Accepted Manuscript

Mineralogy of Bi-sulfosalts and tellurides from the Yaoan gold deposit, south-
west China and its metallogenic implications

Haoyang Zhou, Xiaoming Sun, Tianjian Yang, Yingzhi Ren, Kunjie Zhu, Haijun
Yu, Chun-Kit Lai

PII: S0169-1368(17)30895-8
DOI: https://doi.org/10.1016/j.oregeorev.2018.05.004
Reference: OREGEO 2578

To appear in: Ore Geology Reviews

Received Date: 18 November 2017

Revised Date: 26 April 2018
Accepted Date: 8 May 2018

Please cite this article as: H. Zhou, X. Sun, T. Yang, Y. Ren, K. Zhu, H. Yu, C-K. Lai, Mineralogy of Bi-sulfosalts
and tellurides from the Yaoan gold deposit, southwest China and its metallogenic implications, Ore Geology
Reviews (2018), doi: https://doi.org/10.1016/j.oregeorev.2018.05.004

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
 Mineralogy of Bi-sulfosalts and tellurides from the Yaoan
gold deposit, southwest China and its metallogenic
implications

Haoyang Zhoua, Xiaoming Suna,b,c,*, Tianjian Yanga, Yingzhi Renb, Kunjie

Zhub,e, Haijun Yud, Chun-Kit Laif

a School of Earth Sciences and Engineering, Sun Yat-sen University, Guangzhou

510275, China
b School of Marine Sciences, Sun Yat-sen University, Guangzhou 510006, China
c Guangdong Provincial Key Laboratory of Marine Resources and Coastal
Engineering, Guangzhou 510275, China
d MLR Key Laboratory of Sanjiang Metallogeny and Resources Exploration and
Utilization, Yunnan Geological Survey, Kunming 650051, PR China
e Guangzhou Marine Geological Survey, Guangzhou 510760, China
f ARC Centre of Excellence in Ore Deposits (CODES), University of Tasmania,
Hobart, Tasmania 7001, Australia

*Corresponding author
E-mail addresses: [email protected] (X.M. Sun)
[email protected] (H.Y. Zhou)
Abstract
Bismuth-sulfosalts and tellurides are commonly present in many hydrothermal
gold mineral systems, and can provide important physicochemical constraints
(notably fO2, fS2 and fTe2) on the metallogenesis. The abundant auriferous specular
hematite veins in the Yaoan gold deposit (southwest China) of the Jinshajiang-Red
River alkaline porphyry metallogenic belt contain an assemblage of Bi-sulfosalts and
tellurides. Bismuth-sulfosalts include mainly cuprobismutite homologues (probable
intergrowths of hodrushite and cuprobismutite in submicron-scale), bismuthinite
derivatives (e.g., bismuthinite, paarite, krupkaite, lindströmite and friedrichite-aikinite)
and emplectite, together with minor paděraite and rare matildite. Tellurides are tiny,
comprising tetradymite, tsumoite, melonite, hessite and calaverite. These Bi-sulfosalts
and tellurides are in direct contact with the gold, indicating that the Yaoan gold
metallogenesis was likely linked to the syenite porphyry magmatism, and that the gold
was precipitated in an oxidized condition with high tellurium fugacity (fTe2 = ~10-7.9
and fS2 = ~10-8.5 at ~300°C).
Keywords: Yaoan gold deposit; Bi-sulfosalts; Tellurides; Jinshajiang-Red River
metallogenetic belt; Alkaline porphyry
1. Introduction
Despite being accessory minerals in many hydrothermal gold deposits,
bismuth-sulfosalt and telluride minerals have commonly immediate association with
gold mineralization (Meinert, 2000; Törmänen and Koski, 2005; Oberthür and Weiser,
2008; Cook et al., 2009; Ciobanu et al., 2010; Liu et al., 2013). The fact that
bismuth-sulfosalts and tellurides are sensitive to physicochemical variations, notably
the temperature and fugacities of oxygen, sulfur and tellurium (Afifi et al., 1998a,
1988b; Ciobanu et al., 2005; Voronin and Osadchii, 2013; Xu et al., 2014), provide
valuable constraints on the nature and processes of the gold mineralization (e.g., Cook
and Ciobanu, 2004; Cepedal et al., 2006; Voudouris et al., 2013; Gao et al., 2015;
Zhou et al., 2016; Hassan and Roberts, 2017; Takács et al., 2017).
Along the Jinshajiang-Red River fault zone in southwest China, there are
abundant Eocene-Oligocene post-collisional alkaline porphyries (Fig. 1) that host
considerable gold and copper resources, e.g., the world-class Beiya gold
porphyry-skarn and Yulong porphyry copper deposits (Hou et al., 2003, 2007; Deng et
al., 2014; Zhou et al., 2017a). Detailed investigation into ore-forming geochronology
and thermodynamic conditions of these alkaline porphyry-related deposits are
beneficial to understand the ore-forming processes and relationship between alkaline
intrusions and Au-Cu mineralization (e.g., Wang et al., 2005; Hou et al., 2006; Liang
et al., 2009; Fu et al., 2015; Zhou et al., 2016, 2017a). The Yaoan deposit, containing
abundant auriferous specular hematite veins, is typically related to a syenite porphyry
in the Jinshajiang-Red River metallogenetic province. The genetic link between the
syenite porphyry and gold mineralization at Yaoan had been poorly understood until a
recent study reported the ages of hydrothermal monazite and gold-bearing hematite,
which were coeval with the syenite porphyry (Zhou et al., 2017b). However, the ore
mineralogy and ore-forming conditions remain poorly constrained, hindering better
comprehending the genesis of the Yaoan gold deposit.
Previous studies on the adjacent Beiya porphyry-skarn gold deposit (related to
quartz syenite porphyries) documented abundant Bi- and Te-minerals and successfully
revealed the ore-forming information accordingly (Zhou et al., 2016; 2017a).
Moreover, the presence of Fe-Cu-Pb-Bi-S minerals at Yaoan was noted in an early
paper (Shuai and Wan, 1990), although the mineralogical results therein are not
insufficient due to the limited analytical conditions at that time. This offer a means to
understand the ore-forming conditions of the Yaoan gold deposit in terms of Bi-Te
mineralogy.
In this study, we carried out detailed ore mineralogical study on the Yaoan gold
deposit. New mineral chemistry data of the Bi-sulfosalts and tellurides from Yaoan are
reported and compared with those in the adjacent Beiya gold deposit. We discuss the
physicochemical conditions of the Yaoan gold mineralization and their implications
on the regional alkaline intrusion-related gold metallogenesis.

2. Geological setting
The NW-trending Jinshajiang-Red River belt is located between the South China
and Indochina-Simao blocks (Fig. 1). The belt (a crustal-scale strike-slip fault zone) is
the Cenozoic tectonic reactivation of a Paleo-Tethyan suture zone, which formed by
the diachronous closure of the eastern Paleo-Tethys during the Middle to Late Triassic
(Wang et al., 2000; Lai et al., 2014a, 2014b). The Cenozoic reactivation of the suture
zone was led by the post-India-Asia collisional tectonics (Schärer et al., 1990;
Tapponnier et al., 1990; Yin and Harrison, 2000), during which the overthickened
crustal delamination had also generated abundant Eocene-Oligocene (ca. 40−30 Ma)
alkaline granitoids and lamprophyre dikes along the belt (Turner et al., 1996; Chung
et al., 1997, 1998; Lu et al., 2012). Geochemical studies suggested that these alkaline
intrusive rocks might originate from the partial melting of the residual metasomatized
lithospheric mantle and lower crust (Hou et al., 2003; Lu et al., 2013a, 2013b).
A large number of important alkaline porphyry-related gold and copper deposits
are discovered in the Jinshajiang-Red River belt. The northern segment of the belt is
represented by the Yulong porphyry Cu belt (comprising the Yulong, Zhanaga,
Mangzong, Duoxiasongduo and Malasongduo deposits), which hosts over 9 Mt Cu
resources (Liang et al., 2009). Molybdenite Re-Os dating of the Cu mineralization (ca.
42–36 Ma) suggested that the mineralization was largely coeval with the monzonite
porphyry emplacement (ca. ~44−36 Ma) there (Hou et al, 2006; Liang et al., 2006).
The southern segment of the belt is represented by the alkaline porphyry-related Beiya
and Yaoan gold deposits. Beiya is a giant gold polymetallic deposit, and hosts over
11.9 Moz @ 2.52 g/t Au resource (Mao et al., 2017). The Beiya gold mineralization
(molybdenite Re-Os dating: ca. 36.8–34.7 Ma; Fu et al., 2015; He et al., 2015) is
widely regarded to be genetically linked to the Beiya quartz syenite porphyries (ca.
~36.6−34.7 Ma; Deng et al., 2015; Fu et al., 2015; He et al., 2015).
Yaoan is located ~140 km southwest of Beiya in Yunnan Province and is
geologically situated on the western margin of the South China (Yangtze) Craton.
Many alkaline magmatic rocks are exposed in the area, including (quartz)-syenite
porphyry, biotite monzonite porphyry, leucite porphyry, tephrite, trachyte and
lamprophyre (Qian and Li., 2000; Cheng et al., 2007; Bi et al., 2009). Exposed
stratigraphy at Yaoan mainly include thick Mesozoic red beds, comprising the purplish
to gray (feldspathic)-quartz sandstone, siltstone and mudstone from the Lower
Cretaceous Gaofengshi Formation, and the purplish mudstone and siltstone, and
purplish to greyish-green calcareous mudstone and marl from the Upper Jurassic
Tuodian Formation. These Mesozoic sedimentary sequences are overlain by the
pebbles, sands, clay and volcanic clastic rocks from the Upper Neogene Formation, and
the Quaternary sediments.

