Ore Geology Reviews 56 (2014) 276291

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Ore Geology Reviews

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Gold mineralization in the Guilaizhuang deposit, southwestern

Shandong Province, China: Insights from phase
relations among suldes, tellurides, selenides and oxides
Wen-Gang Xu a, Hong-Rui Fan a,, Fang-Fang Hu a, M. Santosh b, Kui-Feng Yang a,
Ting-Guang Lan a, Bo-Jie Wen a
a
b

Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
China University of Geosciences (Beijing), Beijing 100083, China

a r t i c l e

i n f o

Article history:
Received 19 December 2012
Received in revised form 18 June 2013
Accepted 21 June 2013
Available online 6 July 2013
Keywords:
Gold mineralization
Sulde
Telluride
Selenide
Phase relation
Guilaizhuang gold deposit
China

a b s t r a c t
The Guilaizhuang gold deposit is composed of limestone- and breccia-type ores. In the limestone ores, gold is
hosted by pyrite, As-bearing pyrite and arsenopyrite, whereas in the breccia ores, tellurides are the main gold
carriers. Selenium often isomorphously substitutes for sulfur in suldes in the limestone ores, but occurs as
selenides in the breccia ores. Hematite is the only oxide in the breccia ores, associated with barite and other
tellurides. In this paper, the thermodynamic parameters, especially the Gibbs free energies of formation and
reaction, of related suldes, tellurides, selenides and oxides are computed to explain the distinct mineral styles
in the limestone- and breccia-type ores. We construct the phase relations among minerals delineated by phase
diagrams at 250 C, the temperature for gold precipitation in the Guilaizhuang deposit. According to the phase
relations between suldes and selenides, we propose that gold has been transported as [Au(HS,HSe)2], and
released during rapid formation of pyrite, As-pyrite and arsenopyrite, at logfS2(g) between 12.8 and
11.4 (250 C). In the breccia ores, logfTe2(g) and logfSe2(g) are constrained within 12.9 to 9.4,
and 12.4 to 6.9 (250 C), respectively, based on the mineral assemblages observed in the ores. The
phase relations between tellurides and selenides indicate that calaverite, the only stable gold telluride
mineral in nature, was not stable in the breccia ores at 250 C during the gold precipitation. Based on
EMPA analysis, the so-called calaverite revealed from microscopic observations is in fact AuAg telluride,
probably derived from the decomposition of sylvanite (AuAgTe4) and petzite (AuAg3Te2), the only two stable
AuAg tellurides in nature at high temperature. However, we do not exclude the possibility that calaverite occurs
in this deposit, which may have precipitated in early relatively high tellurium concentration stage preceding gold
mineralization. Selenium was not detected in gold-bearing tellurides, implying that selenide is unrelated with
gold precipitation directly in the breccia ores, but can buffer the tellurium fugacity, and thus inuence the gold
precipitation indirectly. Furthermore, in logfO2(g) range of N 35.4 at 250 C, the majority of the tellurides
and selenides can be stable in the breccia ores, but residual suldes are proposed to be oxidized into sulfate
minerals, which could also free some gold into ores, although less important relative to that formed from
telluride decomposition.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Suldes, mainly pyrite, As-bearing pyrite and arsenopyrite, are the
main carriers of gold in most gold deposits (Benning and Seward,
1996; Boullier et al., 1998; Clark and Williams-Jones, 1990; Emsbo
et al., 2003; Fortuna et al., 2003; Gammons and Williams-Jones,
1997; Hofstra and Cline, 2000; Jugo et al., 1999; Kesler et al., 2002;
Lang and Baker, 2001; Pokrovski et al., 2008; Zezin et al., 2011).
However, gold-bearing tellurides, selenides and oxides have also
been reported from many epithermal AuTe deposits, telethermal
Corresponding author. Tel.: +86 10 82998218; fax: +86 10 62010846.
E-mail address: fanhr@mail.iggcas.ac.cn (H.-R. Fan).
0169-1368/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.oregeorev.2013.06.010

selenide vein-type gold deposits, and epithermal AuAg deposits in

the subaerial volcanic environments (A et al., 1988; Alderton and
Fallick, 2000; Cook and Ciobanu, 2004; Liu et al., 2000; Mills, 1974;
Nasar and Shamsuddin, 1990; Simon and Essene, 1996; Simon et al.,
1997).
Tellurides and selenides of Au, Ag, Cu, Fe and other elements are
commonly reported as trace minerals associated with gold (Ciobanu
et al., 2006; Cooke and McPhail, 2001). The association among tellurium,
selenium and gold has long been recognized by economic geologists,
and is the most evident in the prevalence of AuAg-telluridesselenides
in some ore deposits (Ciobanu et al., 2006). A comprehensive study of
tellurides, selenides, oxides and suldes is signicant for understanding
the processes of gold mineralization. Previous studies have used

W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

thermodynamic properties to calculate relative stabilities of native

elements, suldes, tellurides, selenides and oxides as a function of
fugacity of S2(g), Te2(g), Se2(g) and O2(g) (A et al., 1988; Liu
et al., 2000; Simon and Essene, 1996; Simon et al., 1997). However,
most of these studies principally focus on the thermodynamic characteristics of chemical complexes. In this paper, we provide a more simplied approach with potential application to ore-forming processes.
The Guilaizhuang gold deposit, southwestern Shandong Province,
China, is primarily composed of suldized limestones and oxidized
breccias (Hu, 2005; Teng, 1994; Yu, 2010). In the limestone ores,
gold is invisible and hosted by pyrite, As-bearing pyrite and arsenopyrite. In the breccia ores, suldes are absent, and the main gold-bearing
minerals are tellurides and oxides, with less selenides (Hu, 2005; Yu,
2010). In order to understand the geochemical signicance of these
mineral assemblages for gold precipitation, we have calculated relative
stabilities of native elements, especially Au, sulde, selenide, telluride
and oxide minerals as a function of fugacity of S2(g), Te2(g), Se2(g),
and O2(g) through thermodynamic approach. Our study provides a
better interpretation of the diversity in gold mineralization between
the two type ores in this deposit.

277

be subdivided into two sub-types, limestone- and breccia-type ores. In

the limestone ores, gold is predominantly contained by suldes, mainly
As-bearing pyrite and arsenopyrite, which occurs as disseminations in
limestone (Fig. 4a). The breccia ores, main gold producer in this deposit,
are composed of various kinds of breccias, including porphyritic syenite,
monzodiorite, carbonate rocks and sandstone, which are cemented by
lithic fragments with the same lithology as the breccias (Fig. 4b).
Calaverite (AuTe2) and hessite (Ag2Te) in the breccias are the main
gold-bearing minerals in the deposit, except the native gold associated
with them. Some other telluride minerals were also found in the deposit
by previous researchers (Hu, 2005; Yu, 2010), including weissite, altaite
and coloradoite. Minor hematite, barite, and tiemannite are closely
associated with tellurides. Gold-related uoritization is extensively
developed in the deposit, which is followed by carbonatization.
Silicication was observed locally, but the relationship between
the gold mineralization and silicication is unclear. The paragenetic
sequence of minerals in the limestone and breccia ores is illustrated
in Fig. 5.

3. Methods
2. Geological setting and ore geology
3.1. Mineralogical analysis
The Guilaizhuang gold deposit is located in the eastern margin of the
Luxi Block afliated with the Eastern Block of the North China Craton,
and is bounded by the continental Tan-Lu Fault to the east (Fig. 1a).
The Luxi Block is composed of Neoarchean gneisses, amphibolites and
tonalitic-trondhjemitic-granodioritic gneisses (TTGs), Paleoproterozoic
granitoids, Paleozoic marine carbonates interbedded with clastic rocks,
Mesozoic and Cenozoic continental clastic rocks, volcaniclastics,
intermediate-basic igneous rocks, mac dykes, carbonatites and alkaline rocks (Fig. 1b) (Lan et al., 2012; Zhang et al., 2005; Zhao
et al., 2001, 2005). The Tongshi intrusive complex is the most important magmatic body in this region (Fig. 2), composed of the
ne-grained quartz monzodiorite, porphyritic quartz monzodiorite,
and coarse- to ne-grained porphyritic syenites. LA-ICPMS zircon UPb
ages show that this complex was emplaced at 180.1184.7 Ma
(Lan et al., 2012). Previous researchers inferred that the porphyritic
syenites were genetically related with the Guilaizhuang gold deposit
(Hu, 2005; Teng, 1994; Yu, 2010).
The Guilaizhuang deposit is hosted by the CambrianOrdovician
carbonate rocks, limestone and dolomite, and controlled by the WE
trending fault (Fig. 3a, b). The gold resource is estimated to be
N30 tonnes with an average grade of 8.10 ppm (Hu, 2005; Hu et al.,
2004, 2005; Shen et al., 2001; Yu, 2010). The ores in the deposit can

