Ore Geology Reviews 99 (2018) 1–16

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Ore Geology Reviews

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Multistage pyrite in the Getang sediment-hosted disseminated gold deposit, T

southwestern Guizhou Province, China: Insights from textures and in situ
chemical and sulfur isotopic analyses
⁎
Xinlu Hua,b, , Yongjun Gonga, Guoping Zenga, Zhenjie Zhangc, Jian Wanga, Shuzhen Yaoa,d
a
Faculty of Earth Resources, China University of Geosciences, Wuhan 430074, China
b
National Demonstration Center for Experimental Mineral Exploration Education, China University of Geosciences, Wuhan 430074, China
c
School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, China
d
Key Laboratory of Tectonics and Petroleum Resources, Ministry of Education, Wuhan 430074, China

A R T I C LE I N FO A B S T R A C T

Keywords: Getang is a representative sediment-hosted disseminated gold (SHDG) deposit in the southwestern Guizhou
Pyrite Province, China. The majority of gold is present as structurally bound Au+ in pyrite, with a minor amount
LA-MC-ICP-MS occurring as nanoparticles (Au0). Four generations of pyrite (Py0, Py1, Py2, and Py3) were distinguished based
Sulfur isotope on morphology and paragenesis. Electron microprobe (EMP), laser-ablation inductively coupled plasma mass
Sediment-hosted disseminated gold deposit
spectrometry (LA-ICP-MS), and laser-ablation multi-collector inductively coupled plasma mass spectrometry
Southwestern Guizhou Province
(LA-MC-ICP-MS) analyses were conducted to determine the chemical and sulfur isotopic composition of the
pyrite.
The pre-ore diagenetic pyrite (Py0) has a framboidal texture and is characterized by relatively high con-
centrations of As, Co, Ni, Cu, Zn, Pb, and Mo. It has negative δ34S values of −38.4 to −4.0‰, indicating the
derivation of sulfur by bacterial reduction of marine sulfate during sedimentation and diagenesis. The early ore
stage pyrite (Py1) coexists with arsenopyrite as subhedral-anhedral grains, and contains high concentrations of
As, Ni, Cu, and Zn, with large variation in Co and Pb content. It has positive δ34S values of +3.8 to +17.7‰,
which are interpreted to be complete thermochemical reduction of marine sulfate. The intermediate ore stage
pyrite (Py2) is disseminated in the host rocks, and occurs as overgrowths on Py0 and Py1. It is enriched in Au and
Ag but depleted in As, Co, Ni, Cu, and Bi. The late ore stage pyrite (Py3) occurs as acicular to columnar ag-
gregates, and is intergrown with calcite. It contains high concentrations of As and low concentrations of Pb, Mo,
and Bi. Py2 and Py3 display a comparable narrow range of δ34S values from +1.9 to +8.4‰, which are
interpreted to result from a magmatic source.
All the stable isotope data together with the gravity and magnetic evidences suggests that sulfur, gold, and the
mineralizing fluids in the Getang deposit were probably originated from deep magmatic hydrothermal systems.
The absence of igneous intrusions in southwestern Guizhou may be attributed to the relatively shallow denu-
dation depth in this area.

1. Introduction
Sediment-hosted disseminated gold (SHDG) deposits, also known as
Carlin-style gold deposits, are important producers of gold in the world,
especially in the United States and China (Large et al., 2011, Large et al.,
2016; Groves et al., 2016). This type of gold deposits in China are mostly
concentrated in two “golden triangles”, namely the Yunnan–Guizhou–
Guangxi and Sichuan–Gansu–Shanxi regions (Zaw et al., 2007; Peng et al.,
2014; Chen et al., 2015). The southwestern Guizhou Province is the most
prolific gold-producing area of the Yunnan–Guizhou–Guangxi golden
triangle. Since the discovery of the first SHDG deposit at Banqi in 1978 (Tu,
1990), more than 20 gold deposits with similar characteristics have been
found in southwestern Guizhou (Hu et al., 2002; Gu et al., 2003). The most
important deposits in this area include Shuiyindong (Su et al., 2008, 2012;
Tan et al., 2015; Hou et al., 2016), Jinfeng (Lannigou) (Chen et al., 2011),
Zimudang (Liu et al., 2015), and Getang (Huang et al., 2012). Although the
geological characteristics of these deposits have been well documented, a
widely accepted explanation for their genesis is still lacking. Three major
models have been proposed for the origin of Au and the mineralizing fluids:
(1) the sedimentary model suggest that Au was sourced from pre-enriched

⁎
Corresponding author at: Faculty of Earth Resources, China University of Geosciences, Wuhan, Lumo Road No. 388, Hongshan District, Wuhan 430074, China.
E-mail address: huxinlu00@foxmail.com (X. Hu).

