Applied Geochemistry 15 (2000) 337346

Native gold in mineral precipitates from high-temperature

volcanic gases of Colima volcano, Mexico
Yuri A. Taran a, Alain Bernard b,*, Juan-Carlos Gavilanes c, Fatima Africano b
a
Institute of Geophysics, UNAM, 04510, D.F. Mexico, Mexico
b
Universite Libre de Bruxelles, 50, Ave Roosevelt, 1050 Brussels, Belgium
c
Colima Volcano Observatory, University of Colima, Colima, Mexico
Received 1 July 1998; accepted 27 May 1999
Editorial Handling by R. Fuge

Abstract

Trigonal and pentagonal shaped plates and prism, and octahedra of Au crystals 340 mm in dimension were
found on the inner wall of a silica tube inserted into a 8008C fumarolic vent of Colima volcano, Mexico. Gold
precipitates from the high-temperature and highly oxidized volcanic vapor (a mixture of magmatic gas with more
than 90% of air) cover a narrow temperature range of 5506008C, and occur in association with V-rich NaK-
sulfates. The Au concentration in the volcanic gas condensate is between 0.1 and 0.5 mg/kg. Using thermodynamic
data for Au(c), Au(g), AuH(g) and AuS(g), open- and closed-system cooling of a simplied volcanic gas has been
modeled with the following characteristics of volcanic gas+air mixture: P = 1 bar, fSO2 =0.01 bar; fSO2 xed by
Fe2O3Fe3O4 or Cu2OCuO pairs for open-system cooling, and fSO2 =0.1 bar for closed-system cooling. Volcanic
vapor released from the shallow magma body transports Au as AuH(g) and AuS(g). According to calculations, after
mixing with air, AuS(g) and AuH(g) oxidize to Au(g), and the temperature of the Au deposition depends only on
the initial total concentration of Au species in the vapor. The temperature range of 5506008C for Au precipitation
at a high fSO2 corresponds to a very low initial Au concentration, about 1 ng/kg in the volcanic gas condensate. This
is at least two orders of magnitude lower than the observed Au content in the Colima gas, indicating the presence
of other volatile gold species, e.g. AuClx, Au(OH)x etc., or Au precipitation under non-equilibrium conditions from
a volcanic gas+air mixture with coexisting free H2 and O2. # 1999 Elsevier Science Ltd. All rights reserved.

1. Introduction Gold crystals have previously been reported in natu-

The authors found Au crystals on the inner wall of
a 1 m-long silica tube inserted into a 8008C fumarolic
vent in the crater of Colima volcano, Mexico. This
is the rst direct evidence of the natural precipitation
of Au from volcanic gas. Here the authors describe
their ndings and a model for the transport of Au in
vapor.
* Corresponding author.
E-mail address: abernard@ulb.ac.be (A. Bernard).
ral mineral incrustations around a high-temperature
gas vent on a scoria cone of Tolbachik volcano,
Kamchatka, after the 19751976 eruption (Vergasova
et al., 1982). Gold particles of irregular form have
been found in aerosols discharging from Erebus vol-
cano, Antarctica (Meeker et al., 1991). Enrichment in
Au of high-temperature fumarolic encrustations were
observed on Merapi volcano, Indonesia (Kavaleris,
1994). Concentrations of Au in the range of 0.0110.0
mg/kg are commonly measured in condensates from
high-temperature volcanic gases (e.g. Symonds, 1992;
Hedenquist, 1995).

0883-2927/00/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 8 8 3 - 2 9 2 7 ( 9 9 ) 0 0 0 5 2 - 9
338 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346

Table 1
Composition of high-temperature volcanic gas condensates. Colima (this work), Mt. St. Helens (Bernard, 1985), Momotombo
(Quiset et al., 1989) and Kudryavy (Taran et al., 1995)