Electron microprobe analysis is used to characterize and identify the

chemistry of the suldes, tellurides, oxides and selenides observed in
the deposit.
The analyses were performed on MonoCL equipment (Gatan,
Germany), scanning electron microscope (SEM) (Leo145VP, Germany)
equipped with BSD detector, energy dispersive spectrometer (EDS)
(Inca Energy 300, Oxford Instruments, UK) and EMPA (JXA-8100, JEOL
Company, Japan) equipped with ve X-ray wavelength dispersive
spectrometers (WDS), respectively, at the Institute of Geology and
Geophysics, Chinese Academy of Sciences. For CL analysis, BSE imaging, and X-ray energy spectroscopic determination, the voltage was
1020 keV, and the beam current was adjusted to the voltage
(from 0.1 to 10 nA). For EMPA analyses, Fe, S, As, Sb, Se, Bi, Ag, Cu,
Te, Hg and Au were detected in sulde, telluride and selenide minerals using a 20 keV accelerating voltage, 1020 nA beam current
and a 10s-counting time. Standards used were natural marcasite
for Fe and S, GaAs for As, stibnite for Sb, galena for Pb, cinnabar for
Hg, bismuthite for Bi, and native gold, silver, tellurium, copper,
zinc, nickel, cobalt, and selenium for Au, Ag, Te, Cu, Zn, Ni, Co, and
Se, respectively. The detection limits for the target elements in this
study are: Fe 0.03%, S 0.05%, Au 0.04%, Ag 0.04%, As 0.03%, Te 0.05%,

Fig. 1. (a) Tectonic setting of the Luxi Block, modied after Zhao et al. (2005) and (Santosh (2010). (b) Geological and tectonic map of the Luxi Block and the location of the
Guilaizhuang gold deposit, modied after Lan et al. (2012).

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W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

Fig. 2. Geological map of the Tongshi intrusive complex and the location of the Guilaizhuang gold deposit, modied after Lan et al. (2012).

Cu 0.03%, Pb 0.03%, Zn 0.04%, Hg 0.04%, Ni 0.04%, Co 0.03%, Bi 0.03%,

Se 0.04%, and Sb 0.04%.

range for a solid phase, and fGoT value at room temperature can be
found in thermodynamics handbook. Hence, we can calculate fGoT
value of compound in solid phase at interesting temperature T:

3.2. Phase relations construction methods

The chemical potential equilibrium method was applied in construction of phase relations among various minerals, which has
been described by A et al. (1988) and Simon and Essene (1996).
Here we provide the salient details with specic relevance to
geological applications.
3.2.1. Gibbs free energy of formation
All Gibbs free energies of formation used in this study for sulde,
telluride, selenide and oxide minerals are those from elements in
their stable form at the temperature of interest (T) and pure ideal
S2(g), Te2(g), Se2(g) and O2(g), with notation of fGoT kJ/mol. The fGoT
values have been partially compiled from related works (see tables in
Appendices 1 and 2). The GibbsHelmholtz equation was used as
there was no information on the standard Gibbs free energies of formation from elements in their stable state (particularly in solid state) at
1 bar and the temperature of interest:

o
fTGT
T

f Hm
T2

where fHom represents the molar enthalpy of formation at room temperature (298 K), considered to be constant in a wide temperature

f GT T 


o
f G298
298

f G298

K 


298T
3
=10 :
298 T

Previous microthermometric data on ore-stage uid inclusions in

the Guilaizhuang deposit indicate that gold was precipitated at ca.
250 C (Hu, 2005; Hu et al., 2005; Shen et al., 2001). We therefore
set the temperature of interest to be 250 C (=523.15 K) in this
study. Based on the EMPA results, the metallic elements selected for
phase relation studies include Au, Ag, As (semi-metal element), Bi,
Cu, Fe, Hg, Ni, Pb, Sb, Sn and Zn.
The Gibbs free energies of formation for sulde, telluride, selenide
and oxide minerals in this study are listed in Appendix 1.
3.2.2. Fugacity calculations
The fugacities of S2(g), Te2(g), Se2(g) and O2(g) are useful measures of the relative stability of solid phase, and is independent of
whether we use aqueous solutions or gases to derive the equilibrium
reactions for solid phase (Simon and Essene, 1996).
For a given balanced reaction, the equilibrium constant (lnK) can
be calculated from Gibbs free energy of reaction (fGoT):
lnK

r GoT
RT

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279

Assuming that the solid phases are pure, the equilibrium constant
will be a function of temperature. Therefore, we can obtain the fugacity
for this reaction as form of:
logF lnK=2:303
A et al. (1988) and Simon and Essene (1996) proposed that because
the change in volume for the solids is generally small, the effect of conning pressure on the equilibrium constant is not signicant for a pressure of
up to 1 kbar for most reactions in this study. Previous uid inclusion studies have estimated the mineralization pressure at Guilaizhuang deposit is
lower than 500 bar (Hu, 2005; Shen et al., 2001; Yu, 2010), and therefore,
the inuence of pressure can be neglected in this study.
Here we subdivide the equilibrium mineral systems into two
sub-systems, univariate and bivariate one, for fugacity calculation.
In univariate system, the fugacity of the gaseous member in a
given reaction can be calculated according to the method above.
Taking the balanced reaction below for example:
2AsS 0:5S2 g As2 S3 :
The fugacity of S2(g) of this reaction can be calculated as follows
(T = 523.15 K):
o

r GT523:15 K f GT523:15 K As2 S3


o
o
0:5  f GT523:15 K S2 g 2  f GT523:15

K AsS

The Gibbs free energies of formation of As2S3, S2(g) and AsS

are 83.52, 45.64 and 32.58 kJ/mol, respectively, so we obtain
the Gibbs free energy of this reaction, which equals to 41.18 kJ/mol.
So the equilibrium constant lnK:
o

lnK

r GT523:15
RT

9:47

and
logf S2 g 2 lnK=2:303 8:22:
Fig. 3. Geological map of the Guilaizhuang gold deposit, modied after Yu (2010).
(a) Map view. (b) No. 30 prospecting prole with section line AB in (a).

However, in bivariate system, the functional relationship between the

fugacity of gaseous species should be expressed as the following form:

where R refers to the gas constant, 0.008314 kJ/molK, T temperature

in Kelvin, and:

logf A a logf B b



o
o
o
f GT i f GT res j f GT rea

where A and B represent gaseous species, whereas a and b denote

calculation coefcients. The phase relation between compound with
A and compound with B can be constructed accordingly. Taking the
balanced reaction below as an example:

where res and rea represent resultant and reactant of the reaction,
respectively, and i and j denote the stoichiometric number of
corresponding resultant and reactant.

Ag2 Te 0:5 Se2 g Ag2 Se 0:5 Te2 g:

Fig. 4. Photographs of (a) the limestone ores, with gold-bearing suldes mainly disseminating in the dark bands; and (b) breccia ores.

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W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

4. Results
4.1. Texture and composition

Fig. 5. Paragenetic sequence of minerals in the limestone and breccia ores.

The equilibrium constant lnK can be written as:

o

lnK

r GT523:15
RT

1:37

and



0:5
0:5
log f Te2 g =f Se2 g
lnK=2:303
then the functional relationship between fTe2(g) and fSe2(g) will be:
logf Te2 g logf Se2 g1:19:
Lastly, the phase relation between hessite (Ag2Te) and naumannite
(Ag2Se) can be constructed.
Using the methods mentioned above, we have obtained the fugacities of S2(g), Te2(g), Se2(g) and O2(g) of the equilibrium reactions in
univariate and bivariate systems, and have listed them in Appendix 2.