https://doi.org/10.1016/j.oregeorev.2018.05.020
Received 22 January 2018; Received in revised form 8 May 2018; Accepted 29 May 2018
Available online 30 May 2018
0169-1368/ © 2018 Elsevier B.V. All rights reserved.
X. Hu et al.
Fig. 1. Regional geological sketch map of southwestern Guizhou, showing the locations of the major SHDG deposits (modified after Su et al., 2009a; Tan et al., 2015).
sediments by circulation of meteoric water (Zhang et al., 2003; Peng et al.,
2014); (2) the metamorphic model favors a metamorphic origin of the mi-
neralizing fluids related to crustal thickening and prograde metamorphism
(Su et al., 2009a); (3) the magmatic model argues that Au was derived from
concealed granitic intrusions (Liu et al., 2006; Zhang et al., 2010). Most of
these inferences are based on interpretation of stable isotope data obtained by
conventional analyses of mineral separates from different gold deposits.
Pyrite is the most dominant ore mineral in SHDG deposits, making it
a potential indicator of ore genesis (Morey et al., 2008; Hazarika et al.,
2013; Goldfarb et al., 2014; Gregory et al., 2016). Previous studies have
recognized a close correlation between Au and As, and proposed that a
substantial fraction of Au is present as “invisible gold” within grains of
As-rich pyrite, namely arsenian pyrite, which contains ppm to weight-
percent amounts of As (Arehart et al., 1993; Fleet and Mumin, 1997;
Cline, 2001; Cepedal et al., 2008; Large et al., 2009; Deditius et al.,
2014). However, Au-bearing pyrite or arsenian pyrite in SHDG deposits
is commonly fine-grained and texturally complex (Su et al., 2008, 2012;
Li et al., 2014; Chen et al., 2015), making it difficult to convincingly
define the chemical and sulfur isotopic composition of ore-stage pyrite
by conventional analyses of bulk ore samples or pyrite separates. The
lack of reliable information about the ore-stage and pre- or post ore-
stage pyrite hampers our understanding about the genesis of the SHDG
deposits. Recent microbeam analytical techniques, such as laser-abla-
tion inductively coupled plasma mass spectrometry (LA-ICP-MS) to
determine chemical compositions and laser-ablation multi-collector
inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to de-
termine sulfur isotopic compositions, make it possible to discriminate
and analyze the different generations of pyrite.
The Getang gold deposit contains a proven reserve of about
30 tonnes at 5.1 g/t Au (Zhang et al., 2003; Liu et al., 2013), and the
measured Au resource is still increasing. However, systematic studies
on this deposit are absent because of pervasive weathering and
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Ore Geology Reviews 99 (2018) 1–16
oxidation in the mining district. A series of primary gold orebodies were
not revealed until the past few years, providing an excellent opportu-
nity to determine the metallogenesis of this deposit. In this study, four
generations of pyrite have been distinguished at Getang based on field
and petrographic observations: diagenetic framboidal pyrite in the host
rocks (Py0), fine-grained pyrite associated with arsenopyrite (Py1),
disseminated main ore-stage pyrite (Py2), and pyrite veinlets cross-
cutting earlier formed mineralization (Py3). Here we present miner-
alogical and in situ chemical and S isotopic analyses for distinct vari-
eties of pyrite from the Getang gold deposit, aiming to evaluate the
major and trace elemental compositions of pyrite grains, and to identify
sulfur sources during each stage of pyrite formation. Since the char-
acteristics of Getang are typical of many other SHDG deposits in
southwestern Guizhou Province, the results of this paper may be useful
for identification of Au-bearing sulfide minerals in the region and for
understanding the ore-forming processes of similar SHDG deposits.
2. Geologic setting
The southwestern Guizhou Province is located at the junction be-
tween the southwestern margin of the Yangtze Craton and the north-
western margin of the Youjiang Basin (Peters et al., 2007; Su et al.,
2009a; Tan et al., 2015; Fig. 1A). The Yangtze Craton consists of Pro-
terozoic metamorphic rocks overlain by Devonian to Triassic sedi-
mentary sequences. While the Youjiang Basin lies on lower Paleozoic
basement and evolved in three main stages: rift basin from the early
Devonian to the early Permian, back-arc basin from the late Permian to
the early Triassic, and foreland basin during the late Triassic, in re-
sponse to the opening, subduction, and closing of the Paleo-Tethys
ocean, respectively (Gu et al., 2012; Deng and Wang, 2016).
Exposed and drilled lithologies in southwestern Guizhou are pre-
dominantly Devonian to Triassic in age. The Triassic and Permian strata
X. Hu et al. Ore Geology Reviews 99 (2018) 1–16

Fig. 2. Simplified geologic plan of the Getang gold deposit (modified after Liu et al., 2013).

Fig. 3. Geological cross section of the Getang gold deposit (Wu et al., 2014).

are most widely distributed, while the Devonian and Carboniferous
strata occur sporadically within the cores of some anticlines or domes.
From the northwest to the southeast (Yangtze Craton to Youjiang
Basin), the sedimentary environment changed gradually from con-
tinental through shallow-marine platform to deep-marine basin (Zhang
et al., 2003; Hou et al., 2016). The shallow-marine platform rocks
consist of limestone, bioclastic limestone, dolomite, and argillite. The
deep-marine sedimentary rocks include sandstone, siltstone, argillite,
marl, and black shale.
Regional tectonic framework is dominated by the NE-trending Mile-
Shizhong fault in the northwest, the NS-trending Puding-Ceyang fault in
the east, and the ENE-trending Nanpanjiang fault in the south (Fig. 1B).
Movement of these faults heavily influenced the sedimentation and
structural deformation in southwestern Guizhou from the late Palaeo-
zoic to the Triassic (Zhang et al., 2003). The shallow-marine platform
facies on the northwest side were gently folded or domed and exhibit
brittle deformation, whereas the deep-marine rocks on the southeast
side were tightly folded resulting in ductile-brittle thrusts and high-
angle reverse faults (Peters et al., 2007; Chen et al., 2011).
Igneous rocks outcropping in southwestern Guizhou mainly include

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X. Hu et al.
the late Permian Emeishan flood basalts in the northwest and the al-
kaline ultramafic rocks in the east (Fig. 1B). The Emeishan flood basalts
are composed of basaltic lava, pyroclastics, and breccias. They are
highly variable in thickness but quite uniform in chemical composition,
indicating that they were probably erupted in a tectonically stable in-
traplate environment (Mei, 1980; Ali et al., 2005). The alkaline ultra-
mafic rocks intruded the Permian to Triassic rocks in the form of pipes
and dykes. They are principally distributed along a NS-trending tran-
sitional sedimentary facies belt, and are considered to be controlled by
the Puding-Ceyang fault (Su et al., 2009b; Fig. 1B). These ultramafic
rocks display LA-ICP-MS zircon U-Pb and biotite 40Ar/39Ar ages of ca.
88–85 Ma (Su et al., 2009b; Liu et al., 2010), corresponding to the
extensional phase of the Yanshanian orogenic cycle.
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Ore Geology Reviews 99 (2018) 1–16
Fig. 4. Photographs showing typical features of gold
obodies and ores in the Getang gold deposit. (A)
Surface mining landscape of the Kesa ore block; (B)
Oxidized orebody in the Erlongkou ore block; (C)
Primary orebody in the Longkou ore block; (D)
Disseminated diagenetic pyrite in argillite of the
Longtan Formation; (E) Massive pyrite – arseno-
pyrite aggregate of stage I; (F) Brecciated ore of
stage I wrapped by disseminated ore of stage II; (G)
Disseminated pyrite of stage II; (H) calcite – pyrite
veins of stage III; (I) Sporadic realgar and orpiment
in silicified argillite. Mineral abbreviations: Py –
pyrite, Apy – arsenopyrite, Cal – calcite, Rlg – re-
algar, Orp – orpiment.
SHDG deposits in southwestern Guizhou are traditionally classified
into two types: stratabound deposits and fault-controlled deposits
(Zhuang et al., 1999; Peters et al., 2007; Chen et al., 2015). The stra-
tabound gold deposits generally have laminated or lenticular orebodies
that extend persistently along unconformity surfaces or interlayer
fracture zones associated with anticlines or domes (e.g., Getang and
Nibao). The fault-controlled gold deposits are characterized by steep or
dendritic orebodies controlled by oblique fault systems (e.g., Lannigou
and Yata). Host rocks for the SHDG deposits are mainly siltstone,
limestone, and argillite of the Permian and Triassic age (Peng et al.,
2014; Deng and Wang, 2016). The timing of gold mineralization in the
southwestern Guizhou is still obscure due to the lack of ore-related
minerals which are suitable for isotopic dating. The published age data
X. Hu et al. Ore Geology Reviews 99 (2018) 1–16

