13.

16 Silver Vein Deposits

SA Kissin, Lakehead University, Thunder Bay, ON, Canada
H Mango, Castleton State College, Castleton, VT, USA
ã 2014 Elsevier Ltd. All rights reserved.

13.16.1 Introduction 425

13.16.2 Silver–Lead–Zinc Veins 425
13.16.2.1 Cordilleran Vein Type Deposits 425
13.16.2.2 Silver–Lead–Zinc Veins in Clastic Metasedimentary Terranes 426
13.16.3 Five-Element (Ag–Ni–Co–As–Bi) Veins 426
13.16.4 Epithermal Ag–Au and Ag–Base Metal Veins 428
13.16.4.1 Low-Sulfidation Epithermal Deposits 428
13.16.4.2 High-Sulfidation Epithermal Deposits 429
13.16.5 Silver-Bearing Veins Related to Tin Mineralization 430
13.16.6 Silver-Bearing Veins Related to Skarn Mineralization 430
13.16.7 Discussion 430
Acknowledgments 431
References 431

Glossary Hydrothermal Pertaining to hot water or an aqueous

Discordant Lacking conformity to bedding or structure.
Epigenetic In relation to ore deposits, a deposit formed later
than the enclosing rock.
Epithermal Pertaining to a hydrothermal deposit formed at
shallow depth, less than 1 km, and low temperature.
solution, or to the products precipitated from such a solution.
Hypothermal Pertaining to a hydrothermal deposit formed at
depth and temperatures generally in the range of 300–500
C
Manto A flat lying ore deposit, frequently formed by
replacement of carbonate host rock.

13.16.1 Introduction 13.16.2 Silver–Lead–Zinc Veins

Silver vein deposits are considered here as discordant, epigenetic
veins generally formed by open-space filling. This discussion is
restricted to those deposits in which silver is the principal com-
modity or a coproduct in polymetallic deposits. The source of
metal-bearing solutions is considered by Heinrich and Candela
(see Chapter 13.1). All deposits considered are of hydrothermal
origin, although the source of the solution may be magmatic or
nonmagmatic. In several cases, the source of the hydrothermal
solution is unknown or of controversial origin. Processes of trans-
port and deposition in hydrothermal solutions are considered
elsewhere in this volume (see Chapter 13.2).
The types of deposits considered are as follows:
1. Silver–lead–zinc veins
(a) Cordilleran-type vein deposits
(b) Silver–lead–zinc veins in clastic metasedimentary
terranes
2. Five-element (Ag–Ni–Co–As–Bi) veins
3. Epithermal silver–gold and silver–base metal deposits
(a) Low-sulfidation epithermal deposits
(b) High-sulfidation epithermal deposits
4. Silver-bearing veins related to tin mineralization
5. Silver-bearing veins related to skarn mineralization
Silver accompanied by galena, sphalerite, and chalcopyrite,
usually with abundant pyrite, occurs in veins of various types.
Classification may be difficult and some deposits may perhaps
be classified in more than one category. An example are the
ores of Butte, Montana, which were originally exploited as
hydrothermal veins (Loughlin and Behre, 1933), later as por-
phyry copper deposits. Similarly, some deposits consist of
veins associated with carbonate-replacement mantos. There
are two categories that are distinct types.
13.16.2.1 Cordilleran Vein Type Deposits
These are grouped within the more general grouping of
Cordilleran-type deposits that includes porphyry style deposits,
carbonate-replacement mantos and epithermal gold–silver de-
posits (Sawkins, 1972). Examples of Cordilleran vein type
deposits include the Magma Mine, Arizona; Tintic Mine, Utah;
and Casapalca and Cerro de Pasco, Peru. The source of the ores
in most instances has been attributed to a magmatic-
hydrothermal solution, although an appropriate, genetically re-
lated igneous intrusion is not apparent in some cases. Typical
ores contain pyrite, chalcopyrite, sphalerite, galena, and
tetrahedrite–tennantite series minerals. Silver occurs as the

Treatise on Geochemistry 2nd Edition http://dx.doi.org/10.1016/B978-0-08-095975-7.01118-9 425