Backscattered electron (BSE) images of the suldes, tellurides,

oxides and selenides are shown in Figs. 6 and 7. In limestone-type
ores, the suldes include pyrite, As-bearing pyrite, arsenopyrite and
tetrahedrite. BSE images show that pyrite is commonly surrounded by
As-pyrite which is in turn cemented by tetrahedrite. Tetrahedrite exsolution is noticed in pyrite (Fig. 6). The precipitation of As-pyrite implies
that As concentration in the hydrothermal uids increased gradually
with the decrease of sulfur concentration, and therefore arsenopyrite
likely formed after As-pyrite. The above observation indicates that
As-pyrite and arsenopyrite were preceded by pyrite and followed by
tetrahedrite, from the evolving sulfur-rich uids. In breccia-type ores,
tellurides, calaverite, Cu-telluride and hessite, the main gold producer,
are paragenetically associated, as shown in Fig. 7a and b. Tiemannite
(HgSe) is scattered in the assemblages, locally accompanied by barite
(Fig. 7c and e). Tiny grains of native gold, 24 m in size, are embedded
in calaverite (Fig. 7f). Hematite is also found in the colloidal and grain
forms (Fig. 7g and h), which is considered to be a primary phase by
previous researchers (Hu, 2005; Hu et al., 2005; Shen et al.,
2001). Previous studies also reported native silver, tellurium, electrum, frohbergite, altaite, clausthalite, coloradoite, melonite and
CuAu telluride (Hu, 2005; Hu et al., 2005; Yu, 2010).
The EMPA results from this study and previous work are listed in
Tables 1 and 2. The EMPA analysis of the suldes in limestone-type
ores shows that gold widely occurs in pyrite, As-pyrite, arsenopyrite,
and locally tetrahedrite. The As-pyrite usually contains higher concentrations of Au than other suldes, ranging from 600 to 2500 ppm. Sb
mainly concentrates in tetrahedrite (12.36 to 15.21 wt.%) with minor
in As-pyrite and arsenopyrite. No tellurium can be detected in this
type ore. Gold grains in the breccia ores always host minor silver
(b 6 wt.%). Tellurides in the breccia ores are mainly composed of
AuAg-, Ag-, Cu-, Fe-, Pb-, and Hg-tellurides. Native Te(s) and
Ag(s) can also be detected in previous studies.
In the limestone ores, selenium is widely contained by suldes,
especially enriched in As-pyrite, arsenopyrite and tetrahedrite, ranging
from n 100 to n 1000 ppm with S/Se ratio of n 103. It has been
widely accepted that the concentrations of some trace elements in pyrite
may serve as good genetic indicators (Hawley and Nichol, 1961; Ivor
Roberts, 1982; Liu et al., 2000; Loftus-Hills and Solomon, 1967;
Raymond, 1996). In hydrothermal pyrite, the concentration of Se is
high (2050 ppm), with S/Se ratios between 1 104 and 2.67 104,
and in pyrite associated with volcanics, the Se concentration is even
higher (up to 10002000 ppm), with an S/Se ratio of the order of
n 103. Thus pyrite in the limestone ores at Guilaizhuang probably is
of magmatic origin. Other suldes cogenetic with pyrite should be also
of volcanic origin. All of these suldes were likely precipitated from a
sulfur-rich magmatic vapor containing signicant amount of gold.
4.2. Phase relations among suldes, selenides, tellurides and oxides
4.2.1. Phase diagram construction
Fugacityfugacity diagrams are regarded as a useful tool to investigate the phase relations between paired compounds and predict equilibrium assemblages for a given system and the occurrence forms of
elements such as Au, Ag and Cu. Four types of fugacityfugacity
diagrams were constructed for the Guilaizhuang deposit based on a
common logarithm form at 250 C: logfS2(g)logfSe2(g), logfTe2(g)
logfSe2(g), logfTe2(g)logfO2(g), and logfSe2(g)logfO2(g).
logf S2 g logf Se2 g

diagram:

The logfS2(g)logfSe2(g) diagram (Fig. 8) shows the stability elds

of binary selenides and suldes, and provides useful information on

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281

Fig. 6. Backscattered electron images of suldes in the limestone ores. a: arsenopyrite; b: pyrite grain in perfect pyritohedron shape; c: pyrite (Py), As-bearing pyrite (AsPy),
arsenopyrite (Apy), and tetrahedrite (Td), noting that the AsPy surrounds the Py and is cemented by Td in the last stage; (d) exsolution of Td from Py.

chemical evolution of the hydrothermal uids and gold precipitation

in the limestone ores. Selenides in this diagram are selected based on
the EMPA results, including FeSe, NiSe, AgSe, SbSe, AuSe, CuSe,
HgSe, PbSe and AsSe compounds, most of which are stable in nature at 250 C, and have been reported from many selenide deposits
(A et al., 1988; Ciobanu et al., 2006; Echmaeva and Osadchii,
2009; Liu et al., 2000; Mills, 1974; Simon et al., 1997). Although
many natural minerals occur in the CuSe system, only Cu2SeCuSe
binary is constructed in our study due to their stability in the temperature range of gold mineralization in the Guilaizhuang deposit. In the
FeSe system, the only stable compounds at room temperature are
Fe1 + xSe and FeSe2 (Mills, 1974), and above 200 C, the phase
diagram for this system contains ve compounds, Fe1 + xSe (x =
0.040.06), Fe1 xSe (x = 0.000.28), Fe1 xSe (x = 0.180.37),
FeSe2 and Fe7Se8 (Schuster et al., 1979). Based on the fugacity of
Se2(g) and temperature in our study, only FeSe1.333, the and phase,
and FeSe2 were selected. The upper and lower limits of logfSe2(g)
were set at Se2(g)Se(l) and Ag-naumannite binaries, respectively.
Suldes in this diagram include bornite (Bn), chalcopyrite (Cp), pyrrhotite (Po, Fe0.89S), pyrite (Py), arsenopyrite (Apy), argentite, cinnabar,
stibnite, realgar and orpiment, which are stable in nature and common
in many hydrothermal deposits (Archibald et al., 2002; Franchini et al.,
2011; Halter et al., 2002; Landtwing et al., 2005; Redmond et al., 2004;
Richards, 2011; Young et al., 2003; Zajacz et al., 2011).
In this diagram, native gold is stable and coexists with almost
all selenides and suldes in the common range of logfSe2(g) and
logfS2(g), except native selenium and krutaite (CuSe2) that exist
only at very high logfSe2(g), close to selenium saturation line. When
logfSe2(g) is lower than 16.2, native silver will be stable at this temperature, coexisting with Cu2Se likely, and to form eucairite (CuAgSe)

in the metal-rich part of the system. The stable eld of suldes is

broader than that of selenides, explaining the prevalence of suldes
over selenides in most hydrothermal ore deposits.
The diagram also shows the selenide and sulde assemblages.
For example, naumannite can occur in equilibrium with common
suldes in ore deposits, such as pyrite, arsenopyrite, galena, stibnite,
chalcopyrite and bornite. These mineral assemblages can be used
to constrain fugacity conditions. For example, berzelianite (Cu2Se) +
pyrrhotite (Fe0.89S) chalcopyrite represents an equilibrium assemblage at logfSe2(g) between 10.1 and 14.2 and logfS2(g)
between 16.4 and 18.8 at 250 C.
logf Te2 g logf Se2 g diagrams:
Telluride minerals are the main gold-bearing species in the breccia ores at Guilaizhuang. The common telluride compounds involved
in this study include AuTe, AgTe, FeTe, CuTe, NiTe, HgTe, Bi
Te, SbTe, AsTe, PbTe and ZnTe. In FeTe system, the only iron
telluride mineral is frohbergite (FeTe2), which occurs in a variety of
telluride deposits (A et al., 1988; Simon and Essene, 1996; Simon
et al., 1997). However, in this study, the phase (FeTe0.9) was also
considered for phase equilibrium analysis. The minerals in NiTe
system contain two end compounds of (NiTe2 x; x = 00.9) phase,
NiTe1.1 and NiTe2. The phase diagram for CuTe is complicated by the
presence of compounds containing both Cu+ and Cu2+ in defect structures (A et al., 1988), and the three principal compounds used in the
study are the minerals weissite (Cu2Te), rickardite (Cu4Te3) and
vulcanite (CuTe).
The stability of telluride and selenide minerals is shown in Figs. 9
and 10, as a function of logfTe2(g) and logfSe2(g) at 250 C. The limits of

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W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

Fig. 7. Backscattered electron images of tellurides, selenides, oxides and native gold in the breccia ores. See text for details.

W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

Table 1
EMPA results (wt.%) of suldes in the limestone ores from the Guilaizhuang deposit.a
Sample

Fe

As

Se

Au

Ag

Sb

Te

Cu

Total

Py

52.90
53.18
52.81
53.35
52.62
52.65
52.69
52.70
52.28
51.43
46.60
47.84
45.26
46.29
45.02
45.35
53.12
51.15
47.55
52.24
47.84
52.71
51.38
21.35
22.45
25.63
24.65
24.34
25.64
25.23
25.08
25.13
25.30
25.96
25.74
26.09

45.59
45.84
44.88
45.20
45.68
45.65
45.71
45.83
44.82
45.44
44.98
44.38
45.15
45.27
45.45
45.45
44.19
44.48
44.42
43.84
45.78
45.57
44.51
30.01
30.04
30.26
28.84
29.93
31.02
30.42
0.44
1.96
3.02
2.81
2.18
1.74

u.db
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
7.80
5.30
6.40
4.61
6.88
6.30
2.10
2.32
5.24
3.20
5.25
1.34
3.45
47.03
46.09
43.03
45.63
44.02
44.67
44.12
10.24
9.64
10.26
9.20
8.21
10.20

0.05
u.d
u.d
u.d
0.06
u.d
0.06
0.16
0.04
u.d
0.12
0.16
0.10
0.06
0.09
0.12
0.11
0.13
0.10
0.10
0.09
0.05
0.21
0.05
0.07
0.12
0.16
0.10
0.04
0.06
0.16
0.17
0.15
0.09
0.11
0.08