Fig. 5. Representative wallrock alteration types in the Getang gold deposit. (A) Quartz vein in silicified limestone. (B) Fluorite stockwork in silicified argillite and
limestone; (C) Calcite stockwork filling in fractures of limestone. (D) Calcite vein in argillite. (E) Anhydrite vein in silicified breccias. (F) Kaolinite, illite, and
anhydrite patches in the fracture zone between the orebody and silicified limestone. Mineral abbreviations: Qz – quartz, Fl – fluorite, Cal – calcite, Anh – anhydrite,
Kln – kaolinite, Ilt – illite.

suggest that the SHDG deposits in southwestern Guizhou were chiefly
produced at ca. 200 Ma and 130 Ma (Su et al., 2009b; Chen et al., 2015;
Deng and Wang, 2016).
3. Deposit geology
The Getang gold deposit is situated on the southeastern limb of the
Getang dome (Fig. 1B). Sedimentary sequences in the deposit include
limestone, siltstone, argillite, and shale of Middle Permian to Lower
Triassic ages (Fig. 2). The Middle Permian Maokou Formation is
dominated by thickly bedded massive limestone. The Upper Permian
Longtan Formation can be divided into four stratigraphic units in the
Getang district. The lowest unit consists of argillite and carbonaceous
shale, which are densely fractured. The second unit is composed of
argillite intercalated with coal seams. The third unit is mainly silicified
limestone. The fourth unit includes siltstone, sandstone, and sub-
ordinate limestone. The Upper Permian Changxing and Dalong For-
mations are composed mainly of bioclastic limestone. The Lower
Triassic Yelang Formation is comprised of siltstone and shale inter-
calated with muddy limestone. These strata form the regional Getang
dome, which plunges SE in the vicinity of the mining district (Zhang
et al., 2003).
The dominant structures in the Getang gold deposit include the
interlayer fracture zones and several groups of oblique faults. The in-
terlayer fracture zones are developed along the unconformity between
the Longtan and Maokou Formations. The oblique fault system com-
prises the NE-, EW-, and nearly NS-trending high-angle normal faults
(Wu et al., 2014). The NE-trending faults are most common, and in-
tersect the mineralized zone, indicating that they formed later than gold
mineralization.
The Getang gold deposit consists of several ore blocks, including
Getang, Longkou, Erlongkou, Kesa, and Kehua (Fig. 2). Gold miner-
alization is primarily confined to the interlayer fracture zones at the
base of the Longtan Formation (Fig. 3), and is hosted within silicified,
brecciated limestone and argillite. More than 30 stratoid or lenticular
gold orebodies have been discovered in this deposit. The orebodies
extend discontinuously over an area of about 15 km2, with highly
variable thickness from 0.5 to 30.4 m. The hanging wall of the or-
ebodies is relatively flat, while the foot wall is commonly undulant
along the paleo-karst planes of limestone formations (Fig. 4A). The ores