426 Silver Vein Deposits
silver-rich member of the tetrahedrite–tennantite series, freiber-
gite, as well as some other sulfosalts. The deposits are notably
copper-rich but produce significant coproduct silver. Often pre-
sent are minerals suggesting a high temperature, magmatic origin
such as huebnerite and arsenopyrite (Guilbert and Park, 1986).
Casapalca is an example of the characteristics of this type of
ore deposit in that it has been studied in detail by Rye and
Sawkins (1974). They determined that ore deposition occurred
in three stages: (1) main sulfide stage characterized by simple
sulfide minerals and quartz, (2) late sulfide-sulfosalt stage
and (3) postore calcite stage. Fluid inclusions from the main
sulfide stage yielded homogenization temperatures, uncor-
rected for pressure, of 370 to 320
C, in the sulfide-sulfosalt
stage 320 to 280
C, and 300 to 200
C in the postore
calcite stage. Salinities were found to vary irregularly from 40
to 4 equivalent wt% NaCl in the main stage, but decreased to
12 to 4 equivalent wt% NaCl in postore calcite.
Sulfur isotopic compositions of sulfides and sulfosalts range
from d34S ¼  2.4 to þ2.4%; however, sulfide minerals appear
to have been in isotopic equilibrium. Temperatures calculated
from galena–sphalerite fractionation factors yielded 325–
310
C, in good agreement with fluid inclusion data from the
sphalerite, ranging from 350 to 320
C. dD in main and late-
stage mineralization is in the range 48 to 60%, with
d18O ¼  þ 7. The ore-depositing solutions are consistent with
derivation from a granitic melt with some modification due to
wall-rock interaction. Postore calcite has dD values consistent
with interaction with local meteoric water.
13.16.2.2 Silver–Lead–Zinc Veins in Clastic
Metasedimentary Terranes
Characteristics of these deposits are based on those given by
Beaudoin and Sangster (1992). They defined this category of
silver deposit based on the lack of an igneous source for the
ore-depositing solutions as well as other shared characteristics.
Examples include Keno Hill, Yukon; Coeur d’Alene district,
Idaho; and Přibram, Czech Republic, excluding uranium-
bearing veins in the latter district. Ores contain galena, sphal-
erite, pyrite, pyrrhotite, chalcopyrite, and a suite of sulfosalt
minerals, most notably tetrahedrite, which is usually the prin-
cipal silver carrier. The veins are hosted in sedimentary seq-
uences and are either remote from igneous intrusions or are
clearly younger than the intrusions that they may cut.
Fluid inclusions yield a wide range of homogenization
temperatures from 170 to 450
C, with modes of 250–
300
C, uncorrected for pressure. Salinities vary from nearly
pure water to as much as 26 equivalent wt% NaCl. The ranges
of homogenization temperatures and salinities suggest mixing
of meteoric water with hypogene fluids. Variable amounts of
CO2 are present and hydrocarbon gases are sometimes present
as well. Boiling or CO2 effervescence occurred in deposits and
has been a factor contributing to ore precipitation.
Sulfur isotopic composition of sulfides displays a wide range
of d34S comparable with the composition of country rock host-
ing the veins. Sulfur appears therefore to have been derived from
country rock sources. Carbon isotopic compositions suggest
derivation from both country rock and deep sources via crustal
faults. Based on its isotopic composition, lead appears to have
generally been derived from country rock sources as well.
Consideration of dD–d18O relationships indicates mixing
of two or three solutions including fluid-displaying composi-
tions indicating high-temperature isotopic exchange with
crustal rocks, possibly under metamorphic conditions; a fluid
with modified d18O but relatively unchanged dD as a result of
interaction with upper crustal rocks; and an essentially mete-
oric fluid. Fluid mixing, and possible boiling, appear to be
processes leading to ore deposition.
13.16.3 Five-Element (Ag–Ni–Co–As–Bi) Veins
This category of silver vein has been called the nickel–cobalt–
native silver type (Bastin, 1939), but more recently the five-
element type (Halls and Stumpfl, 1972). Neither terminology
accounts for the significant occurrence of uranium in some
districts, although it is entirely absent in others. Major examples
include the Cobalt-Gowganda district, Ontario; the Kongsberg
Mine, Norway, and the Batopilas district, Sonora, Mexico, all of
which lack uranium. The Great Bear Lake district, Northwest
Territories, Canada, with subdistricts Echo Bay and Camsell
River, and the Black Hawk Mine, New Mexico, on the other
hand, have been significant uranium producers (Kissin, 1992).
The Great Bear Lake deposits have recently been described as
polymetallic, arsenide-rich epithermal vein systems directly as-
sociated with large IOCG-type magmatic-hydrothermal systems
(Mumin et al., 2007, 2010). Only the Bou Azzer district, Moro-
cco, has had recent production, and there have been relatively
few studies on this type of deposit in recent years.
Based on observations of paragenetic sequences at Great
Bear Lake (Changkakoti et al., 1986a), Cobalt (Petruk, 1971),
Thunder Bay (Kissin and Jennings, 1987) and others, five
distinct stages of mineralization have been recognized:
Stage 1: Early barren stage.
Quartz with minor base metal sulfides (pyrite, sphal-
erite, galena).
Stage 2: Uraninite stage.
Uraninite–quartz with hematite.
Stage 3: Ni–Co arsenide–silver stage.
Native silver in association with Ni–Co arsenide min-
erals (rammelsbergite, safflorite, nickeline,
chloanthite, maucherite). Native bismuth may also
occur at this stage. Gangue is usually calcite or dolo-
mite (Figure 1).
Stage 4: Sulfide stage.
Pyrite, sphalerite, galena, chalcopyrite, and other cop-
per sulfides with native silver and argentite in pre-
dominantly calcite gangue with quartz, fluorite, and
barite. Native arsenic and antimony may occur at this
stage. This stage is transitional from the Ni–Co arse-
nide stage and may contain sulfarsenides such as
arsenopyrite and Sb–As–Ag sulfosalts such as freiber-
gite, pyrargyrite, proustite, and stephanite.
Stage 5: Late stage.
Calcite deposited at low temperature but occasionally
accompanied by significant fluorite or barite.
Within a district, a deposit may lack the Ni–Co arsenide
stage, and the uraninite stage is entirely lacking in some
districts; for example, Cobalt-Gowganda, Kongsberg, and
 Silver Vein Deposits 427

