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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
Institute of Geophysics, UNAM, 04510, D.F. Mexico, Mexico
Universite Libre de Bruxelles, 50, Ave Roosevelt, 1050 Brussels, Belgium
Colima Volcano Observatory, University of Colima, Colima, Mexico
Received 1 July 1998; accepted 27 May 1999
Editorial Handling by R. Fuge


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-

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

ern part of the crater. Red glowing holes with tempera-
Colima volcano, the most active in Mexico and tures above 8008C can be seen here between lava
among the most active in the world, is located in the blocks, covered by yellow and greenblue incrusta-
western Mexican volcanic belt. The modern eruptive tions. The structure of the lava dome provides an out-
history and erupted products have been described in ow of very hot and highly oxidized volcanic gases
detail by Luhr and Carmichael (1990). A lava dome due to mixing with air within the dome interior.
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 3. Methodology
average SO2 ux during the last 3 yr of 100 t/day
(Gavilanes, pers. comm., 1997). There are no well- All vents in the Colima crater with temperature
developed fumarolic elds in the crater, but a diuse, from boiling point to above 8008C discharge gas with
`unsaturated' gas ow occurs from under unsorted lava a very high proportion of air. Therefore, it was im-
blocks in all parts of the crater oor. The crater oor possible to use pre-evacuated Giggenbach asks for
can be divided into several zones, with dierent tem- the gas sampling. The authors used a 1.2-m-long silica
peratures of vapor discharge (Connor et al., 1993). The 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)
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)
8 740 Tridymite, hematite, thenardite, wolframite(?), ferberite(?), KNaSO4, (KNaPbZnS) phase, anhydrite,
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 4.1. Chemistry of gas, condensates and distribution of
cooled by ice. More details about gas and condensate minerals
sampling and analysis will be published elsewhere
(Taran et al., 1998). Gas composition of Colima samples collected in al-
The silica tube experiment is the only quantitative kaline traps is quite typical for a subduction type ande-
method to study mineral precipitation from volcanic sitic volcano in terms of water content and elemental
gases under controlled conditions (Le Guern and ratios (on an air-free basis, in mmol/mol): H2O=910
Bernard, 1982). Experiments were conducted at 980, CO2=1040, S(total)=1020, HCl=28,
Colima twice in 1996. Two 1-m-long tubes were HF=0.10.5, Cl/B=30100 (Symonds et al., 1994;
inserted into the high-temperature vent at site Z3. The Giggenbach, 1996). The total S was presented as SO2
rst tube, with a diameter of 20 mm, was left for two and SO3; H2S was below the detection limit. Because
of the high air content, it was impossible to analyze
weeks, and the second one, with a diameter of 35 mm,
the non-condensable gases such as H2, CO, etc.
remained in place for 80 days. From the beginning of
Therefore, it was also impossible to estimate the redox
experiments the only vent temperatures measured were
state of Colima gases from the gas analyses.
at 1 m depth (765 and 8018C, respectively). The tem-
There are signicant dierences between the Colima
perature distribution was measured by a thermocouple
deposits in silica tubes and high-temperature mineral
at the completion of the experiment inside the tube.
deposits from other volcanoes (Le Guern and Bernard,
The temperature gradient in the narrow tube was 780 1982; Quiset et al., 1989; Bernard et al., 1990;
3508C, and in the wide tube 8283808C. About 5 cm Symonds, 1992) with reduced (typically between NNO
of each tube were left above the surface. The gradient and FMQ redox-buers) gases. These dierences are a
depends on the length of the open, `cold' end of the complete lack of halite (NaCl) and sylvite (KCl) as the
tube and on the weather conditions (Korzhinsky et al., main non-silica phases, and a lack of suldes and Cd-
1996), therefore it could have changed during the ex- and Mo-bearing minerals (more details are given in
periment and the nal temperature distribution can be Taran et al., 1998). However, chemical composition of
considered as a crude estimation. the high-temperature condensates of Colima vapors
In the laboratory, the tubes were cut into 10 pieces (Table 1), does not dier signicantly from average
corresponding to 10 temperature zones of each tube, high-temperature (above 7008C) condensates from
and mineral precipitates were studied and analyzed by other volcanoes. This is despite some enrichment of
scanning electron microscopy (SEM), X-ray spec- Colima gases in V, Zn and Cu (Le Guern, 1988;
trometry (EDS) and X-ray diraction techniques. Symonds et al., 1990; Taran et al., 1995). The Au con-
340 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346