0.12
0.06
0.05
0.10
0.07
0.18
0.11
0.04
0.11
0.20
0.25
0.15
0.17
0.14
0.17
0.11
0.07
0.06
0.11
0.09
0.12
0.09
0.10
0.12
0.09
0.06
0.11
0.12
0.09
0.11
0.07
0.05
0.08
0.06
0.06
0.14

u.d
0.05
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.09
0.11
0.09
0.10
0.08
0.09
u.d
0.11
u.d
u.d
0.05
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.10
u.d
0.05
0.05
0.05
0.05

u.d
u.d
0.08
0.04
u.d
u.d
u.d
0.05
0.04
0.08
0.75
0.58
0.24
0.26
u.d
u.d
12.54
u.d
u.d
u.d
u.d
12.03
13.24
0.11
0.09
0.12
0.08
0.09
0.10
0.07
14.01
12.36
15.21
13.37
u.d
u.d

u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d

u.d
u.d
0.04
u.d
0.03
0.03
u.d
u.d
u.d
u.d
u.d
2.24
2.42
1.70
1.47
0.23
0.03
2.10
0.03
u.d
u.d
u.d
u.d
0.12
0.23
0.09
0.11
0.13
0.09
0.14
18.75
38.96
18.27
19.81
19.05
18.36

98.66
99.13
97.86
98.69
98.46
98.51
98.47
98.78
97.29
97.15
99.84
100.65
100.34
98.41
99.42
97.66
99.61
100.75
97.48
99.46
99.11
99.79
99.50
98.79
99.06
99.31
99.58
98.73
100.05
100.05
66.93
89.12
71.13
70.39
70.58
70.63

1
2
3
4
5
6
7
8
9
10
AsPy 1
2
3
4
5
6
7
8
9
10
11
12
13
Apy
1
2
3
4
5
6
7
Tdc
1
2
3
4
5
6
a

Data source: this study.

u.d = under detection limit.
c
The rest component of Td is zinc, which has not been determined in EMPA but can
be detected by energy dispersive spectrometer (EDS).
b

logfTe2(g) and logfSe2(g) can be determined by mineral assemblages

observed in SEM analyses, which will be discussed in a later section.
logf O2 g logf Te2 g and logf O2 g logf Se2 g

diagrams:

Hematite is the only oxide in the breccia ores, which is an important

index to determine the oxygen fugacity. Barite is associated with hematite in the ores (Fig. 7g), which can be used to construct the phase diagrams in this study. Other oxides involved in these diagrams include
CuO, BiO, PbO, AsO, NiO, ZnO, SnO and SbO. Tellurides and
selenides included in these diagrams are the same as those in Figs. 9
and 10. The diagrams are shown in Figs. 11 and 12.
The phase diagrams shown in Figs. 11 and 12 indicate that most selenides, except SnSe2 and SnSe, coexist with hematite over a large range
of logfO2(g) and logfSe2(g), with an exception for Sn and Fe. It is clear
that most metallic oxides are unstable with respect to tellurides, consistent with the absence of oxides except cassiterite, magnetite, or hematite from hypogene telluride ores (A et al., 1988).
5. Discussion
5.1. Limitation of fugacity ranges of S2(g), Te2(g), Se2(g) and O2(g)
5.1.1. LogfS2(g)
Suldes in the limestone ores include pyrite, As-pyrite, arsenopyrite
and tetrahedrite. The phase diagrams of logfS2(g) show that arsenopyrite is only stable at the logfS2(g) range between 14.9 and 11.4,

283

which can be used to limit the fugacity of S2(g) in the limestone ores.
Because of the absence of pyrrhotite, the logfS2(g) for pyrrhotitepyrite
equilibrium must be higher than 12.8. Thus we obtain the logfS2(g)
range between 12.8 and 11.4.
5.1.2. LogfTe2(g)
Tellurides are widely developed in the breccia ores in the
Guilaizhuang deposit (Hu, 2005; Yu, 2010), including calaverite,
hessite, AuAg-telluride, Fe-telluride, Cu-telluride, altaite, coloradoite
and melonite (see Table 2). The presence of native gold indicates that
the upper limit of logfTe2(g) can be dened by the phase equilibrium
of AuAuTe2 binary, which equals to 9.4. The lower limit of logfTe2(g)
is supported by the EMPA results of the tellurides in the breccia ores.
Fe-telluride of num. 19 in Table 2 was determined to be FeTe2.24, close
to FeTe2 in FeTe binary, for which the equilibrium tellurium fugacity
is 12.9. Therefore, the logfTe2(g) is constrained at between 12.9
and 9.4. In this fugacity range, telluride minerals, except calaverite
that will be discussed later, from the Guilaizhuang deposit can be linked
together, and are also consistent with the fact that native gold is widely
distributed in ores.
5.1.3. LogfSe2(g)
Based on microprobe analysis, HgSe is stable in the breccia ores.
Because selenium is extremely low in the Guilaizhuang deposit, it is
reasonable to assume a constant selenium concentration during the
evolution of the hydrothermal system (Echmaeva and Osadchii, 2009;
Okamoto, 1990; Okamoto and Massalski, 1986; Schuster et al., 1979;
Simon and Essene, 1996; Simon et al., 1997), based on which we can
x the lower limit of logfSe2(g) at Hg(l)HgSe binary, equal to 12.4.
Based on thermodynamic and experimental results, Okamoto and
Massalski (1986) pointed out that native gold and native selenium are
unlikely to coexist at any tempe
rature, and AuSe is the only known binary compound in the AuSe system, although it has not yet been identied as a discrete mineral. Thus
the equilibrium logfSe2(g) for AuAuSe (6.9, at 250 C) should be
used to constrain the Se fugacity in this study. The logfSe2(g) range
can be dened as 12.4 to 6.9.
5.1.4. LogfO2(g)
Hematite is the only metallic oxide in the breccia ores and can be
used to limit the oxygen fugacity. The lower limit of logfO2(g) is estimated to be 35.4, the equilibrium oxygen fugacity for magnetite
hematite at 250 C. The upper limit of logfO2(g) is dened by the
fugacity of atmospheric oxygen, although this condition is generally
not attained during telluride and selenide deposition.
The limits of fugacities of S2(g), Te2(g), Se2(g), and O2(g) in phase
diagrams are shown in Figs. 8 to 12.
5.2. Interpretation of the different gold precipitation types
5.2.1. Gold precipitation in the limestone ores
In logfS2(g)logfSe2(g) phase diagram, the S2(g) fugacity range
is extremely limited, indicating that suldes were precipitated rapidly
in a short period under reducing condition. Selenium is highly
chalcophile, and often substitutes for sulfur in sulde minerals due
to the similarity of their crystallochemical properties, especially in
reducing environment (Liu et al., 2000; Simon and Essene, 1996).
Many available experiments and calculations have proven that gold
can form a stable complex with sulfur in a vapor phase (Benning
and Seward, 1996; Gammons and Williams-Jones, 1997; Jugo et al.,
1999; Kamenetsky et al., 1999; Kesler et al., 2002; Metrich and
Clocchiatti, 1996; Pokrovski et al., 2008; Richards, 2011; Simmons
and Brown, 2006; Simon and Ripley, 2011; Tosdal et al., 2009;
Williams-Jones and Heinrich, 2005; Williams-Jones et al., 2009;
Zezin et al., 2011). According to the phase diagram in Fig. 8, the selenium fugacity is not high enough to form AuSe, thus Au is probably

284

W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

Table 2
EMPA results (wt.%) of gold related minerals in the breccia ores, Guilaizhuang deposit.a
Num.

Mineral

Au

Ag

Te

Fe

Cu

Pb

Zn

Hg

Ni

Co

As

Bi

Se

Sb

Total

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43

Native Au(s)
Native Au(s)
Native Au(s)
Native Au(s)
Native Au(s)
Native Au(s)
Electrum
Calaveritec
Calaverite
Calaverite
Calaverite
Calaverite
Calaverite
Calaverite
Calaverite
Calaverite
Hessite
Petzite
Frohbergite
Altaite
Altaite
Altaite
Altaite
Clausthalite
Clausthalite
Cutelluride
Cutelluride
Cutelluride
Cutelluride
Cutelluride
Cutelluride
Cutelluride
Cutelluride
AuAgtelluride
Coloradoite
Melonite
Melonite
Tiemannite
Tiemannite
Tiemannite
Native Te(s)
Native Te(s)
Native Ag(s)

96.81
96.38
96.49
93.08
94.01
90.97
84.14
28.88
28.96
29.62
29.80
25.82
28.76
28.60
25.78
32.54
0.65
25.78
0.28
u.d
u.d
4.26
4.32
u.d
u.d
38.13
30.02
28.43
27.47
26.35
25.41
23.05
21.63
26.33
0.25
u.d
0.06
u.d
u.d
u.d
u.d
u.d
u.d

4.31
4.36
0.98
5.43
3.27
3.91
13.53
8.57
8.99
8.32
8.23
10.76
9.78
8.63
10.37
1.24
59.89
40.58
0.36
1.32
0.87
0.74
0.61
0.64
0.47
0.11
0.53
0.65
0.67
0.22
0.84
0.51
0.14
40.78
0.15
u.d
0.19
u.d
u.d
u.d
0.42
u.d
97.63

u.db
u.d
0.14
u.d
1.2
4.1
0.17
62.52
61.97
61.97
61.32
62.40
61.22
61.64
63.14
61.49
37.77
33.15
82.37
42.38
36.42
15.26
14.93
2.65
2.88
60.27
64.55
65.90
65.76
66.92
70.22
72.10
71.90
32.68
37.44
78.07
85.54
0.14
0.23
0.16
99.04
99.67
2.13