dol sl
rm

Ag

2 cm 0.5 mm
(a) (b)

Figure 1 (a) Polished slab of ore from the Silver Islet Mine, Thunder Bay district, Ontario. At lower right are rosette-textured intergrowths of native
silver and Ni–Co arsenides in darker, fine-grained dolomite. In upper right and center are equant grains of argentite in later, coarse-grained, white
calcite. In upper left are fragments of carbonaceous shale country rock. (b) Silver Islet ore in polished section (reflected light) with rosettes cored
with native silver (Ag) and rimmed with pararammelsbergite (rm). Note that the silver–arsenide intergrowth is separated from later sphalerite (sl) by
dolomite (dol). Reproduced from Kissin SA (1992) Five-element (Ni–Co–As–Ag–Bi) veins. Geoscience Canada 19: 113–124.

Table 1 Fluid inclusion data from five-element veins

Deposit Th (lv)
C Tm (NaCl)
C Tm (ice)
C or Salinity (wt%) Reference

Bou Azzer – 183–240 35 to 47.8 En-Naciri et al. (1997)

Cobalt 100 to 560 193–277 35 to 52 Kerrich et al. (1986),
3 to 26 Marshall et al. (1993)
Great Bear Lake 150–480 – 15–35 wt% Changkakoti et al. (1986a,b)
Thunder Bay 80 to 450 – Kissin and Jennings (1987)
Blackhawk 160–410 2–40 wt% Gerwe (1986)
Wenzel 73–267 – 31.7 to 1.8 Staude et al. (2007)
Kongsberg 250 to 300 – 20–25 wt% Segalstad (2008)

Th (l–v)
C – temperature of homogenization of liquid–vapor inclusions.

Tm (NaCl)
C – temperature of melting (dissolving) of NaCl.
Tm (ice)
C – temperature of melting of ice.