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X. Hu et al.
Fig. 6. Summary of the paragenetic sequence from pre-ore stage to post-ore stage in the Getang gold deposit.
include primary and oxidized varieties (Fig. 4B and C). The dominant
style of primary ores consists of pyrite and minor arsenopyrite dis-
seminated sparsely in silicified breccias (Fig. 4C). The Au grade in-
creases from 2 to 4 ppm in primary ores to 4–8 ppm in oxidized ores
(Zhang et al., 2003; Liu et al., 2013).
Primary ore mineral is pyrite, with minor amounts of arsenopyrite,
stibnite, realgar, and orpiment (Fig. 4D–I). Goethite and jarosite are
also common minerals in oxidized ores. Gangue minerals include
quartz, fluorite, calcite, anhydrite, kaolinite, and illite (Fig. 5A–F).
Sulfide and gangue minerals display disseminated, stockwork, banded,
and brecciated textures. Hydrothermal alteration is pervasive and in-
volves a combination of silicification, carbonatization, argillization,
and sulfidation. Silicification is typically identified as jasperoid quartz
grains and minor quartz veinlets. Carbonatization is most common, and
is preferentially expressed as calcite veins in carbonate host rocks. In
contrast, argillic alteration, characterized by clay minerals of kaolinite
and illite, is mainly present in argillite and carbonaceous shale.
According to the textures, crosscutting relationships, and mineral
assemblages, at least five paragenetic stages can be recognized in the
Getang gold deposit: (1) pre-ore diagenetic stage (pyrite), (2) early ore
stage (pyrite – arsenopyrite), (3) intermediate ore stage (quartz –
pyrite), (4) late ore stage (calcite – pyrite), and (5) post-ore stage
(fluorite – anhydrite). The pre-ore diagenetic stage consists of dis-
seminated framboidal pyrite in argillite and shale (Fig. 4D). The early
ore stage is dominated by semi-massive and dense disseminated ores
composed of pyrite and minor arsenopyrite (Fig. 4E and F). The inter-
mediate ore stage is characterized by jasperoid quartz or milky quartz
veinlets accompanied by disseminated fine-grained pyrite (Figs. 4F–G,
5A). The late ore stage occurs as calcite veins with or without pyrite
grains (Figs. 4H, 5C and D). The post-ore stage is mainly expressed as
fluorite and anhydrite veins that cut the earlier formed disseminated
and vein ores of the previous stages (Fig. 5B and E). The mineral as-
semblages of each stage are summarized in Fig. 6.
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Ore Geology Reviews 99 (2018) 1–16
4. Samples and analytical methods
4.1. Sample preparation
Representative samples of different mineralization stages were col-
lected from non-oxidized outcrops and drill holes of the Kesa, Longkou,
Erlongkou, and Getang ore blocks (Fig. 2). Each sample was prepared as
polished thin sections of 0.5 mm thick for textural, chemical, and sulfur
isotope analyses. Mineralogical and textural studies were conducted on
52 polished sections by reflected-light microscopy and back-scattered
electron (BSE) imaging. The areas of interest were marked and photo-
graphed prior to chemical and sulfur isotope analyses. The major- and
trace-element characterization of pyrite were carried out using electron
microprobe (EMP) analysis and in situ laser-ablation inductively cou-
pled plasma mass spectrometry (LA-ICP-MS), respectively. After com-
positional analyses, in situ sulfur isotope analysis of pyrite was per-
formed by laser-ablation multi-collector inductively coupled plasma
mass spectrometry (LA-MC-ICP-MS).
4.2. EMP analysis
Electron microprobe analysis of pyrite was carried out using a JEOL
JXA-8100 microprobe equipped with wavelength dispersive spectrometers
(WDS) at the State Key Laboratory of Geological Processes and Mineral
Resources, China University of Geosciences, Wuhan. The operating condi-
tions were 20 kV accelerating voltage, 20nA beam current, with focused
diameter of 2 or 5 μm depending on the size of pyrite grains. The following
sulfides and native metals were used as standards: FeS2 (Fe, S), GaAs (As),
PbS (Pb), ZnS (Zn), and Cu0 (Cu). The detection limits for each element
were Fe (83 ppm), S (61 ppm), As (82 ppm), Pb (637 ppm), Zn (176 ppm),
and Cu (139 ppm). Analytical precision and accuracy were better than 3%
based on replicate analyses of the standards.
X. Hu et al.
Fig. 7. Morphological and textural features of different generations of pyrite in
the Getang gold deposit. (A-B) Backscattered electron (BSE) image of Py0
framboids and clusters within argillite of the Longtan Formation. (C) BSE image
of Py0 framboids overgrown by Py1. (D) Reflected light image of Py1 coexisting
with arsenopyrite. (E) BSE image of zoned pyrite clusters. (F) BSE image of
individual Py1 grain overgrown by Py2. (G) Reflected light image of large-sized
Py1 surrounded by Py2 grains. (H) BSE image of acicular Py3 aggregates.
Mineral abbreviations: Py – pyrite, Apy – arsenopyrite.
4.3. LA-ICP-MS analysis
Trace element analysis of pyrite was conducted by LA-ICP-MS at the
Sample Solution Analytical Technology Co., Ltd., Wuhan, China, using
a GeolasPro laser ablation system that consists of a COMPexPro 102 ArF
excimer laser and a MicroLas optical system. The analytical instrument
and procedures follow those described by Zong et al. (2017) and Large
et al. (2007), respectively. An Agilent 7700e ICP-MS instrument was
used to acquire ion-signal intensities. Helium was used as a carrier gas.
Argon was used as the make-up gas and mixed with the carrier gas via a
T-connector before entering the ICP. A “wire” signal smoothing device
is included in this laser ablation system, by which smooth signals are
produced even at very low laser repetition rates down to 1 Hz (Hu et al.,
2015). The analyses were performed in spot mode using a laser beam of
16 or 32 μm diameter and a repetition rate of 5 Hz. Trace element
compositions of pyrites were calibrated against the USGS MASS-1 sul-
fide reference material without using an internal standard (Liu et al.,
2008). Each analysis incorporated a background acquisition of ap-
proximately 20–30 s followed by 50 s of data acquisition from the
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sample. Off-line concentration calculations were performed by the