3. Deposit geology
The Yaoan deposit, with approximately 0.32 Moz Au @ 4−5 g/t (Bi et al., 2009),
is hosted by the Upper Jurassic Tuodian Formation and spatially related to the syenite
porphyry stocks (Fig. 2). The syenite porphyry stocks consist mainly of K-feldspar,
plagioclase, biotite and amphibole and minor quartz. Accessory minerals include
apatite, monazite, zircon, rutile, titanite, magnetite and hematite. Published
geochemical data suggest that the syenite porphyry contains high Na2O + K2O (~9.0
wt.%) and Na2O/K2O (1.1−1.5), and can thus be classified as alkaline and potassic (Bi
et al., 2005; Lu et al., 2013). The Yaoan syenite porphyry was dated to be late Eocene
to earliest Oligocene (ca. ~36−32 Ma; Chen et al., 2007; Li et al., 2011; Lu et al., 2012;
Zhou et al., 2017b). It was suggested that the syenite porphyry may have formed via
fractionation from a lamprophyre-like potassic mafic magma and emplaced at a
shallow crustal level (~1.1 kbar), as supported by whole rock Sr-Nd-Pb isotopes,
zircon Hf-O isotopes, and amphibole barometry (Bi et al., 2009; Lu et al., 2013a).
The Yaoan mineralization is developed along an EW-trending fracture zone in
the syenite porphyry and the purplish to gray mudstone and siltstone from the Upper
Jurassic Tuodian Formation (Figs. 2, 3a). The mineralized zone (~1000 m long and
~500 m wide) hosts ~20 vein-like Au orebodies (20−700 m long and 0.5−2 m thick).
Typical orebodies, represented by KT7 and KT14, have gold grade up to 44 g/t and 20
g/t, respectively. The largest orebody KT7, hosed by the mudstone, marl and siltstone,
occurs as stockwork at shallow depths and as veins in deep part. By contrast, orebody
KT14 is present as veins in the cataclastic endocontacts of the syenite porphyry. Gold
ores occur in veins, stockwork and breccias (Fig. 3b-f).
At Yaoan, potassic alteration is predominately developed in the syenite porphyry,
forming abundant K-feldspar (Fig. 3b). Phyllic and chlorite alterations are common in
the Tuodian Formation mudstone and siltstone (Fig. 3d, e). Carbonate (e.g., calcite,
siderite) and silicic alterations are ubiquitous in the deposit, and occur as vein-filling
or replace the feldspar (phenocrystals or groundmass) of the porphyry (Fig. 3b, d-f).

4. Samples and analytical methods

Representative ore samples were collected from three mining tunnels at 2310-,
2283- and 2200-m level. Mineral textures and semi-quantitative geochemical
composition were investigated under the backscattered electron (BSE) mode using a
ZEISS ΣIGMA scanning electron microscope (SEM) equipped with INCA
X-MAX020 energy-dispersive spectrometer (EDS) at the School of Earth Sciences
and Engineering, Sun Yat-sen University (SYSU), and a TESCAN VEGA II LMU
SEM equipped with INCA Penta FET×3 EDS at the Key Laboratory of Marine
Mineral Resources, Guangzhou Marine Geological Survey. Geochemistry of the
Bi-sulfosalts was analyzed using a JXA-8800R electron probe micro-analyzer (EPMA)
at the Instrument Analysis and Research Center, SYSU. A 20-kV acceleration voltage
and a 20-nA beam current with a < 1-μm beam diameter were employed during the
EPMA analyses. Peak and background counting time for each element are 10 s and 5 s,
respectively. Spectral lines, standards and typical detection limits were as follow: Ag
(Lα, pure Ag, 0.02 wt.%), Au (Lα, pure Au, 0.11 wt.%), Bi (Mα, Bi2Se3, 0.07 wt.%),
Cu (Kα, pure Cu, 0.03 wt.%), Fe (Kα, pyrite, 0.02 wt.%), Pb (Mα, galena, 0.10 wt.%),
S (Kα, pyrite, 0.01 wt.%), Sb (Lα, Sb2Te3, 0.03 wt.%), Se (Lα, Bi2Se3, 0.02 wt.%), Te
(Lα, Sb2Te3, 0.05 wt.%), and Zn (Kα, sphalerite, 0.04 wt.%).

5. Mineralogy and mineral chemistry

Ores minerals at Yaoan are dominated by specular hematite with minor pyrite
and chalcopyrite (Fig. 3). Hematite occurs as specular, platy and acicular crystals with
sizes up to several centimeters. Pyrite and chalcopyrite are present in the hematite
matrix. Other locally minor ore minerals include galena, sphalerite and
tennantite-tetrahedrite series. Equilibrium textures (e.g., crystal intergrowths and 120º
grain boundary triple junctions) are common in these minerals, except sphalerite
micro-veins locally cut chalcopyrite and Bi-sulfosalts (Fig. 3f).
Gold (native gold or electrum) occurs as microfracture-infills or inclusions in
pyrite (Fig. 4a-e). Hematite is also an important gold host mineral, in which gold is
present as intraparticle inclusions (Fig. 4f) or interstitial. Another common host for
gold is chalcopyrite. It is also noted that gold is in direct contact with Bi-sulfosalts
and tellurides.
Bismuth-sulfosalts and tellurides are common accessory components (ca. 1−2
vol.%) in the Yaoan gold ores, but could become abundant locally. Identified
Bi-sulfosalts are dominated by cuprobismutite homologues, paděraite, bismuthinite
derivatives and emplectite, which occur as large interstitial patches (up to several mm)
among hematite grains (Fig. 5a). Intergrowths of Bi-sulfosalts and chalcopyrite are
also common, as stuffing in a hematite framework (Fig. 5f). By contrast, tellurides (in
μm-scale) are much rarer than Bi-sulfosalts, and are found included in pyrite,
chalcopyrite and Bi-sulfosalts (Fig. 8).
5.1 Cuprobismutite homologues and related paděraite
Cuprobismutite homologues are Cu-Bi sulfosalts, which are determined as
intergrowth of two galena-like slabs, i.e., (331)PbS-like octahedral layers, and layers of
metal in tricapped trigonal-prismatic coordination (Makovicky, 1989; Cook and
Ciobanu, 2003; Topa et al., 2003). The general formula is given as
Cu8Me4(N-1)+2Bi8S4N+16, where Me could be Cu, Fe, Ag, Pb and Bi (Makovicky, 1989).
The order number (N) of a cuprobismutite homologue is defined as 2 × (Bi/Cu) − 1.5,
where Bi = Bi + Ag + Pb and Cu = Cu + Fe (Topa et al., 2003). There are three known
natural members for the homologues, i.e., kupčikite (N = 1), hodrushite (N = 1.5) and
cuprobismutite (N = 2). Paděraite, structurally related to the cuprobismutite
homologues series, is a rare Pb-rich Cu-Bi sulfosalt, which has an empirical formula
Cu5.5Ag1.1Pb1.2Bi11S22 derived from compositional determination and a formula
Cu5.9Ag1.3Pb1.6Bi11.2S22 based on structural measurement (Mumme and Žák, 1985;
Mumme, 1986).
At Yaoan, cuprobismutite homologues occur as acicular blades or agglomerate as
bundles (Fig. 5). Coexistence of gold and cuprobismutite homologues is observed
(Fig. 9a). Under the BSE imaging, different contrasts are revealed among blades in
the bundles. Compositional data are listed in Table 1 and plotted on Figure 6. The
results indicate that cuprobismutite homologues contain high Fe (0.44−1.65 wt.%)
and Ag (0.60−1.70 wt.%) contents. Lead concentrations in these cuprobismutite
homologues are below detection limit. Calculated N values of the homologues
successively range from 1.49 to 1.96. On the (Cu + Fe) – Pb – (Bi + Ag) ternary
diagram (Fig. 6), these phases are plotted between hodrushite and cuprobismutite. We
thus interpret them as intergrowths of submicron-scale hodrushite and cuprobismutite
that are indistinguishable under the resolution of EPMA spots. Similar
submicroscopic intergrowths of cuprobismutite homologues were reported in a
granitic pegmatite in southwest Poland (Pieczka and Gołębiowska, 2012) and at the
Ocna de Fier skarn Fe-Cu deposit, southwest Romania (Ciobanu et al., 2004). The
molar ratios of hodrushite (nhod, mol. % hodrushite) in the intergrowths of the samples
are defined based on nhod = (4 – 2N) × 100% (Pieczka and Gołębiowska, 2012).
Calculated values of nhod vary between 100% and 8%.
Compared to cuprobismutite homologues, paděraite is relatively rare in nature.
This phase is bladed and associated with cuprobismutite homologues and bismuthinite
derivatives (Fig. 5e, h). The EPMA data (Table 2) show that the paděraite carries low
Fe (0.02−0.51 wt.%) and variable Ag (0.25−1.67 wt.%) but high Pb (3.75−5.43 wt.%)
contents. Based on 42 atoms, the calculated mean formula of paděraite is as follow:
(Fe0.10Cu6.93)∑7.03(Ag0.38Pb0.86)∑1.24Bi11.79(Se0.01Te0.01S21.92)∑21.94.
In the (Cu + Fe) – Pb − (Bi + Ag) ternary plot (Fig. 6), the paděraite compositions at
Yaoan resemble those from the Ocna de Fier skarn Fe-Cu deposit, but are different
from its empirical or structural formula. This is because Ag is not essential in
paděraite, provided that the excess amount of other components (e.g., Cu) could play
the same roles in balancing the structure (Cook and Ciobanu, 2003).