Thunder Bay. Repeated episodes of mineralization have been
documented at Thunder Bay (Kissin and Jennings, 1987) and
Camsell River (Badham, 1975), indicating that deposition was
a long-lived process.
The characteristic paragenetic sequence seems to be the
result of both declining temperature in the course of deposi-
tion and changes in composition of the ore-depositing fluid.
The unusual mineralogical composition of these ores together
with the changing conditions of deposition and of the compo-
sition of the ore solution must necessarily require a particular
geochemistry.
Fluid inclusion studies in various districts (Table 1) com-
monly yield homogenization temperatures that rise rapidly
from stage 1 to stage 2, occasionally reaching 400–500
C,
although in some districts the peak temperatures are in the
300–350
C range. In stage 3 and 4, temperatures declined to
250–150
C, and stage 5 temperatures are invariably below
125
C. In most investigated districts, salinities are high with
daughter minerals present at room temperature. Salinities are
seen to decrease at lower temperatures, suggesting admixture
perhaps with meteoritic fluids. However, deposition in most
districts has occurred in repeated cycles, indicating that the
process has been of long duration that generated solutions
episodically.
Sulfur isotopic studies have produced results that gen-
erally suggest derivation by reduction from seawater sulfate
although, because of the variable isotopic compositions
obtained, there is some disagreement with this hypothesis.
Isotopic compositions range from d34S 9.3 to þ12.2% at
Thunder Bay (Kissin and Jennings, 1987), d34S 22 to þ24%
at Great Bear Lake (Robinson and Badham, 1974) and at
Cobalt, Goodz et al. (1986) found less variation in sulfur
isotopic composition and concluded that the fluid had a com-
position of d34S ¼ þ5 to þ11%. There is an obvious lack of
isotopic equilibrium between sulfide minerals, indicating se-
quential deposition with changing temperature, as well as
possible differing sources of sulfur. Interpretation of oxygen
and hydrogen isotopic data is complicated by the need to
determine the temperature at which the host mineral crystal-
lized. Many conclusions derived from dD–d18O diagrams are
consistent with evolved basinal brines, although in some in-
stances there is overlap with the fields of magmatic or juvenile
water (Figure 2).
Lead isotopes generally lie on a secondary isochron in lead–
lead plots suggesting mixing of sources of lead (Franklin et al.,
1986; Thorpe et al., 1986). Similar results have been obtained
in strontium isotope studies (Changkakoti et al., 1986b;
Kerrich et al., 1986). Both the lead and strontium data
suggest a complex source involving fluid interaction with
wall rocks. Limited studies on carbon isotopes generally
indicate derivation from organic carbon with fractionation to
bicarbonate in solution in a d13C versus d18O diagram
428 Silver Vein Deposits

60 0 Echo Bay (1), (2)

+ Echo Bay (calcite, quartz, nickeline)
-2 Dolomite trend
Thunder Bay (illite)
40
-4
end
20 -6 Calcite tr
Basinal
brines -8

d 13C (‰)
0 *
SMOW -10

-20 Cobalt -12

fluids
-14
dD (‰)

Thunder Bay
-40 fluids Camsell River (1), (2)
-16
Cobalt
-60 -18 Thunder Bay
++
Juvenile water -20
line