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
The sizes and morphologies of the Au crystals are
Fig. 1. Scanning electron microscope photographs of some very similar to those observed in hydrothermal exper-
mineral phases from silica tubes and natural encrustations: iments (Gammons et al., 1997), as well as in exper-
(A) V-sulfate agregates from the silica tube; (B) V-sulfate iments of Au precipitation in vacuum (Ino, 1966) or
from natural encrustations; (C) anglesite from the silica tube. 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

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 Fig. 3. Diagram showing the stability of AuH(g), AuS(g) and
Au(g) with respect to the oxidation state and temperature for
to reduction of AuS by H2. They also concluded that
a gas with fSO2 =0.01 bar. For reference, the stability bound-
AuS(g) is more stable than Au(g) in the parent Mt aries of fayalitemagnetitequartz (FMQ), hematitemagne-
St.Helens gas. However, in contrast to the reduced vol- tite (HM), Cu2O/CuO and S-gas buer are also shown.
canic gases from Mt St. Helens (logfO2 =16 at 7008C; RH=log(x H2 =xH2 O ).
Gerlach and Casadevall, 1986), the Colima gases are
very oxidized, and do not contain measurable amounts log K2a 3:70 9950=T 3b
of H2S and suldes in mineral precipitates.
If only Au(g), AuS(g) and AuH(g) are the volatile Concentrations of SO2 in Colima gases on an air-
Au species, a possible mechanism for the transport free basis vary from 10 to 20 mmol/mol which corre-
and precipitation in the Colima case may involve the sponds to average fSO2 values of close to 102 bar
release of Au in the form of AuS(g) or AuH(g) from before mixing with air. Fig. 3 shows the relative stab-
the melt and oxidation in the high fO2 environment of ility of AuS(g) (at fSO2 =0.01 bar) and AuH(g) with
the lava dome according to the following reactions: respect to the oxidation state and temperature. For
reference, the stability boundaries of fayalitemagne-
AuS g O2 Au g SO2 1a 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)
4AuH g O2 4Au g 2H2 O 1b are stable at very low to very high H2 fugacity (below
the HM-line up to 7008C), but they are not stable
These reactions may be rewritten as follows: under Cu2O/CuO buer conditions.
This may be the main reason why native Au or
AuS g 2H2 O Au g 2H2 SO2 2a enrichment in Au is observed only in highly oxidized
natural incrustations forming at the surface (Vergasova
et al., 1982; Kavaleris, 1994; Naboko and Glavatskikh,
2AuH g 2Au g H2 2b 1997), but not in silica tubes at other volcanoes, where
minerals precipitate from the air-free volcanic vapor
Temperature dependence of the equilibrium constant with fH2 controlled by the SO2H2S gas buer. The
for reactions (2a) and (2b) can be calculated from the Colima volcano represents a special, exotic case, since
database of Barin et al. (1977) and Knacke et al. there is an outow of very hot and highly oxidized
(1991): gases (because of the high air content) with stable Au
in the vapor phase.
log K2 3:49 17590=T 3a 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 ably occurs at very shallow depth. In a few samples
the saturation value. The latter can be calculated from where non-condensable gases were analyzed by gas
the reaction Au(c)= > Au(g) (GASTHERM database, chromatography, air was always present (up to 99
Symonds and Reed, 1993): mol%) together with high amounts of H2, at a con-
centration of 0.01 mmol/mol. This concentration
log fAu 6:72 19150=T 4 corresponds roughly to fH2 in equilibrium with the
hematitemagnetite buer system, and AuS(g) and
This dependence indicates that Au(g) in volcanic AuH(g) are stable at this H2 fugacity below 700 and
vapor at the mg/kg ((107 bar) concentration, as it was 8708C, respectively (Fig. 3), but not at the measured
measured for most of volcanic gases, should start to O2 concentrations in the Colima gas.
precipitate at high O2 fugacity well above 8008C, 2. Volatile Au species are transported as AuH(g),
before entering the silica tube. In the Colima silica AuS(g) and Au(g), but at high fO2 other species such
tubes, Au was found only in a narrow temperature as AuClx (g), Au(OH)x (g), other halides, sulfates,
zone of 5506008C. There are two main reasons for etc., may be stable. However, thermodynamic data
this: for these species are lacking, and corresponding
equilibrium calculations ``must await future exper-
1. AuS(g) and/or AuH(g) are still stable to 6008C, and
imental and theoretical studies'' (Gammons and
the oxidation state inside the silica tube is controlled
Willams-Jones, 1997).
in a manner more complicated than gas or mineral
buering, due to kinetic eects on gas reactions. Numerical equilibrium calculations were conducted
The mixing of volcanic gas with air at Colima prob- to model cooling from 9008C of a simplied volcanic
344 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346