0.09
u.d
0.07
0.14
u.d
u.d
0.14
0.31
u.d
0.03
u.d
u.d
0.16
u.d
0.07
3.26
0.07
u.d
16.13
0.18
1.21
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.16
0.19
0.12
u.d
u.d
0.03
0.13
u.d

0.07
u.d
0.27
0.33
u.d
u.d
0.08
0.24
0.31
u.d
u.d
0.49
u.d
u.d
0.64
0.78
u.d
u.d
0.35
0.34
0.06
0.22
u.d
u.d
u.d
1.49
4.89
5.02
6.11
6.52
3.53
4.34
6.34
0.07
0.04
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d

u.d
u.d
u.d
u.d
u.d
u.d
0.10
u.d
u.d
0.08
0.03
0.31
u.d
0.91
u.d
u.d
u.d
u.d
u.d
53.17
59.21
64.00
64.62
70.26
69.54
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.13
u.d
u.d
u.d
u.d
0.31
u.d
u.d

u.d
u.d
0.06
0.08
u.d
u.d
0.14
0.14
0.04
u.d
0.08
u.d
0.10
u.d
u.d
u.d
u.d
0.12
0.30
0.74
0.16
0.12
0.10
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.27
0.12
u.d
u.d
u.d
u.d
0.04
u.d
u.d

u.d
u.d
0.05
u.d
u.d
u.d
0.05
0.05
u.d
u.d
u.d
0.06
u.d
u.d
u.d
u.d
0.16
u.d
0.11
1.87
1.43
7.14
7.36
0.50
0.47
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.05
u.d

u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.12
63.64
u.d
u.d
64.34
65.32
63.78
u.d
u.d
u.d

u.d
u.d
0.09
0.18
u.d
u.d
0.06
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.18
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.16
18.01
13.83
u.d
u.d
u.d
u.d
u.d
u.d

u.d
u.d
0.07
0.12
u.d
u.d
0.10
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.11
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.08
0.98
0.09
u.d
u.d
u.d
u.d
u.d
u.d

0.06
u.d
u.d
0.07
0.36
0.37
0.09
u.d
u.d
u.d
0.05
0.16
u.d
0.20
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.21
0.22
u.d
u.d
u.d
u.d
u.d
0.06
0.22

u.d
u.d
0.68
0.40
u.d
u.d
0.89
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
1.46
2.10
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.14
0.13
0.09
u.d
u.d
u.d
u.d
u.d
u.d

u.d
u.d
0.16
0.17
u.d
u.d
0.16
u.d
u.d
u.d
0.06
u.d
u.d
0.04
u.d
u.d
0.19
u.d
0.10
u.d
u.d
8.16
7.92
20.23
20.13
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.21
0.19
u.d
34.56
35.42
36.20
u.d
u.d
u.d

0.15
u.d
0.09
0.18
1.14
1.02
0.18
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.62
0.33
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
u.d
0.32
0.61
u.d
u.d
u.d
u.d
u.d
u.d
u.d

101.49
100.74
99.15
100.17
99.98
100.41
99.71
100.70
100.27
100.02
99.59
100.00
100.02
100.02
100.00
99.93
99.38
99.63
100.00
100.00
99.35
99.90
100.00
95.74
95.60
100.00
99.99
100.00
100.00
100.01
100.00
100.01
99.99
99.38
102.91
98.69
99.99
99.16
100.97
100.14
99.85
99.91
99.98

a
b
c

Data source: Yu (2010) and this study.

u.d = under detection limit.
The calaverite listed in this table is identied by microscopic observation and inherited from previous studies, which will be discussed detailed in text.

complexed by SSe. This allows us to assume the existence of a Au

SSe complex probably in the form of [Au(HS,HSe)2]. Fig. 8 also shows
that FeSe2, Sb2Se3 and As2Se3 are stable in this condition, in equilibrium
with FeS2 (Py), Sb2S3 and arsenopyrite (Apy). In Carlin-type gold deposits, iron in pyrite, As-pyrite and arsenopyrite are considered to
have derived from the ferriferous carbonaceous country rock (Cline et
al., 2005; Heitt et al., 2003; Hofstra and Cline, 2000; Mao, 1991;
Mumin et al., 1994; Palenik et al., 2004; Simon et al., 1999; Su et al.,
2008). Therefore, gold precipitation can be caused by the following
chemical reactions:


2
0

AuHS; HSe2 2Fe Au FeS2 FeSe2 0:5H2 g 3H



2
0
AuHS; HSe2 2Fe 10=3AsAu 2FeAsS 2=3As2 Se3

0:5H2 g 3H


0
AuHS; HSe2 8=3Sb H Au 2=3Sb2 S3 2=3Sb2 Se3
2:5H2 g:

As and Sb were probably carried in the vapor phase, forming arsenopyrite and Zn-bearing tetrahedrite, postdating the precipitation of
pyrite. Gold hosted by pyrite, As-pyrite and arsenopyrite is invisible,
and probably exists as nano-particles in the crystal lattice of suldes,
similar to the occurrence of gold in many Carlin-type deposits (Cabri
et al., 2000; Hofstra and Cline, 2000; Palenik et al., 2004).
5.2.2. Gold precipitation in the breccia ores
In the breccia ores, the oxygen fugacity is generally higher, and
most selenides and tellurides, except Sn selenides and Fe telurides,
coexist with hematite over a large range of logfO2(g), logfSe2(g) and
logfTe2(g) (Figs. 11 and 12), consistent with the observation from
many telluride ores (A et al., 1988). Under such oxidizing condition, suldes are no longer stable and would be oxidized to SO2
4 ,
and selenium would be released from the complex and form selenides (Liu et al., 2000):


2
2
0
AuHS; HSe2 5O2 g 2Ba 2Hg Au 2BaSO4 barite
2HgSetiemannite 2H2 O:

W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

285

Fig. 8. LogfS2(g)logfSe2(g) diagram showing the relative stability of selenides and suldes
at 250 C. The shaded area represents the fugacity range of S2(g) and Se2(g) in this study.
Abbreviations: Apy = arsenopyrite, Bn = bornite, Cp = chalcopyrite, Lo = loellingite,
Po = pyrrhotite.

However, sulfur concentration was dramatically reduced in oreforming uids by the suldization process in the limestone ores,
thus the oxidization reaction shown above is not signicant for gold
precipitation in the breccia ores.
Gold-bearing tellurides (and selenides) are commonly present
as trace minerals in many gold deposits, indicating that tellurium
(and selenium) can be a signicant gold carrier (Cepedal et al.,
2006; Ciobanu et al., 2006; Hu et al., 2006; Novoselov et al., 2006;

Fig. 9. LogfTe2(g)logfSe2(g) diagram showing the relative stability of selenides and

tellurides at 250 C. The shaded area represents the fugacity range of Te2(g) and
Se2(g) in this study.

Fig. 10. LogfTe2(g)logfSe2(g) diagram showing the relative stability of selenides and
tellurides at 250 C. The shaded area represents the fugacity range of Te2(g) and
Se2(g) in this study.

Plotinskaya et al., 2006; Spry and Scherbarth, 2006; Vikentyev,

2006; Voudouris, 2006). Gold is probably complexed by tellurium in
the form of [Au(HTe)2] and/or [HAu(HTe)2]. In the Guilaizhuang deposit, telluride is the main gold-bearing mineral, as shown in Table 2.
However, according to the phase diagrams (Figs. 9 and 10), native
gold cannot coexist with calaverite, because of the high telluride

Fig. 11. LogfO2(g)logfTe2(g) diagram showing the relative stability of selenides and
tellurides at 250 C. The shaded area represents the fugacity range of O2(g) and
Te2(g) in this study.