+
-80 Echo Bay
++ 0 2 4 6 8 10 12 14 16 18 20 22 24
ter

fluids
wa

d 18O (‰)
ric

-100 +
Figure 3 d13C versus d18O for carbonates associated with five-element
teo

veins. Fields for Echo Bay (1) and Camsell River (1) are from Badham
Me

-120
-140
-20 -10 0 10
d 18O (‰)
Figure 2 dD versus d18O of fluid compositions in five-element vein
deposits as determined by fractionation factors calculated at temperatures
determined by fluid-inclusion studies. Arrows indicate ranges of d18O
where no corresponding dD was determined. Fields for basinal brines
and juvenile water are from Ohmoto (1986). Sources of data: Thunder
Bay (Kissin and Sherlock, 1989), Cobalt (Kerrich et al., 1986), Echo Bay
(Changkakoti et al., 1986a). SMOW, standard mean ocean water.
Reproduced from Kissin SA (1992) Five-element (Ni–Co–As–Ag–Bi) veins.
Geoscience Canada 19: 113–124.
(Figure 2). Data from the Wenzel Mine, Germany, plot in a
field similar to that of the deposits shown in Figure 3, but are
widely scattered and attributed to differing sources of carbon
(Staude et al., 2007).
13.16.4 Epithermal Ag–Au and Ag–Base Metal Veins
Ore deposits that are related to igneous activity account for 60%
of all silver discovered and, of these, a significant amount of
silver is found in clearly defined epithermal veins (Singer,
1995). Lindgren (1922) defined epithermal deposits as being
those formed by ascending hydrothermal solutions at relatively
low temperature and pressure; today, epithermal deposits are
further subclassified based on their ore and gangue mineralogy,
which is a function of their geochemical and physical environ-
ment of formation (see Chapter 13.15). The silver content of
epithermal veins is variable, as is the content of associated gold
and base metals; some epithermal vein deposits have been
historically mined for their silver content, whereas silver is a
by-product of other epithermal deposits. These deposits tend to
form at low temperatures (below 300
C; Simmons et al., 2005),
as determined by fluid inclusion data.
et al. (1972); and for Echo Bay (2) and Camsell River (2) from
Changkakoti et al., 1986a. Data from Cobalt and Thunder Bay are from
Kerrich et al. (1986) and Kissin and Sherlock (1989), respectively. Arrows
indicate the trends of decreasing d18O with increasing temperature in
20
both calcite and dolomite in the Great Bear Lake district (Badham et al.,
1972). Reproduced from Kissin SA (1992) Five-element (Ni–Co–As–Ag–
Bi) veins. Geoscience Canada 19: 113–124.
Deposits of this type are concentrated in convergent tec-
tonic zones, primarily in the circum-Pacific region, and are
associated with calc-alkaline to alkaline magmatism
(Simmons et al., 2005). Because these deposits form within
the upper few kilometers of the Earth’s crust (often less than
1.5 km), epithermal deposits are mostly young (Tertiary and
younger), having not yet been removed by erosion. Epithermal
veins are hosted in contemporaneous volcanic rocks as well as
in underlying basement rocks. A critical feature is the presence
of fractures, fissures, zones of leaching, and other open spaces
in which the ore can precipitate from hydrothermal solutions.
The hydrothermal solutions themselves contain varying pro-
portions of meteoric and magmatic water, as evidenced in
dD versus d18O diagrams, in which data plots on mixing
lines between meteoric water and juvenile magmatic water
(cf. Figure 1). The differing solution compositions contribute
to the differing geochemical characteristics by which the de-
posits are classified (Simmons et al., 2005).
Modern analogs of epithermal vein deposits are found in
regions of volcanic and hot spring activity, and observation of
metal transport and deposition in these active environments
has led to a much greater understanding of how epithermal
deposits form (e.g., Hedenquist and Henley, 1985; Hedenquist
and Lowenstern, 1994).
13.16.4.1 Low-Sulfidation Epithermal Deposits
Low-sulfidation epithermal deposits (the ‘adularia-sericite’
deposits of Heald et al., 1987) are the analog of more distal
geothermal systems with neutral-pH hot springs. These dep-
osits are typically silver-rich, with silver occurring in electrum,