Volcano Colima Colima Colima Mt.St.Helens Momotombo Kudryavy

Date: 03. 1997 06.1997 08.1997 1981 1986 1992

T (8C) 742 828 738 710 886 870
Major species (mg/kg)
Cl 10500 6550 7320 1500 6900 15380
SO4 1550 3992 2300 3570 4320
F 310 250 243 316 214 503
B 28 18 26 230 37
Na 36 24 29 5.2 23 26
K 22 26 17 3.9 23 29
SiO2 210 160 120 170 238
Trace elements (mg/kg)
As 433 525 368 1370 2100 1550
Au 0.5 0.1 0.12 0.03 5 0.07
Ba 463 320 450 0.2 74
Ca 1200 1700 1350 11 4600 5500
Cd 55 740 45 41 20 580
Co 2 <2 <2 0.4 16
Cr 169 121 79 12 45
Cu 931 440 870 54 340 130
Fe 3270 4240 2600 200 5500 6800
Mg 1200 1025 1420 5600 1760
Mn 56 8 50 3 220 210
Mo 91 182 97 96 70 270
Ni 23 15 42 55
Pb 451 78 480 540 230 580
Sb 42 130 49 8 1500 20
Se 450 298 370 30 1200 170
Sr 56 16 32 716 130
Ti 623 700 633 400 620
Tl 24 53 34 65
V 263 1040 160 5 98
Zn 5300 8140 4970 20 460 1000

2. General setting highest temperature zone, Z3, is located in the north-

Colima volcano, the most active in Mexico and
among the most active in the world, is located in the
western Mexican volcanic belt. The modern eruptive
history and erupted products have been described in
detail by Luhr and Carmichael (1990). A lava dome
was formed in 19751976 with a at summit crater, of
300  200 m in dimension. The last eruption occurred
in 1994. The volcano is degassing intensively, with an
average SO2 ux during the last 3 yr of 100 t/day
(Gavilanes, pers. comm., 1997). There are no well-
developed fumarolic elds in the crater, but a diuse,
`unsaturated' gas ow occurs from under unsorted lava
blocks in all parts of the crater oor. The crater oor
can be divided into several zones, with dierent tem-
peratures of vapor discharge (Connor et al., 1993). The
ern part of the crater. Red glowing holes with tempera-
tures above 8008C can be seen here between lava
blocks, covered by yellow and greenblue incrusta-
tions. The structure of the lava dome provides an out-
ow of very hot and highly oxidized volcanic gases
due to mixing with air within the dome interior.
3. Methodology
All vents in the Colima crater with temperature
from boiling point to above 8008C discharge gas with
a very high proportion of air. Therefore, it was im-
possible to use pre-evacuated Giggenbach asks for
the gas sampling. The authors used a 1.2-m-long silica
sampling tube and pumping through two or three con-
 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346 339

Table 2
Summary of distribution of minerals along the inner wall of silica tubes inserted in a high-temperature vent Z3 at Colima volcano.
Temperatures measured at the completion of the experiment are given for tube no. 2 with gradient from 828 to 3808C. Minerals
identied by both, EDS and XRD are in italic

Zone T Minerals, mineral assembledges, amorphous phases,

(No.) (8C)

1-2 380-420 amorphous silica, cristobalite thenardite, arcanite, KNaSO4, aphthitalite,

3 450 amorphous silica, crisobalite, hematite, thenardite, arcanite, KNaSO4, aphthitalite, (NaKVZnCuS)
phases
4 550 gold, amorphous silica, cristobalite, hematite,, tenorite, (FeTi) oxides, thenardite, arcanite, KNaSO4,
aphthitalite, V-sulfate, (NaKVCuS) phases, chalcocyanite, barite,
56 600 gold, amorphous silica, cristobalite, hematite, Ti-hematite(?), tenorite, WO3, thenardite, arcanite, V-sulfate,
(KPbCuVS) phases, anglesite, barite, anhydrite, (CaVS) phase, (KCuPbVClS) phases
7 680 Cristobalite, tridymite, hematite, rutile, Ti-hematite(?), WO3, tenorite, planttnerite, (KNaVS) phases,
(CuSn) phase, aphtitalite, arcanite, anglesite, anhydrite, apatite(?), (CuSnZnCl) phase, (CaFeClF)
phase,
8 740 Tridymite, hematite, thenardite, wolframite(?), ferberite(?), KNaSO4, (KNaPbZnS) phase, anhydrite,
uorite,
910 828 Tridymite, hematite, bunsenite, KNaSO4 (NaKPbCuS) phases, (NaKCaS) phase, anglesite, (FeTi
CuS) phase, uorite, (AsSbS) phase, (WVCo) phase

