in
low-sulfide gold-quartz ores. Mine drainage from these
deposits is typically associated with large amounts of iron
oxyhydroxide because of the high iron sulfide content of the
ores. Adsorption of mercury onto iron oxyhydroxide is
effective in removing mercury and methylmercury species
from mine drainage (Rytuba 2000) and thus mercury
accumulates in the iron-rich sediment. An example of this
process occurs in the Tinto and Odiel rivers that are im-
pacted by acid mine drainage from massive sulfide deposits
in the Iberian Pyrite Belt, Spain, the largest massive sulfide
deposit mineral belt in the world (Fig. 3). These rivers have
low pH (2.5–3.0), a sediment bedload dominated by iron
oxyhydroxide, and an elevated particulate mercury con-
centration of up to 330 nmol/g, which is associated with the
abundant iron oxyhydroxide (Cossa and others 2001).
334 Environmental Geology (2003) 43:326–338
Saturation of mine waste with mine drainage enhances
mercury methylation because the dissolution of soluble
mercury phases in mine wastes and the addition of sulfate
provides a favorable environment for sulfate-reducing
bacteria to methylate mercury. Similarly, saturation of
mercury-contaminated soils at mine sites provides a
favorable environment for methylation of mercury (Hines
and others 1999). Methylmercury concentration is highest
in mine drainage water that has reacted with mine wastes
from silica–carbonate-type mercury deposits, ranging
from 1.5 to 75 ng/l (Fig. 5, field I) and constitutes less than
about 0.1% of the total mercury concentration in the wa-
ter. Methylmercury concentration is considerably lower in
mine drainage water at the point of discharge from un-
derground mine workings for both hot-spring and silica–
carbonate-type mercury deposits (Fig. 5, field II). Mine
drainage from low-sulfide gold and VMS deposits that
have not reacted with mine wastes have low concentrations
of methylmercury, with methylmercury constituting about
1% or less of the total mercury concentration. Methyl-
mercury concentration in mine drainage is highest in
unfiltered water samples indicating that transport of
methylmercury from mercury mine sites is predominantly
in particulate phases where methylmercury is sorbed onto
iron oxyhydroxide phases (Rytuba 2000).
By-product mercury production and potential
environmental impact
Mercury recovered from various types of massive sulfide
deposits during the roasting of zinc ores and the smelting of
copper and lead ores accounts for most of the world’s
by-product mercury production. In 1999, the 80 metric tons
(t) of by-product mercury produced from these sources
accounted for about 5% of the world’s 1,800 t of mine
production (Reese 1999). Most of this production came
from base metal concentrates processed in Finland, but
mined from massive sulfide deposits in Sweden. Although
mercury is lost to dust containing mercury-enriched
sphalerite during the crushing and grinding of various types
of massive sulfide ores, most mercury is retained in the base
metal concentrates. In zinc roasters, mercury is removed
from mercury-enriched gases by washing with sulfuric acid,
mixing the mercury-enriched residue with lime, and then
heating in a furnace (Mukherjee and others 2002). However,
some mercury is still released to the atmosphere from zinc
roasters, with up to 5 g of mercury released per ton of zinc
produced. Before 1975, smelting of copper concentrates
in reverberatory furnaces typically resulted in partitioning
of up to 56% of the mercury into copper concentrates, and
the remainder into dust, fly ash, slag, and other wastes
(Jasinski 1994). In the more efficient flash furnaces currently
used, mercury is recovered in the sulfuric acid plant and
electrostatic precipitator and less than 1 g of mercury per
ton of copper is emitted to the atmosphere (Jasinski 1994;
Mukherjee and others 2002). In the past, the smelting
of massive sulfide ores often did not recognize the high
mercury contents of some of these ore concentrates
because mercury was not present as a distinct phase, but
rather in sphalerite. As a result, mercury species were