acanthite, sulfosalts such as proustite–pyrargyrite, miargyrite,
pearcite–polybasite, stephanite and argentian tetrahedrite, and
Ag-selenides and tellurides (Camprubı́ et al., 2001; John, 2001;
Simmons et al., 2005). Gangue minerals include quartz, adu-
laria, illite, pyrite, calcite, and rhodocrosite. Silver-rich deposits
of this type can have Ag/Au ratios >100, as well as economic
quantities of lead and zinc. The style of mineralization is very
striking, with crustiform and colliform banding, breccias, lat-
tice textures, and other features indicative of cyclic open-space
filling (Figure 4). Base metal-rich zones can often be found at
depth, with silver–gold-rich mineralization more abundant at
shallower levels.
Examples of low-sulfidation epithermal deposits are num-
erous in Mexico, for example: Guanajuato, Pachuca-Real del
Monte, Fresnillo, Zacatecas, Batopilas, and Tayoltita among
others. In the United States, examples include Midas, Round
Mountain, Tonopah, Tuscarora, and Comstock in Nevada
(e.g., John, 2001; Leavitt et al., 2004) and Creede and Eureka
in Colorado. Other low-sulfidation deposits are found in Peru,
Chile, Australia, New Zealand, and the western Pacific region.
Low-sulfidation deposits form from near-neutral pH, red-
uced, gas-rich hydrothermal fluids. The fluids are dominated
by meteoric water, but a magmatic component may play a
significant role, particularly as a source of metals and ligands
for metal transport in the hydrothermal solutions. d18O shifts
of 10–20% from the meteoric water line, regardless of host
rock type, indicate that the ore-forming fluids must originally
have contained some magmatic water; significant amounts of
H2S in sulfide fluid inclusions also support this interpretation
(Albinson et al., 2001). Silver is transported largely as chloride
or bisulfide complexes. Research at active geothermal systems
(e.g., Simmons and Browne, 2000) indicates that boiling is the
main process by which precious metals are deposited from
hydrothermal solutions. However, clear evidence of boiling at
epithermal deposits can be elusive, and other deposition
mechanisms, such as dilution by influx of meteoric water
(e.g., Tayoltita, Conrad et al., 1992; Guanajuato, Mango et al.,
1991) or rapid decreases in pressure due to sudden fracture
dilation (e.g., Henley and Hughes, 2000; Sibson, 1987), may
dominate the depositional environment. Most recent investiga-
tors include low-sulfidation precious metal deposits within the
family of mineral deposits associated with porphyry-type mag-
matic-hydrothermal systems (Chang et al., 2011; Hedenquist
et al., 2000; Richards, 2009).
15 cm
(a) (b)
Figure 4 (a) Coarse base metal mineralization, mainly chalcopyrite, in
breccia composed of quartz, chalcedony, and altered wall rock. Precious
metal mineralization (silver sulfides and sulfosalts and electrum) is located
in dark gray bands edging quartz and disseminated in base metal
mineralization. (b) Early stage banded ore composed of quartz, chalcedony,
amethyst, and base and precious metal sulfides brecciated and surrounded
by crustiform banded quartz and base and precious metal sulfides.
Silver Vein Deposits 429
Fluid inclusion salinity varies considerably in low-
sulfidation ores, as seen in a study of 52 Mexican deposits.
Albinson et al. (2001) showed that metal ratios correlate with
fluid inclusion salinity, with precious metals deposits contain-
ing 0–7 wt% NaCl equivalent, and base metal-rich deposits
containing up to 23 wt% NaCl equivalent. Salinities are typi-
cally high in inclusions in sphalerite, which may be represen-
tative of other ore minerals (e.g., Mango, et al., 1991). These
data suggest that chloride complexing is important in the
transport of base metals in these deposits.
John (2001) demonstrated that the relative oxidation and
sulfidation state of low-sulfidation Au–Ag deposits in Nevada
depends on the host igneous assemblage. Bimodal basalt–
rhyolite assemblages host ore minerals deposited at lower
oxygen and sulfur fugacities than ores hosted by andesite.
The higher fugacities of the andesite-hosted low-sulfidation
deposits are transitional with conditions more typical of
high-sulfidation deposits.
13.16.4.2 High-Sulfidation Epithermal Deposits
High-sulfidation epithermal deposits (the ‘acid-sulfate’ de-
posits of Heald et al., 1987) are described by Hedenquist and
Lowenstern (1994) as being the analog of high-temperature
fumaroles and acidic springs near volcanic vents. Examples of
silver-bearing high-sulfidation epithermal deposits are Sum-
mitville and Red Mountain, Colorado; Goldfield, Nevada;
Pascua, Chile/Argentina; and Pueblo Viejo, Dominican
Republic. The presence of advanced acid-sulfate alteration
and minerals similar to those found in porphyry systems