ICPMSDataCal software (Hu et al., 2016, Hu et al., 2017). The un-
certainties and detection limits for each analysis are reported in the
electronic supplement.
4.4. In situ S isotope analysis
In situ S isotope analyses were performed by LA-MC-ICP-MS at the
State Key Laboratory of Geological Processes and Mineral Resources,
China University of Geosciences, Wuhan. The analytical methods are
based on Bendall et al. (2006) and Craddock et al. (2008). A Nu Plasma
II MC-ICP-MS equipped with a Resolution-S155 excimer ArF laser ab-
lation system was used for the analyses. The laser diameter was 16 or
33 μm. The laser frequency was 8 Hz. Each data was acquired for 40 s
for the 34S and 32S isotopic species. Fractionations due to incomplete
combustion were calibrated using the S isotopic standard WS-1. The
isotopic composition of sulfur is reported using the standard δ notation
in units of ‰ relative to Canon Diablo Troilite (CDT) standard. The
analytical precision is about ± 0.2‰ (Liu et al., 2017).
5. Results
5.1. Occurrence and texture of pyrite
Pyrite is the most abundant sulfide mineral in the Getang gold de-
posit, and displays a great variety of textural and structural types. Four
main generations of pyrite have been recognized based on morphology,
texture, and paragenesis. Each generation of pyrite corresponds to its
particular paragenetic stage. The individual pyrite types are discussed
below in paragenetic order.
5.1.1. Pyrite 0
Pyrite 0 (Py0) is the first generation of early diagenetic pyrite, and is
best developed in organic-rich argillite and shale of the Longtan
Formation (Fig. 4D). This type of pyrite commonly shows fine-grained
framboidal texture (Fig. 7A), which is characterized by replacement of
biodetritus or fossils by tiny pyrite aggregates (Fig. 7B). Individual Py0
microcrystals are ∼0.1 to 3 μm in size, and form framboids from 5 to
40 μm across (Fig. 7A–C). Some of the Py0 grains are overgrown by
later generations of pyrite in the ore stages (Fig. 7C).
5.1.2. Pyrite 1
The early ore stage pyrite 1 (Py1) commonly coexists with arseno-
pyrite as subhedral-anhedral grains, and presents as semi-massive ag-
gregates in altered and mineralized rocks of the Maokou and Longtan
Formations (Fig. 4E and F). The Pyl crystals vary from < 10 to 100 μm
in size, with a few being larger than 200 μm (Fig. 7C and D). They
locally surround and overgrow Py0 (Fig. 7C). Some Py1 grains have
overgrowth rims of later generations of pyrite (Fig. 7E–G), interpreted
as pyrite 2 (Py2).
5.1.3. Pyrite 2
The intermediate ore stage Py2 constitutes the most abundant form
of pyrite in disseminated and brecciated ores (Fig. 4F and G). The Py2
grains are anhedral to subhedral, ranging in size from 2 to 60 μm, but
can be greater than 100 μm locally. They are commonly enclosed within
jasperoid quartz or disseminated in the silicified horizon of the host
rocks. They typically form overgrowth rims, with thickness of 5 to
50 μm, around previously formed Py0 and Py1 (Fig. 7E–G).
5.1.4. Pyrite 3
The late ore stage pyrite 3 (Py3) is rather uncommon, and is con-
fined to argillite of the Longtan Formation (Fig. 4H). It is para-
genetically associated with calcite, forming irregular veins cutting gold
ores and hydrothermally altered rocks. Py3 is coarser grained and
X. Hu et al.
Fig. 8. Elemental contents and correlations for different types of pyrites from the Getang gold deposit. (A) S vs. Fe, (B) Au vs. As, (C) Pb vs. Au, (D) Cu vs. Au, (E) Ni
vs. Au, (F) Ni vs. Co. The gold saturation line in (B) is from Reich et al. (2005).
generally more than 100 μm in diameter. It occurs as acicular to co-
lumnar aggregates under microscope and in BSE images (Fig. 7H).
5.2. Chemical composition of pyrite
The results of EMP and LA-ICP-MS analyses on different varieties of
pyrite are summarized in Tables 1 and 2, respectively. Contents and
correlations of representative elements are illustrated in Fig. 8. Ele-
ments such as As, Cu, Pb, and Zn are commonly at contents below or
around the detection limits of EMP, but could be detected by LA-ICP-
MS. Concentrations of As, Cu, and Zn obtained by the two methods are
relatively consistent, but LA-ICP-MS provides more robust data.
5.2.1. EMP major element of pyrite
The major element composition of different pyrite types was de-
termined by EMP on a suite of 45 representative samples (Table 1). The
results show a positive correlation between Fe and S in pyrite (Fig. 8A).
The Fe (44.79–46.23 wt%) and S (52.14–52.68 wt%) contents in Py0
are slightly lower than those in later ore stages, possibly because in-
dividual Py0 crystals are too small to be precisely analyzed by EMP,
although a beam diameter of 2 μm was used. Py1 and Py2 have fairly
consistent Fe (45.69–46.4 wt%) and S (52.08–53.41 wt%) contents. Py3
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exhibits a slightly wider variation range of Fe (44.92–46.55 wt%) and S
(52.35–53.53 wt%) contents (Fig. 8A). All the pyrite types are char-
acterized by low As contents of less than 0.4 wt%, although As is the
most abundant minor element in pyrite (Table 1). A representative
zoned pyrite grain, which consists of a Py1 core and a Py2 rim, was
selected for elemental mapping under the scanning model of EMP
(Fig. 9). The maps show that the core and rim have relatively homo-
geneous distribution of S, Fe, Bi, and Co. The Cu concentration in the
core is higher than in the rim. The core displays locally elevated con-
centrations of As and Au possibly due to the microcracks in it (Fig. 9).
5.2.2. LA-ICP-MS trace element of pyrite
Thirteen trace elements, including Co, Ni, Cu, Zn, As, Se, Mo, Ag,
Sn, Sb, Au, Bi, and Pb, were measured by LA-ICP-MS on 100 re-
presentative pyrite samples (Table 2). Although none of these elements
show systematic changes in concentration through the paragenesis from
Py0 to Py3, some of them were found to have distinct characteristic
signatures for each of the pyrite types (Fig. 8B–F).
Since Py0 was generally too fine grained for LA-ICP-MS analyses, a laser
diameter of 16 μm was used to analyze their aggregates, which contain about
80 vol% Py0. Aggregates of Py0 contain a suite of elevated trace elements,
including As (78.4–2926 ppm), Co (35.40–738 ppm), Ni (60.9–975 ppm), Cu
X. Hu et al. Ore Geology Reviews 99 (2018) 1–16