secutive traps, each one with 30 ml of 46 N NaOH 4. Results and discussion

solution. Condensates for major and trace element
analysis were pumped into two consecutive glass traps
cooled by ice. More details about gas and condensate
sampling and analysis will be published elsewhere
(Taran et al., 1998).
The silica tube experiment is the only quantitative
method to study mineral precipitation from volcanic
gases under controlled conditions (Le Guern and
Bernard, 1982). Experiments were conducted at
Colima twice in 1996. Two 1-m-long tubes were
inserted into the high-temperature vent at site Z3. The
rst tube, with a diameter of 20 mm, was left for two
weeks, and the second one, with a diameter of 35 mm,
remained in place for 80 days. From the beginning of
experiments the only vent temperatures measured were
at 1 m depth (765 and 8018C, respectively). The tem-
perature distribution was measured by a thermocouple
at the completion of the experiment inside the tube.
The temperature gradient in the narrow tube was 780
3508C, and in the wide tube 8283808C. About 5 cm
of each tube were left above the surface. The gradient
depends on the length of the open, `cold' end of the
tube and on the weather conditions (Korzhinsky et al.,
1996), therefore it could have changed during the ex-
periment and the nal temperature distribution can be
considered as a crude estimation.
In the laboratory, the tubes were cut into 10 pieces
corresponding to 10 temperature zones of each tube,
and mineral precipitates were studied and analyzed by
scanning electron microscopy (SEM), X-ray spec-
trometry (EDS) and X-ray diraction techniques.
4.1. Chemistry of gas, condensates and distribution of
minerals
Gas composition of Colima samples collected in al-
kaline traps is quite typical for a subduction type ande-
sitic volcano in terms of water content and elemental
ratios (on an air-free basis, in mmol/mol): H2O=910
980, CO2=1040, S(total)=1020, HCl=28,
HF=0.10.5, Cl/B=30100 (Symonds et al., 1994;
Giggenbach, 1996). The total S was presented as SO2
and SO3; H2S was below the detection limit. Because
of the high air content, it was impossible to analyze
the non-condensable gases such as H2, CO, etc.
Therefore, it was also impossible to estimate the redox
state of Colima gases from the gas analyses.
There are signicant dierences between the Colima
deposits in silica tubes and high-temperature mineral
deposits from other volcanoes (Le Guern and Bernard,
1982; Quiset et al., 1989; Bernard et al., 1990;
Symonds, 1992) with reduced (typically between NNO
and FMQ redox-buers) gases. These dierences are a
complete lack of halite (NaCl) and sylvite (KCl) as the
main non-silica phases, and a lack of suldes and Cd-
and Mo-bearing minerals (more details are given in
Taran et al., 1998). However, chemical composition of
the high-temperature condensates of Colima vapors
(Table 1), does not dier signicantly from average
high-temperature (above 7008C) condensates from
other volcanoes. This is despite some enrichment of
Colima gases in V, Zn and Cu (Le Guern, 1988;
Symonds et al., 1990; Taran et al., 1995). The Au con-
340 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346
Fig. 1. Scanning electron microscope photographs of some
mineral phases from silica tubes and natural encrustations:
(A) V-sulfate agregates from the silica tube; (B) V-sulfate
from natural encrustations; (C) anglesite from the silica tube.
tent of three samples of the Colima condensates ana-
lyzed by ICP-MS varies between 0.1 and 0.5 mg/kg
(Table 1).
Table 2 illustrates the distribution of minerals,
which is the same for both Colima tubes, along the
temperature gradient. The main non-silica phases are
mixed or pure NaK sulfates (thenardite, arcanite,
aphthitalite, KNaSO4) enriched in Zn, Pb, Cu and V.
These sulfates are enriched in V between 400 and
6008C up to pure V-sulfate, which forms aggregates of
yellow to brown needles, 10100 mm in dimension
(Fig. 1a). This is a new anhydrous mineral with a com-
position (VO)2SO4 (Bernard et al., in preparation).
Vanadium minerals have not been reported in silica
tube experiments. However, scherbinaite (V2O5) was
found in air exposed fumarolic encrustations
(Borisenko et al., 1970; Stoiber and Rose, 1974;
Seramova, 1979; Hughes and Finger, 1983). The
high-temperature zone Z3 at Colima is covered by yel-
low to blue incrustations, enriched in V. There is a
sharp border between air exposed, yellow encrustations
with V2O5 and underground, blue ones, enriched in V-
sulfate (Fig. 1b).
Barite and anhydrite are common sulfate minerals,
sporadically dispersed along the tube independent of
the temperature. Anglesite (PbSO4) is abundant in the
high-temperature half of the tube (Fig. 1c). Among the
chlorides, small particles of Cu- and mixed (Cu, Zn)-
and (Ca, Fe)-unidentied phases were found in the
middle of the tube (6007008C). Aggregates of (Cu,
Zn, Sn) unindentied sulfo-chloride phases (?), rare
phases of (Ca, Fe)-chlorides and uorides up to pure
uorite occur in zones 49 (5508008C). Among the
oxides the most abundant phase (except of SiO2) is
hematite, sometimes enriched in Ti, dispersed along
the tube starting from the 4508C zone. Rare small par-
ticles of plattnerite, PbO2, rutile, TiO2, wolframite and
ferberite, (Fe, Mn) WO4, as well as pure WO3, and a
mixed (Cu, Zn, Sn) oxide phases are present in zone 7
(6006508C). A minor amount of bunsenite (NiO) pre-
cipitates in the high-temperature half of the tube.
Gold precipitated in a narrow temperature interval
of 5506008C, associated with V-rich NaK-sulfates.
The most common morphologies of Au crystals
observed were trigonal and pentagonal shaped plates
(Fig. 2), 540 mm in diameter. A smaller pentagonal
prism and an octahedron have also been observed. All
Au crystals are very pure, without traces of Ag or
other metals. They were found in both tubes in the
same temperature interval with the associated V-sulfate
aggregates.
The sizes and morphologies of the Au crystals are
very similar to those observed in hydrothermal exper-
iments (Gammons et al., 1997), as well as in exper-
iments of Au precipitation in vacuum (Ino, 1966) or
from colloidal solutions (Hernandez et al., 1991). Gold
 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346 341