suggests that high-sulfidation deposits may be correlated with
the upper reaches of porphyry deposits (e.g., Gray and
Coolbaugh, 1994).
These deposits form from acidic, oxidized hydrothermal fluids
whose activity closely follows volcanism. They are characterized
by the ore minerals gold, electrum  pyrite, numerous copper
sulfides and sulfosalts, sphalerite and tellurides, and the gan-
gue minerals quartzþ alunite  pyrophyllite  dickite  kaolinite
(Simmons et al., 2005). Extensive vuggy silica and advanced
argillic alteration are characteristic, and indicate the interaction
of acidic magmatic gases (HCl and H2SO4) with host rocks (e.g.,
Pascua; Chouinard et al., 2005). Stoffregen (1987) estimated a
pH of 2 or less for the Summitville deposit based on the stability
of its alteration mineralogy. Precious metal mineralization is
subsequent to this alteration and hosted in the resulting open
spaces. Stable isotope geochemistry supports the contribution of
dominant magmatic fluids with only minor input of meteoric
water (e.g., Deyell et al., 2005; Rye et al., 1992; Vennemann et al.,
1993). Fluid inclusions in high-sulfidation deposits can contain
up to 40 wt% NaCl equivalent and indicate temperatures up to
400
C (e.g., Arribas et al., 1995).
These deposits are mined chiefly for their gold content, with
Ag/Au ratios of 0.2–2. At Summitville, there is a distinct zona-
tion of gold-to-silver ratios, with a ratio of 2:1 near the center
and a ratio of 20:1 near the periphery (Gray and Coolbaugh,
1994). At Pascua, silver (in halides and selenides) is mainly a
late-stage occurrence, associated with the condensation of re-
sidual magmatic gases (Chouinard et al., 2005); silver is zoned
temporally, with Ag/Au ratios <25 in main-stage ore versus a
ratio of >100 as a late-stage overprinting. Similar temporal
430 Silver Vein Deposits
zoning is seen at Pueblo Viejo, where an impermeable silica
cap created during early mineralization was hydrofractured by
later hydrothermal activity that resulted in high-grade precious
metal mineralization (Muntean et al., 1990).
13.16.5 Silver-Bearing Veins Related to Tin
Mineralization
Silver-bearing veins can be related to granite-hosted tin and
tungsten deposits. Ore-forming hydrothermal fluids exsolved
from shallow granitic intrusions transport silver in chloride
complexes and deposit silver and base-metal mineralization
in vein, stockwork, and lode deposits (Černy et al., 2005).
The southern part of the Bolivian tin belt contains a num-
ber of silver-rich polymetallic tin deposits that are related to
volcanic domes (Cunningham et al., 1991). The largest of these
is Cerro Rico de Potosı́, considered to be the largest silver
deposit in the world (Simmons et al., 2005). Veins cut a
rhyodacitic dome and surrounding host rocks, and are zoned,
with deeper cassiterite-rich veins surrounded by shallower,
silver-rich veins that are hosted in an advanced argillic cap.
Silver occurs as native silver and as argentiferous galena
(Kamenov et al., 2002). Hydrothermal activity was associated
with the emplacement of the dome, which introduced a silver-
enriched magma from which hydrothermal solutions could
deposit large quantities of silver for 0.1–0.2 Gy (Kamenov
et al., 2002; Rice et al., 2005).
The Cornwall tin deposits of southwest England have a
distinct silver-bearing zone as part of a general outward zona-
tion of tin, copper, arsenic, and lead deposited in veins out-
ward of and concentric to granitic intrusions. Silver occurs as
argentiferous galena in veins that cross-cut earlier-formed tin
lodes; these veins have textures such as brecciation, cockade
structures, and vugs that indicate deposition in active faults
(Jackson et al., 1989). Quartz is the main gangue mineral,
commonly accompanied by fluorite, barite, and carbonates.
The granitic magmas appear to have had anomalous concen-
trations of metals, with possible substitution for potassium in
biotite and K-feldspar (Černy et al., 2005).
13.16.6 Silver-Bearing Veins Related to Skarn
Mineralization
In addition to silver occurring within skarn mineralization,
economic quantities of silver are also found in veins associated
with, but separate from, some skarn deposits, especially the
zinc-rich skarns of northern and central Mexico and the south-
west United States (Einaudi et al., 1981; Megaw et al., 1988;
Meinert et al., 2005). The silver is found both in Au–Ag veins
(as Ag-sulfosalts) that are distal to associated igneous rocks,
and outside the zone of skarn mineralization, and in polyme-
tallic vein orebodies that may represent the transition from the
skarn to the distal veins (e.g., Hawksworth and Meinert, 1990).
Polymetallic veins record temperatures of formation, cor-
rected for pressure, that are transitional between those of