5.2 Bismuthinite derivatives

Bismuthinite derivatives (bismuthinite-aikinite series) are an isomorphic series
derived from a combination of krupkaite (CuPbBi3S6) with two end members of
bismuthinite (Bi4S6) and aikinite (Cu2Pb2Bi2S6). Based on the substitution mechanism
of Cu + Pb  □ + Bi (□ = vacant tetrahedral position) and (Cu + Pb)/2 + Bi = 8
atoms per formula unit, the generalized formula of bismuthinite derivative is given as
CuxPbyBi8-1/2(x+y)S12, where x should be equal or very similar to y. The parameter
naikinite (mol. % aikinite), calculated as 12.5 × (x + y) %, is defined to depict the
position of a bismuthinite derivative on the bismuthinite-aikinite join, which
represents the ratio of aikinite end member in a bismuthinite derivative.
At Yaoan, bismuthinite derivatives are one of the most abundant Bi-sulfosalt
phases (Fig. 5). Direct contact between gold and bismuthinite derivatives is present
(Fig. 9b-d). The EPMA data of bismuthinite derivatives are shown in Table 3 and
plotted in the Bi – Cu – Pb ternary diagram (Fig. 7). Silver is depleted in most of the
derivatives, while Fe content is variable (0–0.59 wt.%). The data demonstrate equal
amounts of Cu and Pb atoms in each derivative (mean Cu/Pb ratio: 1.07), well
consistent with the aforementioned substitution mechanism. The indicated naikinite
values for all the 28 analyses at Yaoan vary from 2.06 to 97.06. Friedrichite-aikinite
solutions (naikinite = 88.64–97.06) are the dominant bismuthinite derivatives. Five
analyses (naikinite = 48.33–53.33) are krupkaite. Four data (naikinite = 2.06–3.01) are
consistent with bismuthinite composition, one (naikinite = 42.51) mimics paarite, and
one (naikinite = 56.83) mimics lindströmite.
We recalculated the EPMA data of the Fe-Cu-Pb-Bi-S phases presented in an
early paper (Shuai and Wan, 1990). Our results suggest that six analyses of the so
called “Dian Cu-Pb-Bi mineral” (Dian: Yunnan in Chinese) in that paper is
friedrichite-aikinite series with naikinite in the range of 96.27–100. Compared with
those bismuthinite derivatives from Beiya skarn gold ores (Zhou et al, 2016; Fig. 7),
the Cu:Pb ratios of the Yaoan derivatives are closer to 1, whereas those of the Beiya
derivatives show a slight Cu excess (mean = 1.25).

5.3 Other Bi-sulfosalts (emplectite and matildite)

Emplectite (CuBiS2) is another common Bi-sulfosalt at Yaoan (Figs. 5j, 8a-c),
and contain varying Cu (16.87–22.05 wt.%) and Bi (59.54–64.48 wt.%)
concentrations (Table 2). As for trace elements, the Yaoan emplectite contains high Fe
(up to 0.45 wt.%) and Ag (up to 0.30 wt.%) contents, but generally low Pb content.
The general formula of the Yaoan emplectite is as follow:
(Fe0.01Cu0.99) ∑1.00Bi1.01S1.99.
Matildite (AgBiS2) is a rare Bi-phase at Yaoan. Together with another Ag-Bi-S
phase and gold, matildite coexists with pyrite and chalcopyrite (Fig. 9e).

5.4 Tellurides
Telluride minerals are rare at Yaoan but have immediate association with sulfides
and Bi-sulfosalts. Due to their small size, all telluride phases are identified with EDS
to comprise tetradymite, tsumoite, melonite, hessite and calaverite. Tetradymite
(Bi2Te2S) is present as minute blebs in emplectite and bismuthinite derivatives (Figs.
5j, 8a-c), while tiny tsumoite (BiTe) droplets are found in pyrite (Fig. 8f, g). Melonite
(Ni2Te) is found intergrown with chalcopyrite (Fig. 8i), whereas hessite (Ag2Te) is
included inside pyrite and bismuthinite derivatives (Fig. 8d, e). Coexistence of hessite
and tetradymite occurs in assemblage of pyrite and chalcopyrite (Fig. 8h). Calaverite
(AuTe2) is intergrown with gold, filling the cavities in the bismuthinite derivatives
(Fig. 9f). It is common to find 120º grain boundary triple junctions in tellurides,
sulfides and Bi-sulfosalts (Fig. 8e, i).