released with stack gases resulting in contamination of
soils with elemental mercury and other mercury species
sorbed onto particulates. Prior to 1906, zinc was not
recovered from massive sulfide deposits and, thus, waste
rock enriched in mercury within sphalerite may be a poten-
tial source of mercury contamination at these mine sites.
Although individual gold–silver ore deposits generally
produce less than a metric ton of mercury per year, the
variable content of mercury in these ores can result in much
higher by-product mercury when the mercury-rich portions
Original article
Fig. 4
Plot of concentration of total and filtered mercury in
mine drainage as a function of type of mineral
deposit. Highest total mercury concentration occurs
in mine drainage that has reacted with mine wastes
from silica–carbonate type mercury deposits (field I)
and mercury is present primarily as particles
<0.45 lm. Field II consists of mine drainage that has
not reacted with mercury mine wastes. Field III
consists of mine drainage from low-sulfide gold
quartz deposits (Ashley 2002) and field IV is from
massive sulfide deposits
Fig. 5
Plot of concentration of total methylmercury and
mercury in mine drainage as a function of type of
mineral deposit. Highest total methylmercury con-
centration occurs in mine drainage that has reacted
with mine wastes from silica–carbonate type mercury
deposits (field I) and methylmercury constitutes less
than 0.1% of the total mercury present in the water.
Field II consists of mine drainage that has not reacted
with mercury mine wastes, field III is mine drainage
from low-sulfide gold–quartz deposits (Ashley 2002),
and field IV is mine drainage from massive sulfide
deposits
of these ore bodies are mined and processed. This is
especially true for Comstock gold–silver and hot-spring-
type gold deposits that are geologically similar to hot-
spring-type mercury deposits. For instance, the Crofoot/
Lewis gold deposit, Nevada, produced over 20 metric tons
(t) of mercury per year when the mercury-enriched parts of
the ore body was mined. Total by-product mercury pro-
duction from gold–silver deposits in Nevada, one of the
world’s major precious metal producing areas, was 13 t in
1999 and is estimated to increase to 18 t in 2000.
Environmental Geology (2003) 43:326–338 335
 Original article