Table 1
Electron microprobe analyses of different generations of pyrites from the Getang gold deposit (wt%).
Pyrite type Ore block Analysis no. As S Fe Pb Cu Zn Total

Py0 Kesa KS-24-1 b.d. 52.46 45.55 b.d. 0.06 b.d. 98.07
KS-24-2 0.02 52.59 45.54 b.d. 0.03 b.d. 98.18
KS-24-3 b.d. 52.26 45.34 b.d. b.d. b.d. 97.61
KS-37-1 0.01 52.59 44.79 b.d. 0.02 b.d. 97.41
KS-37-2 b.d. 52.68 45.72 b.d. b.d. 0.04 98.44
Erlongkou EL-37-1 0.19 52.14 45.7 b.d. 0.01 b.d. 98.04
EL-37-3 0.18 52.16 45.73 b.d. 0.04 0.04 98.14
EL-37-5 0.19 52.68 46.23 b.d. 0.01 b.d. 99.11
Py1 Getang GT-14-1 b.d. 53.06 46.23 b.d. 0.01 0.02 99.31
GT-14-2 b.d. 52.73 46.21 b.d. b.d. 0.02 98.96
GT-14-3 b.d. 52.76 46.4 b.d. b.d. 0.01 99.17
GT-14-4 b.d. 53.02 45.85 b.d. b.d. b.d. 98.87
GT-14-5 b.d. 53.36 46.31 b.d. b.d. 0.02 99.69
GT-17-1 0.02 52.33 46.03 b.d. b.d. b.d. 98.38
GT-17-3 b.d. 52.87 46.04 b.d. 0.03 0.04 98.97
GT-17-5 b.d. 52.83 46.13 b.d. b.d. 0.01 98.97
GT-17-7 0.01 52.25 45.69 b.d. 0.01 0.02 97.98
GT-17-9 0.01 52.8 46.26 b.d. 0.02 b.d. 99.09
GT-17-11 b.d. 53.2 46.06 b.d. 0.10 b.d. 99.36
GT-17-13 b.d. 52.08 45.74 b.d. b.d. b.d. 97.82
Py2 Getang GT-17-2 b.d. 53.41 46.01 b.d. 0.01 b.d. 99.43
GT-17-4 b.d. 52.81 45.99 b.d. 0.03 0.04 98.87
GT-17-6 b.d. 53.01 46.22 b.d. b.d. 0.01 99.24
GT-17-8 b.d. 52.75 45.87 b.d. b.d. 0.02 98.64
GT-17-10 0.01 52.82 46.03 b.d. 0.01 b.d. 98.87
GT-17-12 b.d. 52.99 46.13 b.d. b.d. b.d. 99.12
GT-17-14 b.d. 53.17 46.4 b.d. 0.01 b.d. 99.58
Erlongkou EL-37-2 0.01 52.65 46.19 b.d. 0.01 0.01 98.86
EL-37-4 b.d. 53.04 46.32 b.d. b.d. b.d. 99.36
EL-37-6 b.d. 52.78 45.79 b.d. b.d. b.d. 98.57
Longkou LK-5-4 b.d. 52.53 46.06 b.d. b.d. b.d. 98.59
LK-5-2 0.01 52.47 46.13 b.d. 0.02 b.d. 98.63
LK-5-3 b.d. 52.59 46.13 b.d. b.d. b.d. 98.72
LK-5-4 b.d. 52.75 45.88 b.d. b.d. 0.03 98.66
Py3 Erlongkou EL-26-1 b.d. 53.06 46.33 b.d. b.d. 0.02 99.41
EL-26-2 b.d. 53.13 46.21 b.d. b.d. b.d. 99.34
EL-26-3 0.01 52.44 45.67 b.d. b.d. b.d. 98.12
EL-26-4 b.d. 52.7 44.92 b.d. 0.02 b.d. 97.64
EL-26-5 0.32 52.4 45.78 b.d. 0.03 b.d. 98.53
EL-26-6 0.07 52.83 46.29 b.d. b.d. b.d. 99.19
EL-26-7 b.d. 52.35 46.36 b.d. b.d. 0.01 98.72
EL-26-8 b.d. 53.53 46.55 b.d. b.d. b.d. 100.08
EL-26-9 b.d. 52.92 46.4 b.d. 0.01 b.d. 99.33
EL-26-10 0.05 52.4 45.78 b.d. 0.01 0.03 98.27
EL-26-11 b.d. 53.39 46.12 b.d. b.d. b.d. 99.51