6. Genetic constraints and metallogenic implications

Bismuth sulfosalts and tellurides are ubiquitous in a variety of hydrothermal
deposits. At Yaoan, bismuth sulfosalts are dominated by assemblages of
cuprobismutite homologues + paděraite + bismuthinite derivatives + emplectite +
matildite. In other locality, bismuthinite derivatives are much more common than
cuprobismutite homologues and paděraite (e.g., Cook and Ciobanu, 2004; Bristol et
al., 2015; Buzatu et al., 2015; Zhou et al., 2016). Therefore, the Yaoan gold deposit
represents a rare locality where the cuprobismutite homologues and paděraite
assemblage dominates.
Predominance of the cuprobismutite homologues and paděraite assemblage are
rare documented but have been found in magmatic-hydrothermal deposits, e.g., the
Rozália Au-Ag epithermal mine, Hodruša–Hámrec (Slovakia), where cuprobismutite,
paděraite and bismuthinite-aikinite series were reported (Jeleň et., 2012); the Ocna de
Fier skarn Fe-Cu deposit (southwest Romania), where bismuthinite derivatives and
intergrowths of cuprobismutite and paděraite with minor hodrushite were reported
(Cook and Ciobanu, 2003); and from a granitic pegmatite at Szklarska Poręba
(southwest Poland), where kupčikite, hodrušite, cuprobismutite and an unnamed N =
2.5 homologue intergrown with bismuthinite derivatives were found (Pieczka and
Gołębiowska, 2012). We thus hypothesize that the similar Bi-Pb-Cu assemblage at
Yaoan is suggestive of a magmatic-hydrothermal affinity. This hypothesis is supported
by previous studies showing both the hydrothermal fluids and ore-forming material
with a magmatic origin, evidenced by (1) He-Ar-S isotopes of pyrite (Bi et al., 2004;
Hu et al., 2004); (2) C isotopes of calcite (Bi et al., 2004); (3) similar REE patterns in
primary igneous perthite, secondary hydrothermal K-feldspar, and pyrite from the ores
(Bi et al., 2002, 2004). Recently, the U-Th-Pb geochronology on hydrothermal
monazite and hematite indicates that the Yaoan gold mineralization took place at
~32–30 Ma (Zhou et al, 2017b), coeval with the emplacement of the syenite porphyry.
Collectively, given that the alteration types (e.g., potassic, phyllic and chlorite
alterations), the ore-forming fluids and materials with a magmatic origin, and the
concurrence of magmatism and mineralization, we argue that Yaoan is very likely to
be a porphyry deposit, rather than an orogenic type (Qian et al., 2000). Although it is
more common to find the presence of magnetite instead of hematite (e.g., Sillitoe,
2010), similar porphyry gold deposits rich in hematite has been reported (e.g., the Lac
Bachelor deposit, Abitibi, Canada; Fayol and Jébrak, 2017)
Cook and Ciobanu (2003) proposed that fluctuating chemical gradients of Cu, Pb,
Ag and Bi could lead to crystallization of the Bi-sulfosalts in the Ocna de Fier skarn
Fe-Cu deposit. We thus argue that the crystallization of Bi-Cu-Pb-Ag assemblage at
Yaoan maybe attributed to the oscillatory in fluid composition as well. This
explanation works well for the formation of intergrowths of hodrushite and
cuprobismutite in submicron-scale.
In the adjacent Beiya porphyry-skarn gold deposit, reported Bi-sulfosalts include
emplectite, wittichenite, galenobismutite, cosalite, matildite, bismuthinite derivatives,
lillianite homologues and galena-matildite solution (Zhou et al., 2016). Taken into
account the comparable assemblage of Bi-sulfosalts at Yaoan, it seems that these
alkaline-related gold ore clusters always contain abundant Bi-sulfosalts, which could
be possibly regarded as mineralogy indicator for gold mineralization. Further
investigation should be carried out to depict the mineralogy of Bi-minerals from other
gold deposits in the Jinshajing-Red River alkaline-porphyry metallogenetic belt, in
order to understand the association between the formation of Bi-minerals and gold
mineralization for alkaline porphyry-related hydrothermal systems.
Telluride minerals could provide valuable physicochemical constraints on
mineralization (Afifi et al., 1998a, 1988b). At Yaoan, tellurides are composed of
tetradymite, tsumoite, melonite, hessite and calaverite. Specifically, the Bi-tellurides
(e.g., tetradymite, tsumoite) are characterized by Bi/(Te + S) ratios ≤ 1, implying a
oxidized condition (Ciobanu et al., 2006, 2010). This condition is well consistent with
the ubiquitous presence of hematite. We argue that the oxidized condition is likely to
derive from the highly oxidized magma, as evidenced by high zircon Ce4+/Ce3+ values
of the syenite porphyry (avg: ~247; Xu et al., 2016). Besides, host rocks from the red
beds of the Upper Jurassic Tuodian Formation could also supply abundant oxidizing
agents (e.g., ferric oxides; Van Houten, 1968) to the hydrothermal system. In contrast,
tellurides from the skarn ores in the adjacent Beiya deposit consist of tsumoite,
tetradymite, Bi2Te (and native bismuth), Ag4Bi3Te3 and (Bi, Pb)3(Te,S)4, with Bi/(Te +
S) ratios above or below 1 (Zhou et al., 2016), indicating fluctuating redox conditions.
The reduced condition (also S-poor) favors the formation of Bi melts when
temperature is above its melting point (271°C). Bismuth melt has been proven to be
an effective gold scavenger (Tooth et al., 2008, 2011), which is one of the most
significant mechanisms for gold enrichment at Beiya (Zhou et al., 2016, 2017a).
However, at Yaoan the more oxidized condition would suppress the fractionation of
native bismuth or Bi melts. We thus suggest that the different redox conditions are one
of reasons contributing to the difference in the ore deposit size between the Yaoan and
Beiya deposits.
Bi et al. (2004) divided the Yaoan gold mineralization into two stages, i.e.,
sulfide stage, which includes fine-grained pyrite-chalcopyrite-galena stringer veins
and disseminated pyrite (gold host) in the potassic zone with their homogenization
temperatures being 292°C (from quartz); and oxide-sulfide stage, which consists of
coarse-grained pyrite and hematite (both gold host) in the breccias and banded ores
with their homogenization temperature being 146°C (from calcite). At Yaoan,
although disseminated pyrite was found in the altered host rock, there is not visible
gold in the pyrite. Moreover, in the potassic-altered syenite porphyry we only found
coarse-grained pyrite in veins. We thus argue that our auriferous ore vein samples
record one homogeneous stage for the gold mineralization, which is roughly similar to
the oxide-sulfide stage in that paper. By contrast, Qian and Li (2000) suggested that
fluid inclusions in the calcite from hematite-calcite assemblage homogenized at
260–196°C. Given that carbonates minerals (e.g., calcite, siderite) always document
the late/post mineralization and obviously cut sulfides and Bi-sulfosalts at Yaoan, their
homogenization temperatures (overall, 146–260°C) bound the lower limits of gold
mineralization conditions. Furthermore, fluid inclusions in hematite decrepitated at
350°C (Yunnan Hecheng Mining Co. Ltd., 2014), which bounds the upper limit of
ore-forming temperatures. Therefore, we reasonably propose that that the gold
mineralization temperatures range from 260–350 °C.
Given a temperature, thermodynamic parameters of mineralization such as fS2
and fTe2 could be obtained exactly. Based on thermodynamic properties of tellurides
and sulfides at 300°C, the coexistence of gold and calaverite and the presence of
melonite and bismuthinite at Yaoan have constrained the fS2 and fTe2 values to be fS2
= ~10-8.5 and fTe2 = ~10-7.9, respectively (Fig. 10). These sulfur and tellurium
fugacities conditions are also favorable for the crystallization of galena, hessite,
chalcopyrite and coexistence of pyrite and hematite, in accordance with the present
assemblage observed at Yaoan. In contrast, the fS2 and fTe2 values of the skarn-type
gold mineralization at Beiya are more variable (fS2 = 10-14–10-8.2 and fTe2 < 10-10 at
300°C; Zhou et al., 2016) and the fTe2 values are lower.

7. Conclusions
The Yaoan gold deposit contains abundant Bi-sulfosalts and tellurides that are in
direct contact with gold. Bismuth-sulfosalts comprise mainly cuprobismutite
homologues (e.g., probably submicroscopic intergrowths of hodrushite and
cuprobismutite), bismuthinite derivatives (e.g., bismuthinite, paarite, krupkaite,
lindströmite and friedrichite-aikinite) and emplectite, as well as minor paděraite and
matildite. Tellurides consist of tetradymite, tsumoite, melonite, hessite and calaverite.
The Bi-Te-minerals assemblage imply a magmatic origin and oxidized conditions at
high fTe2 for gold precipitation (fTe2 = ~10-7.9 and fS2 = ~10-8.5 at ~300°C).

Acknowledgements
This work was jointly supported by the National Natural Science Foundation of
China (No. U1302233, 41672071, 40830425, 40673045), the National Key Basic
Research Program (No. 2015CB452604, 2009CB421006), the Higher School
Specialized Research Fund for the Doctoral Program Funding Issue (No.
200805580031), and the Pearl River Scholar Funded Scheme (2011). The EPMA
analyses were carried out with the assistance of Dr. Wenxia Zhao (Sun Yat-sen
University).

References
Afifi, A.M., Kelly, W.C., Essene, E.J., 1988. Phase relations among tellurides, sulfides, and oxides;

Pt. II, Applications to telluride-bearing ore deposits. Economic Geology, 83: 395–404.

Afifi, A.M., Kelly, W.C., Essene, E.J., 1988. Phase relations among tellurides, sulfides, and oxides;

I, Thermochemical data and calculated equilibria. Economic Geology, 83: 377–394.

Bi, X.W., Cornell, D.H., Hu, R.Z., 2002. REE composition of primary and altered feldspar from

the mineralized alteration zone of alkaline intrusive rocks, western Yunnan Province, China.

Ore Geology Reviews, 19: 69–78.