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
Fig. 5. The dependence of the total Au concentration (in g/ that including other Au volatile species will `stabilize'
kg) in the vapor and temperature of Au precipitation from this sensitivity.
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 5. Conclusions
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 This paper reports the rst nding of Au precipi-
deposition is very sensitive to the total Au content in the
tation from high-temperature (8008C) volcanic vapor
vapor phase. Au can precipitate inside the silica tube only if
in a silica tube experiment. Thermodynamic calcu-
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 lations were used to estimate the temperature, redox
vapor (FMQ), Au (at the mg/kg concentration in the gas and concentration constraints for Au deposition from
phase) should start to precipitate before entering the silica a highly oxidized volcanic vapor+air mixture dischar-
tube. In contrast, gas cooling itself (gas buer) or under ging from the Colima fumaroles. Despite a signicant
NNO conditions will precipitate Au at lower temperature, degree of uncertainity in the calculations due to the
close to or behind the `cool' end of the tube. lack of thermodynamic data for potentially stable vol-
atile Au species, it is possible to make the following
gas at a pressure of 1 bar with fSO2 =0.01 bar, and fO2 Pure Au precipitates from the high-temperature,
controlled by hematite/magnetite (HM), Cu2O/CuO highly oxidized vapor of Colima volcano in the form
and (fSO2 /fH2 S =1)-gas buer, as well as for a closed of triangular or pentagonal shaped thin plates, penta-
system with 0.1 bar of O2. The Cu-oxide buer is used gonal prisms or octahedra 540 mm in dimension, over
to model the high O2 fugacity, i.e. conditions at which a temperature range of 5506008C in association with
Au(g) is stable (Fig. 3). Fig. 4(AD) shows the evol- V-rich NaK sulfates.
ution of the system upon the cooling of Au gas species The observed temperature range of precipitation, as
with initial Au concentration of 0.2 mg/kg (2  1011 well as the measured Au concentration corresponds
mole fraction, corresponding to the Au concentration well to the modeled behavior of Au at fO2 controlled
in Colima condensates) and fSO2 =0.01 bar. At high fO2 by the magnetitehematite buer, but is not in agree-
Au starts to precipitate above 8008C, i.e. before enter- ment with the observed gas composition.
ing the silica tube. At fH2 =105 bar (HM buer) Au This disagreement may be caused either by essen-
precipitates between 500 and 6008C, and if fH2 is con- tially non-equilibrium conditions in the volcanic
trolled by the gas SO2/H2S buer, Au precipitates gas+air mixure (coexistence of free H2 at the redox
below 4008C, i.e. in the `cold' end of the silica tube or state of the HM buer and free O2), or by the uncer-
behind the tube. The calculated relationship between tainity in the calculations due to the lack of thermo-
total Au concentration in the vapor phase and the dynamic data for potentially stable oxidized volatile
temperature of Au condensation is shown in Fig. 5 for Au species.
open systems, with HM, FMQ, Cu2OCuO and gas The modeled behavior of a system containing only
buers, and for a closed system with fO2 =0.1 bar. In AuS(g), AuH(g) and Au(g) in respect to the Au pre-
the case of the HM buer, the temperature of conden- cipitation is very sensitive to the oxidation state of the
Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346 345