Fig. 2. Scanning electron microscope photographs of Au crystals. (A) 4 mm pentagonal plate; (B) 9 mm semi-transparent trigonal
plate; (C) 35 mm trigonal plate; (D) 3 mm octahedron; (E) 3 mm pentagonal prism.
342 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346

particles discovered in aerosols of Mt. Erebus volcano,

Antarctica, (Meeker et al., 1991) are aggregates of irre-
gularly shaped particles of electrum composition and
are likely to be hydrothermal Au from the altered wall
rocks.

4.2. Transport of gold

The problem is to establish the chemical nature and

redox limits for Au transport by high-temperature vol-
canic gas and to explain the narrow temperature inter-
val observed for native Au deposition. Gold transport
by a low-pressure and high-temperature magmatic
uid (i.e. volcanic gas) is still a subject of speculation
due to the lack of experiment and thermodynamical
data for possible volatile Au species. All available in-
formation about the natural gaseous transport of Au
is contained in a few of the high-temperature conden-
sate and volcanic aerosol analyses (Meeker et al., 1991,
and references therein; Symonds, 1992). Symonds and
Reed (1993) modeled the transport of Au in Mt St.
Helens volcanic gases (0.03 mg/kg Au in the conden-
sate, measured by INAA, Bernard, 1985). They calcu-
lated that Au should start to precipitate at 4008C due
to reduction of AuS by H2. They also concluded that
AuS(g) is more stable than Au(g) in the parent Mt
St.Helens gas. However, in contrast to the reduced vol-
canic gases from Mt St. Helens (logfO2 =16 at 7008C;
Gerlach and Casadevall, 1986), the Colima gases are
very oxidized, and do not contain measurable amounts
of H2S and suldes in mineral precipitates.
If only Au(g), AuS(g) and AuH(g) are the volatile
Au species, a possible mechanism for the transport
and precipitation in the Colima case may involve the
release of Au in the form of AuS(g) or AuH(g) from
the melt and oxidation in the high fO2 environment of
the lava dome according to the following reactions:
AuS g O2 Au g SO2 1a
4AuH g O2 4Au g 2H2 O 1b
These reactions may be rewritten as follows:
AuS g 2H2 O Au g 2H2 SO2 2a
2AuH g 2Au g H2 2b
Temperature dependence of the equilibrium constant
for reactions (2a) and (2b) can be calculated from the
database of Barin et al. (1977) and Knacke et al.
(1991):
log K2 3:49 17590=T 3a
Fig. 3. Diagram showing the stability of AuH(g), AuS(g) and
Au(g) with respect to the oxidation state and temperature for
a gas with fSO2 =0.01 bar. For reference, the stability bound-
aries of fayalitemagnetitequartz (FMQ), hematitemagne-
tite (HM), Cu2O/CuO and S-gas buer are also shown.
RH=log(x H2 =xH2 O ).
log K2a 3:70 9950=T 3b
Concentrations of SO2 in Colima gases on an air-
free basis vary from 10 to 20 mmol/mol which corre-
sponds to average fSO2 values of close to 102 bar
before mixing with air. Fig. 3 shows the relative stab-
ility of AuS(g) (at fSO2 =0.01 bar) and AuH(g) with
respect to the oxidation state and temperature. For
reference, the stability boundaries of fayalitemagne-
titequartz (FMQ), hematitemagnetite (HM) and the
Cu2O/CuO pair, as well as the `gas-buer' line are also
shown (Giggenbach, 1987). Both AuS(g) and AuH(g)
are stable at very low to very high H2 fugacity (below
the HM-line up to 7008C), but they are not stable
under Cu2O/CuO buer conditions.
This may be the main reason why native Au or
enrichment in Au is observed only in highly oxidized
natural incrustations forming at the surface (Vergasova
et al., 1982; Kavaleris, 1994; Naboko and Glavatskikh,
1997), but not in silica tubes at other volcanoes, where
minerals precipitate from the air-free volcanic vapor
with fH2 controlled by the SO2H2S gas buer. The
Colima volcano represents a special, exotic case, since
there is an outow of very hot and highly oxidized
gases (because of the high air content) with stable Au
in the vapor phase.
If only Au(g) is stable at high fO2 values, Au will
 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346 343