skarns and epithermal deposits; fluid inclusions in the central
district of New Mexico recorded temperatures up to 405
c, with
evidence of local boiling (Hawksworth and Meinert, 1990). Fluid
salinity in these inclusions averaged 7 wt% NaCl equivalent, and
the depth of formation is estimated at approximately 2 km, in
general agreement with the pressure calculated from fluid inclu-
sions formed in boiling solutions. Distal Ag-bearing veins may
represent ‘fluid escape structures’ (Meinert et al., 2005).
13.16.7 Discussion
In the description of the geochemistry of the various types of
silver vein deposits, a question sometimes arises as to the
classification of a particular deposit, which in turn is related
to its genesis. The epithermal Ag–Au vein category is occasion-
ally inclusive of other categories of deposits. An example can be
seen in the case of the Batopilas, Sonora, district, included here
as an epithermal deposit. However, older literature indicated
that silver was associated with a five-element type assemblage.
It has been proposed that two separate episodes of ore deposi-
tion occurred in this instance (Wilkerson et al., 1988), the
latter related to igneous intrusion.
Some deposits considered as Cordilleran-type vein deposits
also may in part have characteristics of carbonate-hosted
mantos, which are attributed to massive replacement of the
carbonate host rocks. An example is seen in the Magma Mine,
Arizona, which in part consists of veins and in part a manto,
where carbonates form the host rock (Hammer and Peterson,
1968). The ores of the Coeur d’Alene district were also consid-
ered to be of Cordilleran type and of magmatic-hydrothermal
origin; however, Beaudoin and Sangster (1992), in the light of
newer evidence, considered them to be representative of their
classification of silver–lead–zinc veins in clastic metasedimen-
tary terranes.
Similarly, in the case of the Cornwall tin deposits, the silver-
bearing veins, known as cross-courses, transect the granite
hosts to the tin lodes and are more recently attributed to later
events, as evidenced by geochronology, a contribution of ba-
sinal fluids and temperatures in the range of 100
C (Scrivener
et al., 1994). The cross-courses contain five-element type ass-
emblages as well as uranium (Dunham et al., 1978).
Interpretations of isotopic data, particularly dD–d18O dia-
grams, are dependent on knowledge of the temperature of
deposition. Assumptions that temperatures determined from
fluid inclusions in gangue minerals are the same as those of
earlier stages of ore deposition may lead to erroneous interpre-
tations. Temperatures in vein deposits typically vary in the
course of deposition. Another consideration is that tempera-
tures typically determined for a deposit are indicative of the
temperature of deposition, but do not reflect the temperature
of transport. As decreasing temperature is a factor leading to
precipitation, higher temperature during transport would gen-
erally be expected to prevail.
Whereas in the other types of deposits considered, the ge-
netic factors in the origin of the deposit are not a great problem,
the same is not true for the five-element vein type. Kissin (1992)
listed seven hypotheses for the genesis of this type of deposit,
some of which differ considerably. The underlying problem may
be that, if this distinctive type of ore deposit has a common
origin, no hypothesis adequately accounts for all examples of
these deposits. A particular difficulty is seen in the Ni–Co arse-
nide assemblage in which base metal sulfides are generally

absent. Kissin (1993) proposed that the solubility of Ni and Co
is enhanced in high-temperature and high-salinity solutions.
The solubility of base metals is also enhanced under these
conditions; however, if the solution depositing the ores was
relatively oxidized at least at or above the sulfide–sulfate bound-
ary in pO2/pH space, Ni–Co arsenates might precipitate if re-
duction of arsenate preceded reduction of sulfate. Precipitation
at a site of local reduction is noted at Thunder Bay in the form of
carbonaceous shales (Franklin et al., 1986) and at Kongsberg in
the form of fahlbands, minor zones of sulfide minerals in host
rock (Segalstad et al., 1986). This hypothesis lacks many ele-
ments for its proof, however. As well as needing more geochem-
ical data from many deposits that have not been studied by
modern methods, evaluation of geochemical reactions is not
possible given the absence of thermodynamic data for the min-
eral species involved.
Acknowledgments
We should like to thank Roger Mitchell and Hamid Mumin, as
well as editor Steve Scott for their constructive reviews of the
manuscript. Diagrams were prepared by Sam Spivak.
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