Bi, X.W., Hu, R.Z., Cornell, D.H., 2004. The alkaline porphyry associated Yao'an gold deposit,

Yunnan, China: rare earth element and stable isotope evidence for magmatic-hydrothermal

ore formation. Mineralium Deposita, 39: 21–30.

Bi, X.W., Hu, R.Z., Hanley, J.J., Mungall, J.E., Peng, J.T., Shang, L.B., Wu, K.X., Suang, Y., Li,

H.L., Hu, X.Y., 2009. Crystallisation conditions (T, P, fO2) from mineral chemistry of Cu-

and Au-mineralised alkaline intrusions in the Red River–Jinshajiang alkaline igneous belt,

western Yunnan Province, China. Mineralogy and Petrology, 96: 43–58.

Bi, X.W., Hu, R.Z., Peng, J.T., Wu, K.X., Su, W.C., Zhan, X.Z., 2005. Geochemical

characteristics of the Yao'an and Machangqing alkaline-rich intrusions. Acta Petrologica

Sinica, 21: 115–126 (in Chinese with English abstract).

Bristol, S.K., Spry, P.G., Voudouris, P.C., Melfos, V., Mathur, R.D., Fornadel, A.P., Sakellaris,

G.A., 2015. Geochemical and geochronological constraints on the formation of shear-zone

hosted Cu–Au–Bi–Te mineralization in the Stanos area, Chalkidiki, northern Greece. Ore

Geology Reviews, 66: 266–282.

Buzatu, A., Damian, G., Dill, H.G., Buzgar, N., Apopei, A.I., 2015. Mineralogy and geochemistry

of sulfosalts from Baia Sprie ore deposit (Romania) — New bismuth minerals occurrence.

Ore Geology Reviews, 65: 132–147.

Cepedal, A., Fuertes-Fuente, M., Martín-Izard, A., González-Nistal, S., Rodríguez-Pevida, L.,

2006. Tellurides, selenides and Bi-mineral assemblages from the Río Narcea Gold Belt,

Asturias, Spain: genetic implications in Cu–Au and Au skarns. Mineralogy and Petrology, 87:

277–304.

Cheng, J., Xia, B., Zhang, Y.Q., 2007. Petrological and geochemical characteristics of Yao'an

alkaline complex in Yunnan province. Geotectonica et Metallogenia, 31: 118–125 (in

Chinese with English abstract).

Chung, S.L., Lee, T.Y., Lo, C.H., Wang, P.L., Chen, C.Y., Yem, N.T., Hoa, T.T., Genyao, W.,

1997. Intraplate extension prior to continental extrusion along the Ailao Shan-Red River

shear zone. Geology, 25: 311–314.

Chung, S.L., Lo, C.H., Lee, T.Y., Zhang, Y.Q., Xie, Y.W., Li, X.H., Wang, K.L., Wang, P.L.,

1998. Diachronous uplift of the Tibetan plateau starting 40 Myr ago. Nature, 394: 769–773.

Ciobanu, C.L., Pring, A., Cook, N.J., 2004. Micron- to nano-scale intergrowths among members

of the cuprobismutite series and paděraite: HRTEM and microanalytical evidence.

Mineralogical Magazine, 68: 279–300.

Ciobanu, C.L., Birch, W.D., Cook, N.J., Pring, A., Grundler, P.V., 2010. Petrogenetic significance

of Au–Bi–Te–S associations: The example of Maldon, Central Victorian gold province,

Australia. Lithos, 116: 1–17.

Ciobanu, C.L., Cook, N.J., Pring, A., 2005. Bismuth tellurides as gold scavengers. In: J. Mao and

F.P. Bierlein (J. Mao and F.P. Bierlein) (J. Mao and F.P. Bierleins), Mineral Deposit

Research: Meeting the Global Challenge: Proceedings of the Eighth Biennial SGA Meeting

Beijing, China, 18–21 August 2005. Springer Berlin Heidelberg, Berlin, Heidelberg, pp.

1383–1386.

Cook, N.J., Ciobanu, C.L., 2004. Bismuth tellurides and sulphosalts from the Larga hydrothermal

system, Metaliferi Mts., Romania: Paragenesis and genetic significance. Mineralogical

Magazine, 68: 301–321.

Cook, N.J., Ciobanu, C.L., 2003. Lamellar minerals of the cuprobismutite series and related

paděraite: a new occurrence and implications. The Canadian Mineralogist, 41: 441−456.

Cook, N.J., Ciobanu, C.L., Spry, P.G., Voudouris, P., 2009. Understanding

gold-(silver)-telluride-(selenide) mineral deposits. Episodes, 32: 249–263.

Deng, J., Wang, Q., Li, G., Hou, Z., Jiang, C., Danyushevsky, L., 2015. Geology and genesis of

the giant Beiya porphyry–skarn gold deposit, northwestern Yangtze Block, China. Ore

Geology Reviews, 70: 457–485.

Deng, J., Wang, Q., Li, G., Santosh, M., 2014. Cenozoic tectono-magmatic and metallogenic

processes in the Sanjiang region, southwestern China. Earth-Science Reviews, 138: 268–299.

Fayol N., Jébrak M., 2017. Archean Sanukitoid gold porphyry deposits: A new understanding and

genetic model from the Lac Bachelor gold deposit, Abitibi, Canada. Economic Geology, 112:

1913–1936.

Fu, Y., Sun, X.M., Lin, H., Zhou, H.Y., Li, X., Ouyang, X.Q., Jiang, L.Y., Shi, G.Y., Liang, Y.H.,

2015. Geochronology of the giant Beiya gold-polymetallic deposit in Yunnan Province,

Southwest China and its relationship with the petrogenesis of alkaline porphyry. Ore Geology

Reviews, 71: 138–149.

Gao, S., Xu, H., Zhang, D., Shao, H., Quan, S., 2015. Ore petrography and chemistry of the

tellurides from the Dongping gold deposit, Hebei Province, China. Ore Geology Reviews, 64:

23−34.

Hassan, L.Y., Roberts, M.P., 2017. Tellurides associated with volcanogenic massive sulfide (VMS)

mineralization at Yuinmery and Austin, Western Australia. Ore Geology Reviews, 80:

352–362.

He, W.Y., Mo, X.X., He, Z.H., White, N.C., Chen, J.B., Yang, K.H., Wang, R., Yu, X.H., Dong,

G.C., Huang, X.F., 2015. The geology and mineralogy of the Beiya skarn gold deposit in

Yunnan, Southwest China. Economic Geology, 110: 1625–1641.

Hou, Z.Q., Zhong, D.L., Deng, W.M., 2004. A tectonic model for porphyry

copper-molybdenum-gold metallogenic belts on the eastern margin of the Qinghai-Tibet

Plateau. Geology in China, 31: 1–14 (in Chinese with English abstract).

Hou, Z.Q., Ma, H.W., Khin, Z., Zhang, Y.Q., Wang, M.J., Wang, Z., Pan, G.T., Tang, R.L., 2003.

The Himalayan Yulong porphyry copper belt: Product of large-scale strike-slip faulting in

eastern Tibet. Economic Geology, 98: 125–145.

Hou, Z.Q., Zeng, P.S., Gao, Y.F., Du, A.D., Fu, D.M., 2006. Himalayan Cu–Mo–Au

mineralization in the eastern Indo–Asian collision zone: constraints from Re–Os dating of

molybdenite. Mineralium Deposita, 41: 33–45.

Hou, Z., Zaw, K., Pan, G., Mo, X., Xu, Q., Hu, Y., Li, X., 2007. Sanjiang Tethyan metallogenesis

in S.W. China: Tectonic setting, metallogenic epochs and deposit types. Ore Geology

Reviews, 31: 48–87.

Hu, R.Z., Burnard, P.G., Bi, X.W., Zhou, M.F., Pen, J.T., Su, W.C., Wu, K.X., 2004. Helium and

argon isotope geochemistry of alkaline intrusion-associated gold and copper deposits along

the Red River–Jinshajiang fault belt, SW China. Chemical Geology, 203: 305–317.

Jeleň, S., Pršek, J., Kovalenker, V.A., Topa, D., Sejkora, J., Števko, M., Ozdín, D., 2012. Bismuth

sulfosalts of the cuprobismutite, pavonite and aikinite series from the Rozália Mine,

Hodruša–Hámre, Slovakia. The Canadian Mineralogist, 50: 325–340.

Lai, C.K., Meffre, S., Crawford, A.J., Zaw, K., Halpin, J.A., Xue, C.D., and Salam, A., 2014a, The

Central Ailaoshan ophiolite and modern analogs: Gondwana Research, v. 26, p. 75–88.