vapor phase in a complex way: temperatures of the Au tals produced by colloidal methods. Langmuir 7, 1546
precipitation are close in highly reduced and highly 1549.
oxidized environments. Hughes, J.M., Finger, L.W., 1983. The crystal chemistry of
shcherbinaite, naturally occurring V2O5. Am. Miner. 68,
Ino, 1966. Epitaxial growth of metals on rocksalt faces
Acknowledgements cleaved in vacuum. II. Orientation and structure of gold
particles formed in ultrahigh vacuum. J. Phys. Soc. Jpn.
21, 346362.
We thank E. Lounejeva for the ICP-MS analyses of
Kavaleris, I., 1994. High Au, Ag, Mo, Pb, V and W content
condensates and XRD identication of minerals and of fumarolic deposits at Merapi volcano, Central Java,
A. Cortes and J.C. Navarro for eld assistance. We Indonesia. J. Geochem. Explor. 50, 480492.
thank J. Hedenquist and R. Symonds for their reviews Knacke, O., Kubaschewski, O., Hesselmann, K., 1991.
of the rst version of the manuscript. Constructive Thermochemical Properties of Inorganic Substances.
comments by A.E. Williams-Jones and K. Brown sig- Springer-Verlag, Berlin, Heidelberg.
nicantly improved the paper. This work was sup- Korzhinsky, M.A., Tkachenko, S.I., Bulgakov, R.F.,
ported by grants from DGAPA-UNAM (No. Shmulovich, K.I., 1996. The condensate composition and
IN104197) and INTAS (No. 94-3129). native metals in sublimates from high-temperature vents of
Kudryavy volcano, Iturup, Kurile Islands. Geochem. Int.
36, 11751182.
Le Guern, F., Bernard, A., 1982. A new method for sampling
References and analyzing sublimates. Application to Merapi volcano,
Java. J. Volcanol. Geotherm. Res. 12, 133146.
Barin, I., Knacke, O., Kubaschewski, O., 1977. Le Guern, F., 1988. Ecoulements gazeux reactifs a haute tem-
Thermodynamic Properties of Inorganic Substances. perature: measures et modelisation. These de doctorat,
Springer-Verlag, Berlin and New York, NY Suppl. 1977. Universite Paris 7.
Bernard, A., Symonds, R.B., Rose, W.I., 1990. Volatile trans- Luhr, J.F., Carmichael, I.S.E., 1990. Petrological monitoring
port and deposition of Mo, W and Re in high temperature of cyclical eruptive activity at Volcan Colima, Mexico. J.
magmatic uids. Appl. Geochem. 5, 317326. Volcanol. Geotherm. Res. 42, 235260.
Bernard, A., 1985. Les mecanismes de condensation des gaz Meeker, K.A., Chuang, R.L., Kyle, P.R., Palais, J.M., 1991.
volcaniques. Ph.D thesis, University of Brussels, Belgium. Emission of elemental gold particles from Mount Erebus,
Borisenko, L.F., Seramova, E.K., Kazakova, M.E., Ross Island, Antarctica. Geoph. Res. Lett. 18, 14051408.
Shumayatskaya, N.V., 1970. First nd of crystalline V2O5 Naboko, S.I., Glavatskikh, S.F., 1997. Gold and silver in vol-
in the products of a volcanic eruption in Kamchatka. canogenic uids. Volcanol. Seismol. 18, 631652.
Doklady (Trans.) Acad. Sci. USSR 193, 683686. Quiset, J.P., Toutain, J.P., Bergametti, G., Javoy, M.,
Connor, C.B., Clement, B.M., Song, X., Lane, S.B., West Cheynet, B., Person, A., 1989. Evolution versus cooling of
Thomas, J., 1993. Continuous monitoring of high-tempera- gaseous volcanic emissions from Momotombo volcano,