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W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

Fig. 13. Phase relations in the system AuAgTe at 250 C, modied after Cabri (1965)
and A (1988). EMPA data of AuAg tellurides in Table 2 (num. 818 and 34) are
plotted in the diagram denoted by the solid dots.
Fig. 12. logfO2(g)logfSe2(g) diagram showing the relative stability of selenides and
oxides at 250 C. The shaded area represents the fugacity range of O2(g) and Se2(g)
in this study.

fugacity for calaverite formation. Based on the EMPA results, the

calaverite identied from microscopic observations is in fact a
AuAg telluride as shown in Fig. 13, except num. 16 in Table 2,
which approximates to AuTe2 in stoichiometric composition.
As reported in previous studies (A et al., 1988; Cabri, 1965;
Echmaeva and Osadchii, 2009; Voudouris, 2011; Voudouris et al.,
2011), Au and Ag can be complexed by Te to form AuAgTe ternary
system. In this system, minerals stable along the binary AuTe and
AgTe joins include electrum, krennerite ((Au,Ag)Te2), sylvanite
(AuAgTe4) and petzite (AuAg3Te2) (Fig. 13).
Sylvanite and petzite are stable in higher temperature (b354 C),
which represent the main form of gold precipitating primarily from
the ore-forming uids in the oxidized and acidic condition:


Au; AgHTe2 1:75O2 3H 2HTe AuAgTe4 sylvanite

3:5H2 O




Au; AgHTe2 2 AgOH2 3H

2:25O2 AuAg3 Te2 petzite 4:5H2 O:
Sylvanite and petzite are unstable as temperature decreases,
and decompose into hessite and calaverite at temperature below
~ 120 C (A et al., 1988; Cabri, 1965; Echmaeva and Osadchii,
2009; Voudouris et al., 2011). At the relatively low temperature of
gold precipitation estimated in this study (ca. 250 C), the decomposition process should be buffered by other stable tellurides such as
PbTe, Bi2Te3, FeTe2 and HgTe (Figs. 9 and 10), producing native
gold, hessite and AuAg tellurides with composition on the tie lines
among calaverite, sylvanite and petzite, as the plotted dots shown
in Fig. 13:
AuAgTe4 Aux0 1 AgTe4 1xAu
e

and 50 C into a mixture of petzite, hessite, stutzite, krennerite and

sylvanite. The plotted dots on the tie lines among calaverite, sylvanite
and petzite in Fig. 13 could probably represent the solid solutions
produced by the decomposition of the - and -phases, but due to
limited thermodynamic data, the decomposition reactions of these
two phases could not be provided here.
According to the phase relations between selenides and tellurides,
pure calaverite cannot coexist with native gold produced by the abovementioned decomposition process. Therefore, we interpret that the
data num. 16 in Table 2, represented by the solid dot close to AuTe2
end member in Fig. 13, is actually a supergene alteration product of
AuAg tellurides lying on the tie lines, with byproducts of native silver.
However, we do not exclude the possibility that this data point may
represent the occurrence of calaverite which precipitated before the
gold under a relatively high tellurium fugacity, similar with the cases
in other AuTe deposits, such as the Sandaowanzi deposit of China
(Han et al., 2011; Yu et al., 2012). Native tellurium found in this deposit
should have precipitated in the early extremely high tellurium fugacity
stage preceding gold mineralization.
As shown by EMPA results, selenium is absent in AuAg tellurides
at Guilaizhuang, implying that selenium is not directly related with
gold precipitation in the breccia ores. The equilibrium between selenides and tellurides can buffer tellurium fugacity, which could probably inuence the decomposition process of AuAg tellurides and gold
precipitation indirectly.
As shown in Fig. 9, no Cu-tellurides are stable in our study, because of the high selenium fugacity. Cu-tellurides, num. 26 to 33
(Table 2), are not pure (e.g. kostovite), which should be incorporated
by gold and/or other metallic elements to form a AuCuTe system
similar to the case of the AuAgTe system discussed above (A
et al., 1988; Simon and Essene, 1996; Simon et al., 1997; Voudouris
et al., 2011), consistent with the EMPA results in this study.
5.3. Potential mineral predictions in ores

AuAg3 Te2 Auy0 1 Agz2 3 Te2z4 1yAu 3zAgTe2 :

e
e
Besides, as indicated by A et al. (1988) and Ciobanu et al.
(2004), the - and -phases of AgAuTe system can be stable at
high temperature and decompose rapidly on cooling below 120 C

Because of isomorphic substitution of selenium for sulfur in suldes, independent selenide will not form under high sulfur fugacity.
In the breccia ores, except for FeTe compounds, Sb2Te3, SnTe,
FeSe1.333 and SnSe compounds, the majority of tellurides and selenides
are stable in logfO2(g) range. For frohbergite (FeTe2) (num. 19 in
Table 2), we propose that some other metallic elements, such as Au,

W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

Ag, Cu and Zn, were also incorporated, which probably changed the
thermodynamic property of FeTe system, maintaining stability in this
logfO2(g) range, although the precise change remains unknown. As
constrained by logfSe2(g), NiTe2 (melonite) turns to be the only stable
compound in the NiTe system in this study. The CuTe system is unstable only if some other metallic elements are incorporated as discussed
previously. As and Bi can be complexed by tellurium and selenium in
the form of As2Te3 and Bi2Te3, and As2Se3 and Bi2Se3, respectively, but
as shown in Fig. 10, Bi2Se3 and As2Se3 should be the predominant
phases.
6. Conclusions
The fugacities of S2(g), O2(g), Te2(g) and Se2(g) have played signicant roles on the different gold mineralization types in the
Guilaizhuang deposit. The volcanic vapor phase containing signicant
amounts of S, Se, As, Sb and Au, in which gold was complexed by S
and Se in the form of [Au(HS,HSe)2], led to suldization of the nearby limestone along the main fault zone in the deposit. During this
suldization process, gold complex reacted with the iron in limestone, liberating nano-particles of gold in the crystal lattices of pyrite,
As-pyrite and arsenopyrite. As the sulfur-rich vapor phase was

287

exhausted, tellurium-rich uids from the underlying magmatic chamber moved into the fault and cemented the breccias. Oxygen fugacity
was higher enough to oxidize the residual suldes into sulfate minerals such as barite and anglesite. Gold was complexed by tellurium
in the form of AuAg tellurides, probably sylvanite (AuAgTe4) and
petzite (AuAg3Te2). As temperature decreased, the sylvanite and
petzite became unstable, and decomposed into native gold, hessite
and more stable AuAg tellurides at 250 C. Calaverite, native silver
and tellurium found in the deposit are considered to be the supergene
alteration products of AuAg tellurides decomposed from sylvanite
and petzite. However, minor calaverite is not excluded which precipitated prior to the main gold mineralization stage under relatively
high tellurium fugacity.
Acknowledgments
We are grateful to Qian Mao and Yu-Guang Ma for their help during
EMPA and BSE analyses. Dr. P. Voudouris and an anonymous referee are
thanked for their constructive and valuable comments which greatly
contributed to the improvements of the manuscript. This study was
nancially supported by the Natural Science Foundation of China
(41172083) and 100 Talents Program of Chinese Academy of Sciences.

Appendix A
Appendix 1
The standard Gibbs free energy of formation fGoT = 523.15 K(kJ/mol) of compounds used in this study (the fGoT = 523.15 K of simple substance in solid form is dened to be zero and
not listed in this table).
Component
S2(g)
Se2(g)
Te2(g)
O2(g)
Ag2S
AsS
As2S3
Cu2S
CuS
CuFeS2
Cu5FeS4
FeS
Fe0.89S
FeS2
FeAs2
FeAsS
HgS
MoS2
PbS
Sb2S3
SnS
Sn2S3
SnS2
ZnS
Ag2Te
Ag1.64Te
As2Te3
AuTe2
Bi2Te3
Cu2Te
Cu4Te3
CuTe
FeTe0.9
FeTe2
HgTe
MoTe2
NiTe1.1
NiTe2
PbTe
Sb2Te3
SnTe
ZnTe
Ag2Se

Mineral species

Argentite
Realgar
Orpiment
Chalcocite
Covellite
Chalcopyrite (Cp)
Bornite (Bn)
Troilite
Pyrrhotite (Po)
Pyrite (Py)
Loellingite (Lo)
Arsenopyrite (Apy)
Cinnabar
Molybdenite
Galena
Stibnite
Herzenbergite
Ottemannite
Vaesite
Sphalerite
Hessite

Calaverite
Tellurobismuthite
Weissite
Rickardite
Vulcanite
Frohbergite
Coloradoite

Mellonite
Altaite
Tellurantimony

Naumannite

fGoT = 523.15 K
45.64
56.59
77.93
0
46.44
32.58
83.52
91.77
52.70
193.41
409.31
103.67
100.10
148.84
58.84
110.95
38.82
253.47
94.64
145.47
103.19
241.67
136.27
195.00
48.10
40.65
41.43
16.02
75.89
40.69
95.90
25.91
30.40
58.40
25.34
91.25
57.18
81.24
66.16
60.31
61.03
112.12
52.81

References
Barin (1989)
Barin (1989)
Barin (1989)
Barin (1989)
Craig and Barton (1973)
Barin (1989); O'Hare (1993)
Calculated
Calculated
Robie and Hemingway (1995); Robie et al. (1994)
Robie and Hemingway (1995); Robie et al. (1994)
Grnvold and Stlen (1992)
Grnvold and Stlen (1992)
Robie and Hemingway (1995)
Barton and Skinner (1979)
Barton and Skinner (1979)
Barin (1989); Mills (1974)
Robie and Hemingway (1995)
Barin (1989)
Robie and Hemingway (1995); Seal et al. (1992)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Robie and Hemingway (1995)
Barin (1989); Mills (1974)
A et al. (1988)
A et al. (1988)
A et al. (1988); Mills (1974)
Barin (1989)
A et al. (1988)
A et al. (1988)
A et al. (1988)
Mills (1974); Shukla et al. (1990)
A et al. (1988); Mills (1974)
Mills (1974); Nasar and Shamsuddin (1990)
Mallika and Sreedharan (1988)
A et al. (1988)
A et al. (1988)
A et al. (1988); Mills (1974)
A et al. (1988); Mills (1974)
A et al. (1988); Mills (1974)
Mills (1974); Nasar and Shamsuddin (1990)
Barin (1989)
(continued on next page)