b.d. = below detection limit.

(61.4–316 ppm), Zn (1.9–247 ppm), Pb (2.94–1276 ppm), and Mo
(11–768 ppm) (Figs. 8B–E, 10A and B). These contents may have a little
deviation because the influence of the matrix hasn’t been taken into account.
The early ore stage Py1 displays higher contents of As (7.3–245.1 ppm), Ni
(0.1–170 ppm), Cu (0.7–527 ppm), and Zn (0.2–16.8 ppm) and a large var-
iation range of Co (< 0.1–136 ppm) and Pb contents (0.01–481 ppm)
(Fig. 10C and D). The intermediate ore stage Py2 has higher contents of Au
(0.06–16.28 ppm) (Fig. 8B) and Ag (0.04–0.82 ppm) and lower contents of As
(0.1–1380 ppm), Co (< 0.1–74.1 ppm), Ni (0.1–601 ppm), Cu
(0.9–174 ppm), and Bi (< 0.01–16.3 ppm) (Fig. 10E and F). The late ore
stage Py3 is characterized by higher contents of As (4.2–1307 ppm) and
lower contents of Pb (0.03–0.23 ppm), Mo (0.02–0.91 ppm), and Bi
(0.01–3.65 ppm) (Fig. 10G and H). The overall contents of As, Pb, Cu, and Ni
in pyrite show a scattered pattern, and no clear correlation (R = −0.17 to
−0.08) is observed between these elements and Au (Fig. 8B–E). However, Co
and Ni contents in pyrite display a definite positive correlation (R = 0.85)
(Fig. 8F). Most of the Co/Ni ratios fall between 0.1 and 1, with some below
0.1. The Co and Ni contents decrease gradually from Py0, Py1, Py3, to Py2
(Fig. 8F).
5.3. S isotope compositions of pyrite
45 representative pyrite samples were selected for S isotopic ana-
lyses by LA-ICP-MS (Table 3; Fig. 12). Each generation of pyrite has a
distinct range of S isotope compositions. The 15 analyses of Py0 show a
large variation of δ34S values from −38.4 to −4.0‰, with a majority of
−30 to −15‰ and an average of −18.3‰. The 14 analyses of Py1
range from +3.8 to +17.7‰, with most between +10 and +16‰.
The 12 analyses of Py2 range from +1.9 to +8.4‰, with most of them
falling between +2 to +5‰. The 4 analyses of Py3 grains yield a
narrow range of δ34S values from +5.3 to +6.4‰, with an average of
+6.0‰.
6. Discussion
6.1. Gold distribution in pyrite
The results of LA-ICP-MS analyses for Au in Py0 to Py3 are

9
X. Hu et al.
Fig. 9. EMP-BSE image (A) and maps of S (B), Fe (C), As (D), Au (E), Cu (F), Bi (G), and Co (H) in zoned pyrite consisting of a Py1 core and a Py2 rim.
illustrated in Fig. 11. The measured Au concentrations in different
generations of pyrite show great variation from 0.01 to 16.28 ppm
(average 1.4 ppm). The maximum abundance of Au progressively in-
creases from 1.49 ppm in Py3, to 4.01 ppm in Py0, to 5.62 ppm in Py1,
and 16.28 ppm in Py2. Compared with other generations of pyrite, Py2
contains definitely higher levels of Au (0.06–16.28 ppm, average
2.48 ppm), indicating its formation during the main stage of gold mi-
neralization. Py0 in the Getang gold deposit contains relatively higher
concentrations of Au than is expected for common sedimentary pyrite
(Gregory et al., 2015, 2016), possibly because that the sedimentary
strata are enriched in Au, or that Au was adsorbed onto the surface of
Py0 during subsequent hydrothermal activities.
In this study, no visible Au was found in terms of optical microscopy
observations and BSE imaging, even for the pyrites with maximum
concentrations of Au (16.28 ppm in Py2). This suggests that Au is either
structurally bound (e.g. Au+) or occurs as nanoparticles of native Au
(Au0) (Simon et al., 1999). According to the Au versus As diagram
(Fig. 8B), most of the pyrite analyses plot below the solubility limit of
invisible gold in pyrite determined by Reich et al. (2005), implying that
the solutions were dominantly undersaturated with respect to native
Au, and that the majority of Au may present as structurally bound
(Au+). This is also consistent with the relatively homogeneous dis-
tribution of Au in the EMP map of representative pyrite grain (Fig. 9E).
However, unlike most of the SHDG deposits, very few of the pyrites
from Getang are enriched in both Au and As. The Py2 grains typically
10
Ore Geology Reviews 99 (2018) 1–16
exhibit elevated Au contents irrespective of their low As contents. The
lack of positive correlation between Au and As may indicate the pre-
sence of Au as Au-Ag or Au-Te minerals, or native Au nanoparticles
(Hazarika et al., 2013). Owing to the integral low contents of Au in the
analyzed pyrites, it is generally difficult to judge the existing state of Au
in pyrite based on the features of gold signals in the LA-ICP-MS spectra
(Fig. 10A–D, G and H). However, some of the pyrite grains with ele-
vated Au contents display irregular gold signals across a specific portion
of the time resolved LA-ICPMS output graphs (Fig. 10E and F), which
can be regarded as indicating the presence of Au nanoparticles
(Ciobanu et al., 2009; Gregory et al., 2014, 2015).
Considering that the vast majority of pyrites have Au concentrations
well below the Au saturation line (Fig. 8B), we propose that most of the
gold was incorporated into the pyrite lattice as Au+, with a small
fraction of Au present as nanoparticles (Au0) within pores and inter-
stices of pyrites. Such mineralogical form of Au in pyrite has also been
documented in other SHDG deposits (Simon et al., 1999; Su et al., 2008;
Liang et al., 2013). The formation of gold nanoparticles may be at-
tributed to two possible mechanisms: (1) Au exceeded its solubility
limit in pyrite; (2) Au was exsolved from metastable pyrite owing to a
later event in the history of the deposit (Palenik et al., 2004). As for the
Getang gold deposit, only few analyses of Py2 plot above the Au sa-
turation line (Fig. 8B), implying that the first mechanism is unlikely.
The zoned compositional textures in pyrite and the mineral paragenesis
in different ore stages recorded a complex history of hydrothermal
X. Hu et al. Ore Geology Reviews 99 (2018) 1–16