Lai, C.K., Meffre, S., Crawford, A.J., Zaw, K., Xue, C.D., and Halpin, J.A., 2014b, The Western

Ailaoshan Volcanic Belts and their SE Asia connection: A new tectonic model for the

Eastern Indochina Block: Gondwana Research, v. 26, p. 52–74.

Li, Y., Mo, X.X., Yu, X.H., Huang, X.K., He, W.Y., 2011. Zircon U-Pb dating of several selected

alkali-rich porphyries from the Jinshajiang-Ailaoshan Fault Zone and geological significance.

Geoscience, 25: 189–200 (in Chinese with English abstract).

Liang, H.Y., Campbell, I.H., Allen, C., Sun, W.D., Liu, C.Q., Yu, H.X., Xie, Y.W., Zhang, Y.Q.,

2006. Zircon Ce4+/Ce3+ ratios and ages for Yulong ore-bearing porphyries in eastern Tibet.

Mineralium Deposita, 41: 152–159.

Liang, H.Y., Sun, W.D., Su, W.C., Zartman, R.E., 2009. Porphyry copper-gold mineralization at

Yulong, China, promoted by decreasing redox potential during magnetite alteration.

Economic Geology, 104: 587–596.

Liu, J.L., Zhao, S.J., Cook, N.J., Bai, X.D., Zhang, Z.C., Zhao, Z.D., Zhao, H.B., Lu, J., 2013.

Bonanza-grade accumulations of gold tellurides in the Early Cretaceous Sandaowanzi deposit,

northeast China. Ore Geology Reviews, 54: 110–126.

Lu, Y.J., Kerrich, R., Cawood, P.A., McCuaig, T.C., Hart, C.J.R., Li, Z.X., Hou, Z.Q., Bagas, L.,

2012. Zircon SHRIMP U–Pb geochronology of potassic felsic intrusions in western Yunnan,

SW China: Constraints on the relationship of magmatism to the Jinsha suture. Gondwana

Research, 22: 737–747.

Lu, Y.J., Kerrich, R., Kemp, A.I.S., McCuaig, T.C., Hou, Z.Q., Hart, C.J.R., Li, Z.X., Cawood,

P.A., Bagas, L., Yang, Z.M., Cliff, J., Belousova, E.A., Jourdan, F., Evans, N.J., 2013.

Intracontinental Eocene-Oligocene porphyry Cu mineral systems of Yunnan, western

Yangtze Craton, China: compositional characteristics, sources, and implications for

continental collision metallogeny. Economic Geology, 108: 1541–1576.

Lu, Y.J., Kerrich, R., Mccuaig, T.C., Li, Z.X., Hart, C.J.R., Cawood, P.A., Hou, Z.Q., Bagas, L.,

Cliff, J., Belousova, E.A., Tang, S.H., 2013. Geochemical, Sr–Nd–Pb, and zircon Hf–O

isotopic compositions of Eocene–Oligocene shoshonitic and potassic adakite-like felsic

intrusions in western Yunnan, SW China: petrogenesis and tectonic implications. Journal of

Petrology, 54: 1309–1348.

Makovicky, E., 1989. Modular classification of sulphosalts-current status: Definition and

application of homologous series. Neues Jahrb. Miner. Abh., 160: 269−297.

Mao, J.W., Zhou, Y.M., Liu, H., Zhang, C.Q., Fu, D.G., Liu, B., 2017. Metallogenic setting and

ore genetic model for the Beiya porphyry-skarn polymetallic Au orefield, western Yunnan,

China. Ore Geology Reviews, 86: 21–34.

Meinert, L.D., 2000. Gold in skarns related to epizonal intrusion. Reviews in Economic Geology,

13: 347–375.

Mumme, W.G., Žák, K., 1985. Paderaite, Cu5.9Ag1.3Pb1.6Bi11.2S22, a new mineral of the

cuprobismutite–hodrushite group. Neues Jahrbuch für Mineralogie Monatshefte: 557−567.

Mumme, W.G., 1986. The crystal structure of paderaite, a mineral of the cuprobismutite series.

The Canadian Mineralogist, 24: 513−521.

Pieczka, A., Gołębiowska, B., 2012. Cuprobismutite homologues in granitic pegmatites from

Szklarska Poręba, Karkonosze massif, southwestern Poland. The Canadian Mineralogist, 50:

313–324.

Qian, X.G., Li, Z.W., 2000. Geological and geochemical characteristics of the Yaoan gold ore

deposit in central Yunnan. Geotectonica et Metallogenia, 24: 31–36 (in Chinese with English

abstract).

Qian, X.G., Li, Z.W., Bai, J., 2000. A preliminary study on the genetic mechanism of Yao'an Au

deposit. Yunnan Geology, 21: 42–49 (in Chinese with English abstract).
Schärer, U., Tapponnier, P., Lacassin, R., Leloup, P.H., Zhong, D.L., Ji, S.C., 1990. Intraplate

tectonics in Asia: A precise age for large-scale Miocene movement along the Ailao Shan-Red

River shear zone, China. Earth and Planetary Science Letters, 97: 65–77.

Shuai, D.Q., Wan, Y.M., 1990. An assemblage of Fe-Cu-Pb-Bi-S-bearing sulfosalt minerals in the

Yaoan gold deposit. Yunnan Geology, 9: 154−161 (in Chinese).

Sillitoe, R.H., 2010. Porphyry copper systems. Economic Geology, 105: 3–41.

Takács, Á., Molnár, F., Turi, J., Mogessie, A., Menzies, J.C., 2017. Ore mineralogy and fluid

inclusion constraints on the temporal and spatial evolution of a high-sulfidation epithermal

Cu-Au-Ag deposit in the Recsk ore complex, Hungary. Economic Geology, 112: 1461–1481.

Tapponnier, P., Lacassin, R., Leloup, P.H., Scharer, U., Dalai, Z., Haiwei, W., Xiaohan, L.,

Shaocheng, J., Lianshang, Z., Jiayou, Z., 1990. The Ailao Shan/Red River metamorphic belt:

Tertiary left-lateral shear between Indochina and South China. Nature, 343: 431–437.

Tooth, B., Brugger, J., Ciobanu, C., Liu, W., 2008. Modeling of gold scavenging by bismuth melts

coexisting with hydrothermal fluids. Geology, 36: 815–818.

Tooth, B., Ciobanu, C.L., Green, L., O Neill, B., Brugger, J., 2011. Bi-melt formation and gold

scavenging from hydrothermal fluids: An experimental study. Geochimica et Cosmochimica

Acta, 75: 5423–5443.

Topa, D., Makovicky, E., Balić-Žunić, T., 2003. Crystal structures and crystal chemistry of

members of the cuprobismutite homologous series of sulfosalts. The Canadian Mineralogist,

41: 1481–1501.

Törmänen, T.O., Koski, R.A., 2005. Gold enrichment and the Bi-Au association in pyrrhotite-rich

massive sulfide deposits, Escanaba Trough, Southern Gorda Ridge. Economic Geology, 100:

1135–1150.

Turner, S., Arnaud, N., Liu, J., Rogers, N., Hawkesworth, C., Harris, N., Kelley, S., Van Calsteren,

P., Deng, W., 1996. Post-collision, Shoshonitic Volcanism on the Tibetan Plateau:

Implications for Convective Thinning of the Lithosphere and the Source of Ocean Island

Basalts. Journal of Petrology, 37: 45−71.

Van Houten, F.B., 1968. Iron Oxides in Red Beds. Geological Society of America Bulletin, 79:

399–416.
Voronin, M.V., Osadchii, E.G., 2013. Thermodynamic properties of silver and bismuth sulfosalt

minerals, pavonite (AgBi 3S5) and matildite (AgBiS2) and implications for ore deposits.

Economic Geology, 108: 1203–1210.

Voudouris, P.C., Spry, P.G., Mavrogonatos, C., Sakellaris, G., Bristol, S.K., Melfos, V., Fornadel,

A.P., 2013. Bismuthinite derivatives, lillianite homologues, and bismuth sulfotellurides as

indicators of gold mineralization in the Stanos shear-zone related deposit, Chalkidiki,

northern Greece. The Canadian Mineralogist, 51: 119–142.

Wang, D.H., Qu, W.J., Li, Z.W., Yin, H.L., Chen, Y.C., 2005. Mineralization episode of porphyry

copper deposits in the Jinshajiang-Red River mineralization belt: Re-Os dating. Science in

China Series D: Earth Sciences, 48: 192–198.