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W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

Appendix 1 (continued)
Component
AsSe
As2Se3
AuSe
Bi2Se3
Cu2Se
CuSe
CuSe2
FeSe0.961
FeSe1.333
FeSe2
HgSe
MoSe2
Ni3Se2
NiSe1.05
NiSe2
PbSe
Sb2Se3
SnSe
SnSe2
ZnSe
As2O3
BaO
BaSO4
Bi2O3
CuO
Cu2O
Fe2O3
Fe3O44
HgO
NiO
PbO
PbSO4
Sb2O3
SnO2
ZnO
ZnSO4

Mineral species
Laphamite
Guanjuatite
Berzelianite
Klockmannite
Krutaite

Ferroselite (Fo)
Tiemannite
Drysdallite

Clausthalite
Antimonselite

Stilleite

Barite
Bismite
Tenorite
Cuprite
Hematite
Magnetite
Montroydite
Bunsenite
Litharge
Anglesite
Valentinite
Cassiterite
Zincite

fGoT = 523.15 K

References

36.13
96.18
6.06
137.66
78.64
42.66
43.90
67.69
75.68
90.51
34.08
217.78
170.98
74.84
102.06
96.99
123.07
85.70
103.10
151.45
476.98
505.96
1268.40
433.71
106.04
123.87
679.63
936.45
34.50
190.53
166.72
730.28
565.02
469.05
298.04
790.74

Mills (1974)
O'Hare et al. (1990)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Mills (1974)
Mills (1974)
Mills (1974)
Mills (1974)
Mills (1974)
Barin (1989); Mills (1974)
O'Hare et al. (1987)
Calculated
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Barin (1989); Mills (1974)
Calculated
Calculated
Calculated
Barin (1989)
Calculated
Calculated
Calculated
Calculated
Barin (1989); Mills (1974)
Calculated
Calculated
Calculated
Barin (1989)
Robie and Hemingway (1995)
Calculated
Calculated

Appendix 2
Equilibrium constant (lnK) and gaseous substance fugacity (logf) of the reactions in each mineral pair at 523.15 K.
Mineral pair
Univariate system
Suldes
CpBn + Po
Apy + AsLo
Sb2S3Sb
Bi2S3Bi
Ag2SAg
PoFe
PyPo
Cu2SCu
CuSCu2S
HgSHg(l)
Apy + AsAsS + Py
As2S3AsS
AsSAs
Bn + PyCp
S(l)S2(g)
Tellurides
SnTeSn
ZnTeZn
PbTePb
Sb2Te3Sb
Bi2Te3Bi
As2Te3As
Cu2TeCu
Cu2TeCu4Te3
Cu4Te3CuTe
NiTe2NiTe1.1
NiTe1.1Ni
FeTe2FeTe0.9
FeTe0.9Fe
As2Te3As
Ag2TeAg
Ag1.64TeAg2Te
AuTe2Au

Reactions

lnK

400/89Po + Bn + (3200/89)S2(g) = 5Cp

2FeAs2 + S2(g) = 2FeAsS + 2As
4/3Sb + S2(g) = 2/3Sb2S3
4/3Bi + S2(g) = 2/3Bi2S3
4Ag + S2(g) = 2Ag2S
0.89Fe + 0.5S2(g) = Po
Po + 0.39S2(g) = 0.89Py
2Cu + 0.5S2(g) = Cu2S
Cu + 0.5S2(g) = CuS
2Hg(l) + S2(g) = 2HgS
FeAsS + As + 1.5S2(g) = 2AsS + FeS2
2AsS + 0.5S2(g) = As2S3
As + 0.5S2(g) = AsS
5CuFeS2 + 7S2(g) = Cu5FeS4 + 5FeS2
S2(g) = 2S(l)

32.70
34.47
32.79
31.13
31.85
28.26
11.53
26.35
17.36
28.34
39.43
9.47
12.74
116.32
10.49

2Sn + Te2(g) = 2SnTe

Zn + 0.5Te2(g) = ZnTe
Pb + 0.5Te2(g) = PbTe
4/3Sb + Te2(g) = 2/3Sb2Te3
4/3Bi + Te2(g) = 2/3Bi2Te3
4/3As + Te2(g) = 2/3As2Te3
2Cu + 0.5Te2(g) = Cu2Te
2Cu2Te + 0.5Te2(g) = Cu4Te3
Cu4Te3 + 0.5Te2(g) = 4CuTe
NiTe1.1 + 0.45Te2(g) = NiTe2
Ni + 0.55Te2(g) = NiTe1.1
FeTe0.9 + 0.55Te2(g) = FeTe2
Fe + 0.45Te2(g) = FeTe0.9
4/3As + Te2(g) = 2/3As2Te3
4Ag + Te2(g) = 2Ag2Te
0.82Ag2Te + 0.09Te2(g) = Ag1.64Te
Ag + Te2(g) = AuTe2

45.98
34.74
24.17
27.16
29.55
24.27
19.05
12.30
10.74
13.59
23.00
16.29
15.05
24.27
40.03
1.89
21.60

Equilibrium fugacity
LogfS2(g)
18.9
14.9
14.2
13.5
13.8
24.5
12.8
22.9
15.1
12.3
11.4
8.2
11.1
7.2
4.56
LogfTe2(g)
20.0
30.2
21.0
11.8
12.8
10.53
16.5
10.7
9.3
13.2
18.2
12.9
14.5
10.5
17.4
9.1
9.4

W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

289

Appendix 2 (continued)
Mineral pair

Reactions

HgTeHg(l)
Te2(g)Te(s)
Selenides
CuSeCu2Se
Cu2SeCu
AuSeAu
FeSe2FeSe1.333
FeSe1.333 + As2Se3Lo
FeSe1.333Fe
HgSeHg
Sb2Se3Sb
As2Se3As
Ag2SeAg
SnSe2SnSe
SnSeSn
Bi2Se3Bi
NiSe2NiSe1.05
NiSe1.05Ni3Se2
Ni3Se2Ni
ZnSeZn
PbSePb
Se2(g)Se(l)
Oxides
NiONi
SnO2Sn
HgOHg
Cu2OCu
CuOCu2O
PbOPb
ZnOZn
Bi2O3Bi
Sb2O3Sb
As2O3As
Fe2O3Fe3O4

2Hg(l) + Te2(g) = 2HgTe

Te2(g) = 2Te(s)

29.57
17.92

Cu2Se + 0.5Se2(g) = 2CuSe

2Cu + 0.5Se2(g) = Cu2Se
2Au + Se2(g) = 2AuSe
FeSe1.333 + 0.3335Se2(g) = FeSe2
Lo + 2.167Se2(g) = FeSe1.333 + As2Se3
Fe + 0.667Se2(g) = FeSe1.333
2Hg + Se2(g) = 2HgSe
4/3Sb + Se2(g) = 2/3Sb2Se3
2As + 1.5Se2(g) = As2Se3
4Ag + Se2(g) = 2Ag2Se
SnSe + 1/2Se2(g) = SnSe2
Sn + 1/2Se2(g) = SnSe
4/3Bi + Se2(g) = 2/3Bi2Se3
NiSe1.05 + 0.475Se2(g) = NiSe2
Ni3Se2 + 0.575Se2(g) = 3NiSe1.05
3Ni + Se2(g) = Ni3Se2
Zn + 0.5Se2(g) = ZnSe
Pb + 0.5Se2(g) = PbSe
Se2(g) = 2Se(l)

8.04
24.59
15.80
7.75
54.18
26.08
28.68
31.87
41.63
37.29
10.51
26.21
34.11
12.44
19.79
52.32
41.32
31.26
13.01

Mineral pair

Ni + 0.5O2(g) = NiO
Sn + O2(g) = SnO2
Hg + 0.5O2 = HgO
2Cu + 0.5O2(g) = Cu2O
Cu2O + 0.5O2(g) = 2CuO
Pb + 1/2O2(g) = PbO
Zn + 1/2O2(g) = ZnO
4/3Bi + O2(g) = 2/3Bi2O3
4/3Sb + O2(g) = 2/3Sb2O3
4/3As + O2(g) = 2/3As2O3
2Fe3O4 + 0.5O2(g) = 3Fe2O3
Reactions

lnK

43.81
114.05
7.93
28.48
21.05
38.32
68.52
66.48
86.60
73.11
40.80
lnK

Equilibrium fugacity

2.225Cu2Se + Po + 1.78S2(g) = 0.89Bn + 1.1125Se2(g)