Fig. 4. Equilibrium concentrations of Au species, H2 and O2, calculated for cooling of a simplied volcanic gas at 1 bar total press-
ure. Gas contains H2O, H2, SO2, SO3, H2S, S2, O2 and Au species. Mole fraction of the total Au in the initial, 9008C gas is
2  1011 (corresponding to the average measured value of 0.2 mg/kg in the condensate). (A) Closed system cooling with the initial
fO2 =0.1 bar (mixture with air); (B) open system cooling with the Cu2O/CuO oxygen buer; (C) open system cooling with the gas
buering (fSO2 fH2 S ). (D) Open system cooling with the hematite/magnetite fO2 -buer. The diagram illustrates that Au should pre-
cipitate from the high oxidized Colima vapor above 8008C, before entering the silica tube. The observed temperature range of the
Au deposition corresponds to the cooling at fO2 close to the HM-buering.

start to precipitate from the vapor when fAu reaches
the saturation value. The latter can be calculated from
the reaction Au(c)= > Au(g) (GASTHERM database,
Symonds and Reed, 1993):
log fAu 6:72 19150=T
This dependence indicates that Au(g) in volcanic
vapor at the mg/kg ((107 bar) concentration, as it was
measured for most of volcanic gases, should start to
precipitate at high O2 fugacity well above 8008C,
before entering the silica tube. In the Colima silica
tubes, Au was found only in a narrow temperature
zone of 5506008C. There are two main reasons for
this:
1. AuS(g) and/or AuH(g) are still stable to 6008C, and
the oxidation state inside the silica tube is controlled
in a manner more complicated than gas or mineral
buering, due to kinetic eects on gas reactions.
The mixing of volcanic gas with air at Colima prob-
ably occurs at very shallow depth. In a few samples
where non-condensable gases were analyzed by gas
chromatography, air was always present (up to 99
mol%) together with high amounts of H2, at a con-
centration of 0.01 mmol/mol. This concentration
4 corresponds roughly to fH2 in equilibrium with the
hematitemagnetite buer system, and AuS(g) and
AuH(g) are stable at this H2 fugacity below 700 and
8708C, respectively (Fig. 3), but not at the measured
O2 concentrations in the Colima gas.
2. Volatile Au species are transported as AuH(g),
AuS(g) and Au(g), but at high fO2 other species such
as AuClx (g), Au(OH)x (g), other halides, sulfates,
etc., may be stable. However, thermodynamic data
for these species are lacking, and corresponding
equilibrium calculations ``must await future exper-
imental and theoretical studies'' (Gammons and
Willams-Jones, 1997).
Numerical equilibrium calculations were conducted
to model cooling from 9008C of a simplied volcanic
344 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346
Fig. 5. The dependence of the total Au concentration (in g/
kg) in the vapor and temperature of Au precipitation from
the cooling of a vapor at FMQ, NNO and HM rock-buers,
S-gas buer and at high fO2 (Cu2O/CuO buer and closed sys-
tem with fO2 =0.1 bar). The gas buer lines are shown at two
dierent values of fSO2 =fH2 S (1 and 10). This plot illustrates,
that in the case of the HM-cooling, the temperature of the Au
deposition is very sensitive to the total Au content in the
vapor phase. Au can precipitate inside the silica tube only if
its concentration in the vapor is in the range 0.11.0 mg/kg.
From an O2-rich vapor, as well as from a highly reduced
vapor (FMQ), Au (at the mg/kg concentration in the gas
phase) should start to precipitate before entering the silica
tube. In contrast, gas cooling itself (gas buer) or under
NNO conditions will precipitate Au at lower temperature,
close to or behind the `cool' end of the tube.
gas at a pressure of 1 bar with fSO2 =0.01 bar, and fO2
controlled by hematite/magnetite (HM), Cu2O/CuO
and (fSO2 /fH2 S =1)-gas buer, as well as for a closed
system with 0.1 bar of O2. The Cu-oxide buer is used
to model the high O2 fugacity, i.e. conditions at which
Au(g) is stable (Fig. 3). Fig. 4(AD) shows the evol-
ution of the system upon the cooling of Au gas species