Wang, J.H., Yin, A., Harrison, T.M., Grove, M., Zhang, Y.Q., Xie, G.H., 2001. A tectonic model

for Cenozoic igneous activities in the eastern Indo–Asian collision zone. Earth and Planetary

Science Letters, 188: 123–133.

Wang, X.F., Metcalfe, I., Jian, P., He, L.Q., Wang, C.S., 2000. The Jinshajiang–Ailaoshan Suture

Zone, China: tectonostratigraphy, age and evolution. Journal of Asian Earth Sciences, 18:

675–690.

Xu, L.L., Bi, X.W., Hu, R.Z., Qi, Y.Q., Tang, Y.Y., Wang, X.S., Zhu, J.J., 2016. Redox states and

genesis of magmas associated with intra-continental porphyry Cu–Au mineralization within

the Jinshajiang–Red River alkaline igneous belt, SW China. Ore Geology Reviews, 73:

330–345.

Xu, W.G., Fan, H.R., Hu, F.F., Santosh, M., Yang, K.F., Lan, T.G., Wen, B.J., 2014. Gold

mineralization in the Guilaizhuang deposit, southwestern Shandong Province, China: Insights

from phase relations among sulfides, tellurides, selenides and oxides. Ore Geology Reviews,

56: 276–291.

Yin, A., Harrison, T.M., 2000. Geologic evolution of the Himalayan-Tibetan orogen. Annual

Review of Earth and Planetary Sciences, 28: 211–280.

Yunnan Hecheng Mining Co. Ltd., 2014. Reserves Verification Report of Mingzhu Gold Deposit,

Yaoan, Yunnan Province. Yunnan Hecheng Mining Co. Ltd., Yaoan (in Chinese).
Zhou, H.Y, Sun, X.M., Cook, N.J., Lin, H., Fu, Y., Zhong, R.C., Brugger, J., 2017a. Nano- to

micron-scale particulate gold hosted by magnetite: a product of gold scavenging by bismuth

melts. Economic Geology, 112: 993–1010.

Zhou, H.Y., Sun, X.M., Wu, Z.W., Liao, J.L., Fu, Y., Li, D., Pete, H., Liu, Y., Lin, H., Lin, Z.Y.,

2017b. Hematite U-Pb geochronometer: insights from monazite and hematite integrated

chronology of the Yaoan gold deposit, southwest China. Economic Geology, 112:

2023–2039.

Zhou, H.Y., Sun, X.M., Fu, Y., Lin, H., Jiang, L.Y., 2016. Mineralogy and mineral chemistry of

Bi-minerals: Constraints on ore genesis of the Beiya giant porphyry-skarn gold deposit,

southwestern China. Ore Geology Reviews, 79: 408–424.

 Figure captions

Fig. 1. Tectonic map of southwest China, showing the distribution of Cenozoic

alkaline intrusions in the Jinshajiang-Red River belt (modified after Wang et al.,
2001; Hou et al., 2004).

Fig. 2. Geological map (a) and simplified cross-section of prospecting line 72 (b) at
the Yaoan gold deposit, indicating the occurrence of alkaline porphyry, host rocks
and orebodies (modified after Yunnan Hecheng Mining Co. Ltd., 2014).

Fig. 3. Typical field and hand specimen photographs illustrating the Yaoan gold
mineralization. (a) Hematite (Hm) + pyrite (Py) mineralization developed along the
contact between the hematitized syenite porphyry and chlorite- and carbonate-altered
mudstone. (b) Hematite + calcite (Cc) veins accompanied by potassic alteration with
remnants of syenite porphyry. (c) Brecciated purplish mudstone (from the Tuodian
Formation) cemented by specular hematite and pyrite. (d) Coexistence of pyrite and
chalcopyrite (Cp) in a hematite matrix in mudstone-hosted veins. Note chloritized
selvage developed along hematite veins and the mudstone is chlorite, carbonate and
silicic altered. (e) Stockwork of specular hematite with chalcopyrite and pyrite
cutting phyllic-altered siltstone. The latter is also cut by calcite veinlets. (f)
High-grade gold ore comprising abundant specular hematite and chalcopyrite and
minor pyrite, being cut by calcite veins. Other abbreviations: Chl = Chlorite, Qz =
quartz.

Fig. 4. Photomicrographs showing common occurrence of gold (Au) in the Yaoan

gold deposit. (a) Gold as inclusion in pyrite. (b) Coexistence of gold and
chalcopyrite in pyrite. (c) Gold occurring as inclusions together with chalcopyrite in
pyrite, or filling the micro-fractures of pyrite. (d) Gold-bearing pyrite intergrown
with hematite and Bi-sulfosalts. (e) Minerals inclusions composed of gold, hematite,
pyrite and siderite (Sid) hosted by pyrite. (f) Gold as inclusion in specular hematite.
Figures a-d are under reflected light, whereas others are BSE images.

Fig. 5. Photomicrographs showing Bi-sulfosalts in the Yaoan gold deposit. (a) Large
patches of Bi-sulfosalts filling the intergranular spaces of hematite. (b-e) and (g-i)
Bi-sulfosalt patches composed of cuprobismutite homologues, paděraite (Pad) and
bismuthinite derivatives. (f) Intergrowths of chalcopyrite and Bi-sulfosalts stuffing
into a hematite framework. (j) Tiny inclusions of friedrichite-aikinite (Fri-Aik) and
tetradymite (Ttd) in emplectite (Emp), enveloped in chalcopyrite and hematite.
Figures a, f, g, i are under reflected light, while others are BSE images. Other
abbreviations: Bis = bismuthinite, Cbs = cuprobismutite, Hod = hodrushite, Kru =
krupkaite.

Fig. 6. Ternary (Cu + Fe) – Pb – (Bi + Ag) plot, indicating composition of

cuprobismutite homologues and paděraite in the Yaoan gold deposit. The empirical
formula (paděraite-emp.) and structure-based formula (paděraite-str.) of paděraite are
from Mumme and Žák (1985) and Mumme (1986), respectively. The paděraite from
the Swartberg pegmatite (SwP), South Africa and the Ocna de Fier skarn Fe-Cu
deposit (OFP), southwest Romania (Cook and Ciobanu, 2003) are shown for
comparison.

Fig. 7. Ternary Cu – Pb – Bi plot, showing composition of bismuthinite derivatives

from the Yaoan and the Beiya gold deposits.

Fig. 8. Photomicrographs of the occurrence of tellurides from the Yaoan gold deposit.
(a) Irregular tetradymite bleb enclosed with assemblage of emplectite and
cuprobismutite homologues. (b) Tetradymite coexisting with friedrichite-aikinite and
emplectite. (c) Intergrowths of bismuthinite, emplectite, krupkaite and tetradymite.
(d) Strings of galena (Gn) blebs and hessite (Hs) inclusions in pyrite. (e) Hessite in
friedrichite-aikinite coexisting with chalcopyrite and cuprobismutite homologues.
(f,g) Tiny tsumoite (Tsm) droplets in pyrite. (h) Coexistence of pyrite + chalcopyrite
with assemblage of tetradymite + hessite. (i) Melonite (Mel) intergrowing with
chalcopyrite. Note the ~120º grain boundary triple junctions between chalcopyrite,
Bi-sulfosalts and tellurides in (e) and (i). Figure e are under reflected light, whereas
others are BSE images.

Fig. 9. BSE images illustrating association of gold with Bi-sulfosalts and tellurides
in the Yaoan deposit. (a) Direct contact of gold with cuprobismutite homologues,
chalcopyrite and pyrite. (b) Intergrowth of gold and krupkaite. (c) Gold, chalcopyrite
and friedrichite-aikinite inclusions enveloped in pyrite. (d) Blebs composed of
bismuthinite, friedrichite-aikinite, gold, hessite and sphalerite (Sp) enclosed with
pyrite. (e) Intergrowths of gold, matildite (Mld) and another unknown Ag-Bi-S
mineral coexisting with chalcopyrite and pyrite. (f) Coexistence of gold and
calaverite (Cal) filling the void in krupkaite.