0.445Cu2Se + Po + 0.39S2(g) = 0.89Cp + 0.2225Se2(g)
2FeSe2 + Cu2Se + 2S2(g) = 2Cp + 2.5Se2(g)
Sb2Se3 + 1.5S2(g) = Sb2S3 + 1.5Se2(g)
HgSe + 0.5S2(g) = HgS + 0.5Se2(g)
As2Se3 + 1.5S2(g) = As2S3 + 1.5Se2(g)
0.5As2Se3 + FeSe1.333 + 0.5S2(g) = Apy + As + 1.417Se2(g)
As2Se3 + S2(g) = 2AsS + 1.5Se2(g)
0.89FeSe1.333 + 0.5S2(g) = Po + 0.59Se2(g)
FeSe2 + S2(g) = Py + Se2(g)
Bi2Se3 + 1.5S2(g) = Bi2S3 + 1.5Se2(g)
Ag2Se + 0.5S2(g) = Ag2S + 0.5Se2(g)
PbSe + 0.5S2(g) = PbS + 0.5Se2(g)

19.48
9.71
17.69
1.37
0.17
6.69
27.19
16.15
5.10
10.89
4.46
2.72
1.80

logfSe2(g) = alogfS2(g) + b
a
b
1.15
7.60
1.75
18.96
0.80
3.07
1.00
0.40
1.00
0.15
1.00
1.94
0.35
8.33
0.67
4.68
0.85
3.75
1.00
4.73
1.00
1.29
1.00
2.37
1.00
1.56

Ag2Te + 0.5Se2(g) = Ag2Se + 0.5Te2(g)

Ag1.64Te + 0.41Se2(g) = 0.82Ag2Se + 0.5Te2(g)
HgTe + 0.5Se2(g) = HgSe + 0.5Te2(g)
AuTe2 + 0.5Se2(g) = AuSe + Te2(g)
Cu2Te + 0.5Se2(g) = Cu2Se + 0.5Te2(g)
Cu4Te3 + Se2(g) = 2 Cu2Se + 1.5Te2(g)
2CuTe + 0.5Se2(g) = Cu2Se + Te2(g)
FeTe0.9 + 0.667Se2(g) = FeSe1.333 + 0.45Te2(g)
FeTe2 + 0.667Se2(g) = FeSe1.333 + Te2(g)
FeTe2 + Se2(g) = FeSe2 + Te2(g)
SnTe + 0.5Se2(g) = SnSe + 0.5Te2(g)
3NiTe1.1 + Se2(g) = Ni3Se2 + 1.65Te2(g)
NiTe1.1 + 0.525Se2(g) = NiSe1.05 + 0.55Te2(g)
NiTe2 + 0.525Se2(g) = NiSe1.05 + Te2(g)
NiTe2 + Se2(g) = NiSe2 + Te2(g)
Bi2Te3 + 1.5Se2(g) = Bi2Se3 + 1.5Te2(g)
Sb2Te3 + 1.5Se2(g) = Sb2Se3 + 1.5Te2(g)
As2Te3 + 1.5Se2(g) = As2Se3 + 1.5Te2(g)
ZnTe + 0.5Se2(g) = ZnSe + 0.5Te2(g)
PbTe + 0.5Se2(g) = PbSe + 0.5Te2(g)

1.37
3.01
0.44
13.70
6.27
0.25
5.25
11.03
5.27
2.48
3.22
16.68
1.04
12.56
0.12
6.84
7.07
5.23
6.59
4.64

LogfTe2(g) = alogfSe2(g) + b
1.00
1.19
0.82
2.62
1.00
0.39
0.50
5.95
1.00
5.45
0.67
0.07
0.50
2.3
1.48
10.64
0.67
2.29
1.00
1.08
1.00
2.80
0.61
4.39
0.95
0.82
0.525
5.45
1.00
0.05
1.00
1.98
1.00
2.05
1.00
1.51
1.00
5.72
1.00
4.03

Bivariate system
SuldesSelenides
Cu2Se + PoBn
Cu2Se + PoCp
Cu2Se + FeSe2Cp
Sb2Se3Sb2S3
HgSeHgS
As2Se3As2S3
FeSe1.333 + As2Se3Apy + As
As2Se3AsS
FeSe1.333Po
FeSe2Py
Bi2Se3Bi2S3
Ag2SeAg2S
PbSePbS
TelluridesSelenides
Ag2TeAg2Se
Ag1.64TeAg2Se
HgTeHgSe
AuTe2AuSe
Cu2TeCu2Se
Cu4Te3Cu2Se
CuTeCu2Se
FeTe0.9FeSe1.333
FeTe2FeSe1.333
FeTe2FeSe2
SnTeSnSe
NiTe1.1Ni3Se2
NiTe1.1NiSe1.05
NiTe2NiSe1.05
NiTe2NiSe2
Bi2Te3Bi2Se3
Sb2Te3Sb2Se3
As2Te3As2Se3
ZnTeZnSe
PbTePbSe

Equilibrium fugacity
12.8
7.8
LogfSe2(g)
7.0
21.4
6.9
10.1
10.9
17.0
12.4
13.8
12.1
16.2
9.1
22.8
14.8
11.4
14.9
22.7
35.9
27.1
5.6
LogfO2(g)
38.0
49.5
6.89
24.7
18.3
33.3
59.5
28.9
37.6
31.7
35.4

(continued on next page)

290

W.-G. Xu et al. / Ore Geology Reviews 56 (2014) 276291

Appendix
2 (continued)
Appendix
2 (continued)
Mineral pair
OxidesSelenides
ZnOZnSe
HgOHgSe
SnO2SnSe
SnO2SnSe2
NiONi3Se2
NiONiSe1.05
NiONiSe2
Sb2O3Sb2Se3
Bi2O3Bi2Se3
As2O3As2Se3
PbOPbSe
Cu2OCu2Se
Fe3O4FeSe1.333
Fe3O4FeSe2
Fe2O3FeSe2
OxidesTellurides
ZnOZnTe
HgOHgTe
SnO2SnTe
PbOPbTe
NiONiTe1.1
NiONiTe2
Sb2O3Sb2Te3
Bi2O3Bi2Te3
As2O3As2Te3
Cu2OCu2Te
Fe3O4FeTe0.9
Fe3O4FeTe2
Fe2O3FeTe2

Reactions

lnK

ZnSe + 0.5O2(g) = ZnO + 0.5Se2(g)

HgSe + 0.5O2(g) = HgO + 0.5Se2(g)
SnSe + O2(g) = SnO2 + 0.5Se2(g)
SnSe2 + O2(g) = SnO2 + Se2(g)
Ni3Se2 + 1.5O2(g) = 3NiO + Se2(g)
NiSe1.05 + 0.5O2(g) = NiO + 0.525Se2(g)
NiSe2 + 0.5O2(g) = NiO + Se2(g)
Sb2Se3 + 1.5O2(g) = Sb2O3 + 1.5Se2(g)
Bi2Se3 + 1.5O2(g) = Bi2O3 + 1.5Se2(g)
As2Se3 + 1.5O2(g) = As2O3 + 1.5Se2(g)
PbSe + 0.5O2(g) = PbO + 0.5Se2(g)
Cu2Se + 0.5O2(g) = Cu2O + 0.5Se2(g)
3FeSe1.333 + 2O2(g) = Fe3O4 + 1.99Se2(g)
3FeSe2 + 2O2(g) = Fe3O4 + 3Se2(g)
2FeSe2 + 1.5O2(g) = Fe2O3 + 2Se2(g)

27.20
6.41
81.63
71.15
79.09
19.77
7.33
82.09
48.55
68.06
9.52
3.89
137.33
113.96
89.58

ZnTe + 0.5O2(g) = ZnO + 0.5Te2(g)

HgTe + 0.5O2(g) = HgO + 0.5Te2(g)
SnTe + O2(g) = SnO2 + 0.5Te2(g)
PbTe + 0.5O2(g) = PbO + 0.5Te2(g)
NiTe1.1 + 0.5O2(g) = NiO + 0.55Te2(g)
NiTe2 + 0.5O2(g) = NiO + Te2(g)
Sb2Te3 + 1.5O2(g) = Sb2O3 + 1.5Te2(g)
Bi2Te3 + 1.5O2(g) = Bi2O3 + 1.5Te2(g)
As2Te3 + 1.5O2(g) = As2O3 + 1.5Te2(g)
Cu2Te + 0.5O2(g) = Cu2O + 0.5Te2(g)
3FeTe0.9 + 2O2(g) = Fe3O4 + 1.35Te2(g)
3FeTe2 + 2O2(g) = Fe3O4 + 3Te2(g)
2FeTe2 + 1.5O2(g) = Fe2O3 + 2Te2(g)

33.79
6.85
84.85
14.15
20.80
7.21
89.16
55.39
73.26
10.17
170.27
121.39
94.53

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Equilibrium fugacity
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