ture fumaroles on an active lava dome, Volcan Colima, Nicaragua: thermodynamical model and observations.
Mexico: evidence of mass ow variation in response to at- Geochim. Cosmochim. Acta 53, 25912608.
mospheric forcing. J. Geoph. Res. 98, 19,71319,722. Seramova, E.K., 1979 (Mineralogy of sublimates of
Gammons, C.N., Willams-Jones, A.E., 1997. Chemical Kamchatkan volcanoes). Nauka, Moscow (in Russian).
mobilty of gold in the porphyry-epithermal environment. Stoiber, R.E., Rose, W.I., 1974. Fumarole incrustations at
Econ. Geol 92, 4559. active Central American volcanoes. Geochim. Cosmochim.
Gammons, C.H., Yu, Y., Williams-Jones, A.E., 1997. The dis- Acta 38, 495516.
proportionation of gold(I) chloride complexes at 25 to Symonds, R.B., Reed, M.H., 1993. Calculation of multicom-
2008C. Geochim. Cosmochim. Acta 61, 19711983. ponent chemical equilibria in gassolidliquid systems: cal-
Gerlach, T.M., Casadevall, T.J., 1986. Evaluation of gas data culation methods, thermochemical data and applications
from high-temperature fumaroles at Mount St. Helens, to studies of high-temperature volcanic gases with
19801982. J. Volcanol. Geotherm. Res. 28, 107140. examples from Mount St. Helens. Am. J. Sci. 293, 758
Giggenbach, W.F., 1996. Chemical composition of volcanic 864.
gases. In: Scarpa, R., Tilling, R.I. (Eds.), Monitoring and Symonds, R.B., 1992. Getting of gold from the gas: how
Mitigation of Volcano Hazards. Springer-Verlag, pp. 221 recent advances in volcanic gas research have provided
256. new insight on metal transport in magmatic uids. Rept.
Giggenbach, W.F., 1987. Redox processes governing the Geol. Surv. Jpn. 279, 170175.
chemistry of fumarolic gas discharges from White Island, Symonds, R.B., Rose, W.I., Bluth, G.J.S., Gerlach, T.M.,
New Zealand. Appl. Geochem. 2, 143161. 1994. Volcanic gas studies: methods, results and appli-
Hedenquist, J.W., 1995. The ascent of magmatic uid: dis- cations. In: Carroll, M.R., Holloway, J.R. (Eds.), Volatiles
charge versus mineralization. Mineralogical Association of in Magmas. Miner. Soc. Am, pp. 166.
Canada. Short Course 23, 263289. Symonds, R.B., Rose, W.I., Gerlach, T.M., Briggs, P.H.,
Hernandez, R., Diaz, G., Vazquez, A., Reyes-Gasga, J., Jose- Harmon, R.S., 1990. The evaluation of gases, condensates
Yacaman, M., 1991. Structural study of gold single crys- and SO2 emissions from Augustine volcano, Alaska: the
346 Y.A. Taran et al. / Applied Geochemistry 15 (2000) 337346

degassing of a Cl-rich volcacnic system. Bull. Volcanol. 52, A., Armienta M.A., 1998. Chemistry and mineralogy of
355374. high-temperature gas discharges from Colima volcano,
Taran, Y.A., Hedenquist, J.W., Korzhinsky, M.A., Mexico: implications for the mamatic gasatmosphere inter-
Tcachenko, S.I., Shmulovich, K.I., 1995. Geochemistry of action. J. Volcan. Geoth. Res., submitted for publication.
magmatic gases from Kudryavy volcano, Iturup, Kurile Vergasova, L.P., Naboko, S.I., Seramova, E.K., 1982.
Islands. Geochim. Cosmochim. Acta 59, 17491761. Exhalational native gold. Doklady (Trans.) Acad .Sci.
Taran Y.A., Bernard A., Gavilanes J.C., Lounejeva E.S. Cortes USSR 264, 201203.

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