Fig. 10. Stability diagrams of logfS2 and logfTe2 for tellurides and sulfides at 300°C
(modified after Afifi et al., 1998a), showing the field of the Yaoan gold
mineralization.
 Table 1. EPMA results of cuprobismutite homologues from the Yaoan deposit.
Wt.% 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Fe 0.48 0.47 0.76 0.77 0.51 0.80 0.53 0.60 0.67 0.44 0.80 0.47 0.49 0.68 1.65 0.71
Cu 13.23 13.56 12.77 12.80 12.94 12.51 12.78 12.69 12.56 12.80 12.02 12.55 12.61 12.06 11.23 12.48
Ag 0.85 0.98 1.48 1.34 1.20 1.70 1.36 1.31 1.42 1.51 0.97 1.28 1.61 0.97 1.58 1.36
Bi 66.10 67.56 65.14 66.50 67.23 65.81 66.61 66.74 66.47 66.20 65.35 65.70 66.02 65.60 65.86 67.23
Sb - - - - 0.04 - - - - - - 0.05 - - 0.03 0.04
S 18.67 18.28 18.92 18.86 18.70 18.28 18.69 18.85 18.82 18.96 19.12 18.71 18.93 19.30 19.15 18.70
Se 0.04 - - 0.06 - 0.03 0.03 - 0.04 0.03 0.04 0.03 0.02 0.05 0.03 -
Te - 0.07 0.03 - 0.11 - - - 0.08 - 0.09 - - - 0.05 -
Total 99.39 100.91 99.10 100.33 100.73 99.13 100.01 100.23 100.06 99.96 98.40 98.82 99.68 98.68 99.60 100.52
N 1.49 1.50 1.54 1.57 1.63 1.63 1.64 1.65 1.66 1.66 1.66 1.67 1.69 1.69 1.69 1.70
Hod% 100 100 93 85 74 74 71 70 68 68 67 65 61 61 61 60

Wt.% 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
Fe 0.47 0.44 0.45 0.61 1.09 0.45 0.54 0.52 0.59 0.46 0.72 0.51 0.60 0.72 0.71 0.62
Cu 12.31 12.16 12.20 12.07 11.63 12.26 12.07 12.11 11.94 12.42 11.63 11.93 11.86 11.51 11.49 11.47
Ag 0.68 1.08 1.06 1.11 1.30 0.60 1.36 0.98 1.19 1.48 1.47 1.15 0.85 1.52 1.25 1.58
Bi 66.62 65.36 65.93 66.35 66.46 67.26 65.36 66.23 65.62 67.08 65.12 66.08 66.95 66.15 67.12 66.27
Sb 0.06 0.03 - - - - - 0.05 0.03 0.06 - - - - - -
S 18.99 19.19 19.03 19.35 19.22 18.49 19.24 19.16 19.40 18.57 19.11 18.77 18.78 18.73 18.93 18.99
Se 0.04 0.03 0.02 0.06 0.03 0.04 0.02 0.04 - 0.03 0.02 0.03 0.04 - 0.03 0.03
Te 0.07 0.09 0.12 - - - - 0.09 - - - 0.05 0.11 - - -
Total 99.25 98.37 98.81 99.57 99.74 99.12 98.62 99.16 98.79 100.10 98.11 98.54 99.19 98.67 99.52 99.02
N 1.72 1.74 1.75 1.76 1.76 1.76 1.76 1.77 1.77 1.79 1.82 1.82 1.83 1.90 1.94 1.96
Hod% 56 51 50 49 48 48 48 46 45 42 36 35 35 19 12 8
- = below detection limit (Au, Pb and Zn of all analyses are below detection limits and thus are not listed).
 Table 2. Representative EPMA results of paděraite and emplectite from the Yaoan deposit.

Wt.% Paděraite Emplectite

Fe 0.09 0.02 0.51 0.12 0.09 0.09 0.45 0.12 0.12 0.12 0.04 0.04 0.11 0.09 0.36
Cu 11.93 11.96 11.35 11.46 11.32 10.73 22.05 18.54 18.51 18.57 18.50 19.58 16.92 16.90 16.87
Ag 1.01 1.02 1.13 1.67 1.31 0.25 0.30 0.03 0.05 0.03 0.11 0.04 - - 0.06
Pb 4.08 4.39 3.75 5.01 5.43 5.13 - - - - - - 2.54 - -
Bi 63.98 64.04 65.50 63.67 63.15 64.28 59.54 62.97 61.07 62.61 62.90 60.95 61.31 63.42 64.48
Sb - - - - - - 0.05 - - 0.08 0.05 0.03 - - 0.03
S 18.39 18.46 18.63 18.18 17.91 18.18 18.26 18.93 18.78 18.55 18.70 19.03 18.29 18.79 18.22
Se - 0.04 - 0.02 - 0.02 0.05 0.04 0.06 0.03 0.04 - 0.04 - -
Te - - 0.06 - 0.11 - - - 0.06 - - - - - -
Total 99.53 99.94 100.94 100.18 99.32 98.70 100.70 100.63 98.65 99.99 100.35 99.66 99.21 99.20 100.02

Chemical formula on the basis of: 42 atoms 4 atoms

Fe 0.06 0.01 0.35 0.08 0.06 0.06 0.03 0.01 0.01 0.01 0.00 0.00 0.01 0.01 0.02
Cu 7.18 7.17 6.75 6.92 6.93 6.61 1.14 0.98 0.99 1.00 0.99 1.03 0.93 0.92 0.92
Ag 0.36 0.36 0.40 0.59 0.47 0.09 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Pb 0.75 0.81 0.68 0.93 1.02 0.97 0.00 0.00 0.00 0.00 0.00 0.00 0.04 0.00 0.00
Bi 11.70 11.68 11.84 11.69 11.75 12.04 0.94 1.02 1.00 1.02 1.02 0.98 1.02 1.05 1.07
Sb 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
S 21.93 21.94 21.96 21.76 21.73 22.20 1.88 1.99 2.00 1.97 1.98 1.99 1.99 2.03 1.98
Se 0.01 0.02 0.01 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Te 0.01 0.01 0.02 0.01 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
- = below detection limit (Au and Zn of all analyses are below detection limits and thus are not listed).
 Table 3. Representative EPMA data of bismuthinite derivatives from the Yaoan deposit.
Bismuthinite Paarite Krupkaite Lindströmite Friedrichite-aikinite
Wt.% (n = 4) (n = 1) (n = 5) (n = 1) (n = 17)
Fe 0.05 0.02 0.05 0.09 0.06 0.27 0.10 - 0.08 0.04 0.20 0.48 0.15 0.12 0.09 0.59
Cu 0.34 0.38 4.84 5.48 5.64 5.56 6.43 6.17 8.90 9.54 9.48 9.24 9.51 9.75 9.70 10.55
Ag - 0.10 - - - - 0.06 - - - - - - - 0.04 -
Pb 0.52 0.90 16.93 18.19 18.80 19.79 19.57 22.25 34.25 33.42 34.24 34.32 34.17 34.36 36.00 33.62
Bi 80.57 79.73 61.49 57.58 57.33 56.81 56.88 53.89 40.27 39.71 39.64 38.75 37.55 37.49 37.26 37.56
Sb 0.06 - - - - - - - - - - - - 0.05 - -
S 18.18 18.07 17.55 17.13 17.62 17.18 17.30 17.54 16.43 16.84 16.98 16.38 17.03 16.64 16.96 16.27
Se - - 0.04 - 0.04 - 0.05 0.07 0.09 - - 0.03 - 0.03 0.02 0.04
Te - - - 0.09 0.07 - 0.07 - - - - - 0.06 0.05 - 0.13
Total 99.77 99.21 100.90 98.55 99.57 99.65 100.46 99.94 100.03 99.55 100.54 99.20 98.50 98.49 100.07 98.79
Cu:Pb 2.12 1.39 0.93 0.98 0.98 0.92 1.07 0.90 0.85 0.93 0.90 0.88 0.91 0.93 0.88 1.02
naikinite 2.43 3.01 42.51 48.33 49.54 51.33 53.33 56.83 88.64 90.18 91.19 92.59 93.73 94.38 95.88 97.06

- = below detection limit (Au and Zn of all analyses are below detection limits and thus are not listed).
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Fig. 10
 Highlights

1. Bismuth-sulfosalts principally comprise bismuthinite derivatives, paděraite, cuprobismutite homologues, and emplectite, which are
characterized by replacement textures resulting from the changes in fluid composition.

2. Tellurides/Bi-chalcogenide include tsumoite, melonite, hessite, calaverite, and tetradymite, indicating the precipitation of gold under oxidizing
conditions with initial high fTe2.

3. The Yaoan gold metallogenesis was likely linked to the syenite porphyry magmatism that was originally sourced from a regional lithospheric
mantle probably metasomatized by subducted Te-rich sediments