with initial Au concentration of 0.2 mg/kg (2  1011
mole fraction, corresponding to the Au concentration
in Colima condensates) and fSO2 =0.01 bar. At high fO2
Au starts to precipitate above 8008C, i.e. before enter-
ing the silica tube. At fH2 =105 bar (HM buer) Au
precipitates between 500 and 6008C, and if fH2 is con-
trolled by the gas SO2/H2S buer, Au precipitates
below 4008C, i.e. in the `cold' end of the silica tube or
behind the tube. The calculated relationship between
total Au concentration in the vapor phase and the
temperature of Au condensation is shown in Fig. 5 for
open systems, with HM, FMQ, Cu2OCuO and gas
buers, and for a closed system with fO2 =0.1 bar. In
the case of the HM buer, the temperature of conden-
sation is very sensitive to the initial Au concentration,
changing from 800 to 4008C over the 1010 to 1011
range of the Au mole fraction. The observed tempera-
ture interval of 5506008C corresponds to a mole frac-
tion of 2  1011, or about 0.2 mg/kg, which is close to
the measured Au concentration in Colima gases.
Under highly oxidized conditions, such as that rep-
resented by the Cu2OCuO buer as well as in a
closed system, the temperature of Au condensation
corresponds to the temperature dependence for the
fugacity of the saturated Au vapor (Eq. (4)). Highly
reduced conditions (along FMQ) also shift the Au con-
densation temperature to high values. However, under
the NNO and gas-buer conditions, Au starts to pre-
cipitate at considerably lower temperature.
In summary, a system containing Au(g), AuS(g) and
AuH(g) is very sensitive to the oxidation state of the
gas phase in respect to Au precipitation. It might be
that including other Au volatile species will `stabilize'
this sensitivity.
5. Conclusions
This paper reports the rst nding of Au precipi-
tation from high-temperature (8008C) volcanic vapor
in a silica tube experiment. Thermodynamic calcu-
lations were used to estimate the temperature, redox
and concentration constraints for Au deposition from
a highly oxidized volcanic vapor+air mixture dischar-
ging from the Colima fumaroles. Despite a signicant
degree of uncertainity in the calculations due to the
lack of thermodynamic data for potentially stable vol-
atile Au species, it is possible to make the following
conclusions:
Pure Au precipitates from the high-temperature,
highly oxidized vapor of Colima volcano in the form
of triangular or pentagonal shaped thin plates, penta-
gonal prisms or octahedra 540 mm in dimension, over
a temperature range of 5506008C in association with
V-rich NaK sulfates.
The observed temperature range of precipitation, as
well as the measured Au concentration corresponds
well to the modeled behavior of Au at fO2 controlled
by the magnetitehematite buer, but is not in agree-
ment with the observed gas composition.
This disagreement may be caused either by essen-
tially non-equilibrium conditions in the volcanic
gas+air mixure (coexistence of free H2 at the redox
state of the HM buer and free O2), or by the uncer-
tainity in the calculations due to the lack of thermo-
dynamic data for potentially stable oxidized volatile
Au species.
The modeled behavior of a system containing only
AuS(g), AuH(g) and Au(g) in respect to the Au pre-
cipitation is very sensitive to the oxidation state of the
 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346
vapor phase in a complex way: temperatures of the Au
precipitation are close in highly reduced and highly
oxidized environments.
Acknowledgements
We thank E. Lounejeva for the ICP-MS analyses of
condensates and XRD identication of minerals and
A. Cortes and J.C. Navarro for eld assistance. We
thank J. Hedenquist and R. Symonds for their reviews
of the rst version of the manuscript. Constructive
comments by A.E. Williams-Jones and K. Brown sig-
nicantly improved the paper. This work was sup-
ported by grants from DGAPA-UNAM (No.
IN104197) and INTAS (No. 94-3129).
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