In gold–silver deposits where cyanide solution is used to generates fine-grained secondary mercury phases during
recover precious metals, leached mercury forms com- the roasting and condensing process. These phases are
plexes with cyanide and various methods are used to concentrated in mine wastes, such as calcines, condenser
precipitate mercury from the leach solution. In deposits soot, and contaminated soils, and are released and trans-
where gold is associated with iron-sulfide minerals and not ported from mine sites as mercury-enriched particles and
amenable to direct cyanide leaching, the ore is pretreated colloids. At mercury mines impacted by mine drainage,
by heating in an autoclave or roaster to oxidize the ore. At these wastes may also be a source of methylmercury where
modern gold mines, mercury liberated during this pre- mine drainage saturates and reacts with mine wastes. The
treatment phase is captured using wet scrubbers, reported secondary mercury phases in mercury mine wastes are
to a sulfuric acid plant or mercury-removal plant, and more soluble than the primary ore mineral, cinnabar, and in
captured on carbon filters (van Zyl and Eurick 2000). aquatic environments mercury-enriched particles, and
Elemental mercury is recovered from leach solutions using colloids can release ionic mercury that can be methylated by
electrowinning precipitation on metal cathodes followed sulfate-reducing bacteria. Methylmercury can become in-
by heating of the metal-bearing sludge from the cathodes corporated into organisms in the lower part of the food
and condensing of mercury vapor (van Zyl and Eurick chain and become highly concentrated in biota in the upper
2000). Some mercury is released to the atmosphere during part of the food chain through the process of
each of these processes, but the resulting gold mine tailing bioaccumulation.
liquids and solids have relatively low concentrations of In mineral deposits where mercury is not the primary ore
mercury. At gold mines using the heap leach process, the mineral, mercury-enriched ores are processed by methods
cyanide solution can become enriched in mercury, and that typically do not generate large amounts of secondary
mercury can be removed from the cyanide solution and mercury phases in the mine wastes. In these deposits,
fixed in the waste rock of the heap as an organic sulfide mercury is released primarily in stack gases during the
(Wickens 2000). At older mines where mercury was not roasting or smelting of massive sulfide ores, or during the
recovered, soils may be contaminated with mercury spe- refining of gold–silver ores. At older mineral-processing
cies, primarily elemental mercury, released during the sites and in countries with limited regulations on mercury
refining process, and waste rock may contain significant emissions, mercury has and continues to be released to the
concentrations of mercury, primarily as cinnabar. atmosphere with other stack gases and accumulates in soils
Other ore deposit types that have not produced by-product downwind from smelter sites. These soils are a potentially
mercury may also have a significant impact on the envi- significant source of mercury-enriched particles, especially
ronment. In a notable example, mercury-enriched mine in areas where smelters have processed ores from VMS and
tailings generated from stamp mills that processed basaltic sedex deposits enriched in mercury for long periods of time.
copper ores were released into Lake Superior, Michigan, At historic VMS and sedex deposits, mine wastes can con-
resulting in contamination of near-shore sediments and tain significant concentrations of mercury, primarily within
generation of methylmercury (Kerfoot and others 2000). sphalerite because zinc ores were not processed, but, rather,
Other deposit types that may release mercury-enriched were discarded with other mine wastes. The processing of
mine tailings include manganese, barite, and antimony other types of ores enriched in mercury, such as basaltic
deposits. Although phosphate deposits have low mercury copper, has generated mine tailings with mercury species
concentrations, the gypsum waste rock (phosphogypsum) similar to that in the primary ore and these tailings can have
produced during processing of these ores may be enriched significant impact on the environment.
in mercury. This waste rock can contain up to 22.7 nmol/g In the past 5 years, primary world production of mercury
mercury and has been shown to be a significant source of has decreased to 56% of the amount produced in 1995, but
soluble mercury that impacts the Tinto River, Spain (Cossa by-product mercury production has slightly increased. Al-
and others 2001). though mercury is present in several mineral deposit types,
most mercury by-product production has and continues to
come from several types of massive sulfide deposits. With
the continuing concern about mercury in the environment
Conclusions and imposition of more restrictive regulations on the release
of mercury, more by-product mercury will likely be
Mercury is present in several types of ore deposit at con- produced from massive sulfide deposits as well as several
centrations sufficient to make many of these ore deposits a types of gold deposits. Thus, while the world’s primary
potentially significant source of mercury to the environ- mercury production will continue to decrease from mercury
ment. The speciation of mercury in these ores, and the deposits because of environmental concerns, by-product
method of ore-processing used, are important factors that mercury will continue to become an increasingly more
control the amount and type of mercury species released, important source of primary mercury for similar
and their potential impact on the environment. Ores from environmental reasons.
mercury deposits contain the highest mercury concentra-
tion, but ores from several types of gold–silver and massive Acknowledgements Collaboration with Dr. Gordon Brown,
sulfide deposits can also be highly enriched in mercury. Dr. Chris Kim, Dr. Sam Shaw, and Dr. Greg Lowry at Stanford
Mercury deposits have a high potential to impact the University and Dr. Mae Gustin at the Desert Research Institute as
environment because the processing of mercury ores part of a USEPA Star research grant has provided a context for

336 Environmental Geology (2003) 43:326–338

 Original article

the development of many of the ideas presented in this paper. I environments, vol 1. USEPA Office of Research and
wish to thank Boris Kotlyar for his assistance with this manu- Development, Washington, DC
script and two USGS reviewers, Don Singer and Randy Koski, for Gustin MS, Coolbaugh MF, Engle M, Fitzgerald B, Keislar R,
their constructive comments. Lindberg S, Nacht D, Quashnick J, Rytuba, JJ, Sladek C, Zhang
H, Zehner R (2002) Atmospheric mercury emissions from mine
wastes and surrounding geologically enriched terrains. Environ
Geol (in press). DOI 10.1007/s00254-002-0630-z
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