Table 2
LA-ICP-MS trace element analyses of different generations of pyrites from the Getang gold deposit (ppm).
Pyrite Ore block Analysis no. Co Ni Cu Zn As Se Mo Ag Sn Sb Au Bi Pb

Py0 Kesa KS-24-1 198 266 140 28.7 295.4 8.4 12.9 0.24 0.24 2.37 0.93 0.03 132
KS-24-2 170 258 116 28.6 305.1 16.7 16.2 0.33 2.31 1.86 0.86 0.07 54.5
KS-24-3 558 877 196 22.1 364.3 45.3 11 0.43 5.35 11.6 0.10 0.26 175
KS-24-4 97.8 153 80.7 28.2 190.5 3.8 14.2 0.18 1.62 0.38 0.19 0.04 4.19
KS-24-5 212 368 120 27.8 168.5 22.4 17.5 0.2 0.89 0.79 0.35 0.09 15.1
KS-24-6 231 371 151 29 131.3 42.1 19.6 0.26 4.9 1.07 0.74 0.28 36.1
KS-24-7 516 641 220 25.3 304.7 65.9 14 0.69 5.26 3.83 0.06 0.14 120
KS-24-8 35.4 81.7 61.4 27.2 181.1 51.6 17.1 0.09 0.99 0.40 0.70 0.06 2.94
KS-24-9 738 975 277 23.3 241.3 23.4 12.4 0.45 3.17 3.52 0.92 0.25 64.1
KS-24-10 394 637 207 24.9 215.8 36.6 16.2 0.28 3.76 1.18 0.07 0.08 41.2
KS-24-11 66.7 259 67.7 28.5 78.4 9.3 26.5 0.04 0.87 1.09 1.27 0.06 8.51
KS-24-12 80.8 145 79.7 28.4 152.3 35.6 15.8 0.03 1.51 0.46 0.07 0.04 8.05
KS-37-1 52 101 226 54.7 95.5 53.1 138 0.25 5.36 14.1 4.00 0.87 23.2
KS-37-2 86.6 219 261 247 133.7 84.5 119 0.39 5.98 5.53 3.49 1.45 34.4
KS-37-3 92.7 155 267 135 219.6 86.6 104 0.30 8.34 8.58 0.43 1.25 37.2
KS-37-4 62.4 101 179 97.8 297.5 88.9 60.1 0.14 5.42 5.47 1.62 0.63 21.4
KS-37-5 38.3 60.9 180 32.8 87.4 82.4 93.2 0.14 2.16 9.38 2.09 0.59 20.9
KS-37-6 65.6 181 303 172 177.3 244 110 0.40 7.94 5.83 0.92 1.45 51.5
KS-37-7 132 181 275 123 113.4 70.4 106 0.28 5.94 7.73 1.98 1.3 46.8
KS-37-8 79.4 119 210 107 401 66.7 82.7 0.24 4.09 11.7 4.01 0.84 23.6
KS-37-9 93.7 182 316 119 124.1 134 135 0.31 9.6 10 1.63 1.63 44.7
KS-37-10 53 144 216 137 121.8 54.2 69.1 0.14 5.66 14.6 0.29 1.28 41.5
KS-37-11 75.9 177 243 149 173.1 217 90.9 0.29 8.57 8.13 1.36 1.13 47.1
KS-37-12 143 243 228 132 132.9 29 87 0.21 10.2 8.91 2.09 1.38 52.5
Erlongkou EL-37-1 84 215 127 4.6 2926 0.5 601 0.66 2.12 85.2 0.31 1.64 178
EL-37-3 82.2 184 156 4.7 1635 1.7 768 0.35 1.63 84.5 0.23 2.34 129
EL-37-5 143 337 177 3.5 2834 1.9 150 0.65 1.69 83.6 0.99 3.99 355
EL-37-7 97.8 243 218 1.9 1824 3.8 230 0.82 0.54 56.4 0.46 7.62 311
EL-37-9 81.9 206 211 3.6 1680 21.5 224 0.05 0.22 62.9 0.29 7.73 313
EL-37-11 106 868 224 4 1667 7.5 65.1 0.86 0.55 111 0.27 12.9 1276
EL-37-13 82.7 599 187 3.3 1498 15.3 87.9 0.53 0.07 95.5 0.66 13.3 1058
EL-37-15 50.2 287 201 3.1 1381 16.5 80.5 0.96 1.91 59.4 0.10 9.29 452
EL-37-17 95.3 349 214 6.1 1892 0.7 85.1 0.18 0.58 126 0.62 11.7 1122
Py1 Getang GT-14-1 0.1 18.3 0.9 0.8 11.1 39.8 0.07 0.06 0.23 0.02 0.32 0.01 0.13
GT-14-2 5.4 32.7 2.4 9.1 24.6 15.3 0.09 0.11 0.62 0.71 0.53 0.03 0.34
GT-14-3 0 1.6 1.5 0.9 21.7 0 0.07 0.08 0.49 0.03 0.39 0.01 0.12
GT-14-4 0.1 0.3 1.1 0.4 10 6.4 0.06 0.06 0.54 0.01 0.53 0.05 0.14
GT-14-5 0 29 1 0.7 8.4 15 0.03 0.05 0.11 0.10 0.32 0.01 0.01
GT-14-6 0.5 0.2 9.7 16.8 43 7.3 0.42 0.05 0.51 1.23 0.71 0.06 0.25
GT-14-7 0 2.3 16.4 0.2 21.4 0 0.14 0.09 0.52 0.02 0.25 0.2 1.39
GT-14-8 136 170 18.2 0.5 27.5 9.1 0.04 0.14 0.62 0.16 0.23 0.21 0.98
GT-14-9 0 0.1 1.7 1.2 8.5 25.8 0.01 0.05 0.82 0.62 0.50 0.16 0.04
GT-14-10 0.3 5.6 0.7 0.2 12.1 88 0.03 0.09 0.3 0.10 0.45 0.01 0.04
GT-14-11 0 5.1 3.3 0.4 7.3 25 0.02 0.06 0.85 0.37 0.37 0.01 0.01
GT-14-12 0 0.1 4.4 0.5 36.7 50.2 0.03 0.13 0.06 0.06 0.19 0.64 0.46
GT-17-1 14.2 76.7 304 4.4 103.8 4.8 88 0.31 1.18 11.3 0.44 1.93 108
GT-17-3 18.7 74.9 141 2.1 132.1 3.2 237 0.53 1.64 9.93 2.21 1.67 72.6
GT-17-5 13.6 73 72.1 3.5 152.9 3.2 97.8 0.07 1.53 15.4 0.34 0.59 119
GT-17-7 33.7 137 40.7 5.2 75.8 6.9 4.07 0.96 0.06 22.8 1.32 0.06 481
GT-17-9 15.3 60 180 1.5 157.5 0 66.5 0.18 4.07 18 5.62 1.34 79.34
GT-17-11 11.6 41.4 92.2 1.5 116.4 0 217 0.04 0.79 13.1 0.33 0.89 77.99
GT-17-13 30.5 104 251 1.7 245.1 18.2 120 0.05 1.4 18.7 0.14 2.57 102
GT-17-15 22.8 95.1 219 2.5 146 9.7 97.1 0.14 1.27 12.4 1.60 0.77 91.3
GT-17-17 46.2 167 527 3.3 203.2 4.8 122 0.04 1.92 13.4 0.28 8.06 125
Py2 Getang GT-17-2 6.4 17.8 37.2 0.9 23.2 0 78.5 0.55 2.79 2.67 0.73 0.53 9.69
GT-17-4 0.1 2.6 2.4 0.7 0.3 0 1.51 0.17 1.5 0.07 0.23 0.02 0.48
GT-17-6 0.1 1.7 4.2 0.5 7.2 0.7 2.40 0.11 2.76 2.15 0.95 0.12 0.48
GT-17-8 0.2 3.5 5.2 0.8 1.2 0.1 1.83 0.27 4.16 3.99 2.11 0.03 4.07
GT-17-10 12.5 41.8 58.5 1.2 107.7 1 226 0.08 1.29 10.4 0.16 0.58 44.97
GT-17-12 23.8 50 29.7 2.1 183.6 5.8 79 0.04 0.74 14.4 0.33 0.43 74.68
GT-17-14 2.1 9.5 10.8 0.7 9.3 0 6.27 0.26 2.61 0.68 0.18 0.26 2.89
GT-17-16 0.1 0.6 1.8 0.8 0.1 19.4 1.59 0.11 1.59 0.04 0.39 0.01 0.14
GT-17-18 0.1 2.8 0.9 0.5 0.2 1.0 0.36 0.12 3.94 0.05 1.33 0.01 0.23
Erlongkou EL-37-2 14.4 49.5 61.8 2.2 618.1 0.7 88.4 0.18 5.36 35.2 0.91 0.65 49.9
EL-37-4 0.1 26.5 2.5 0.9 37.3 0.3 0.02 0.36 3.88 0.07 0.38 0.02 0.31
EL-37-6 0.2 15.5 9 1.4 0.7 0.8 0.12 0.82 3.91 0.72 0.06 0.04 0.32
EL-37-8 0.3 9.7 11.8 0.8 11.4 0.6 1.51 0.26 4.22 0.50 0.94 0.02 0.99
EL-37-10 0.2 15.3 5 1.2 1.9 8.4 0.22 0.18 10.5 1.37 0.21 0.01 0.67
EL-37-12 0.2 3.5 3.4 0.8 0.7 7.4 0.04 0.38 12.4 0.03 0.18 0.01 0.52
EL-37-14 0.1 8.3 7.5 1.9 6.5 32.2 0.73 0.07 10.1 10.2 1.02 0.12 2.35
EL-37-16 74.1 601 174 4.5 1380 11.4 79.1 0.44 1.58 94.6 0.06 16.3 924
EL-37-18 66.1 239 168 2.6 1286 0 84.2 0.56 0.93 71.8 0.88 8.06 679
Longkou LK-5-1 0.1 0.5 7.6 6.7 0.2 6.4 0.01 0.64 1.37 0.06 12.70 0.01 0.07
LK-5-2 0.1 0.6 5.7 7 0.6 0 0.08 0.05 1.76 0.04 0.51 0.01 0.12
(continued on next page)

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Table 2 (continued)

Pyrite Ore block Analysis no. Co Ni Cu Zn As Se Mo Ag Sn Sb Au Bi Pb

LK-5-3 0.3 1.6 8.4 7.8 28.7 0 0.50 0.26 0.85 1.13 9.53 0.01 0.34
LK-5-4 0.1 0.2 5.2 9.1 3.8 0 0.07 0.62 0.93 0.17 1.24 0.01 0.04
LK-5-5 0.3 1.3 14.7 8.2 32.5 64.7 1.26 0.06 0.39 1.33 16.28 0.01 0.12
LK-5-6 0.1 0.4 6.7 8.8 12 27.3 0.16 0.26 0.65 0.84 3.85 0 0.3
LK-5-7 0.1 0.1 5.9 7.3 0.7 0 0.12 0.09 0.77 0.03 0.33 0 0.04
LK-5-8 0.4 1.4 4.1 7.1 1.3 0 0.40 0.32 0.4 0.04 0.48 0 0.11
LK-5-9 0 0.3 5.1 5.1 2.9 0 0.33 0.11 0.03 0.19 0.82 0.01 0.07
LK-5-10 0.4 0.3 4.1 7.6 15.6 50.7 2.70 0.35 0.83 1.62 5.09 0.02 0.29
LK-5-11 0.3 1 7.8 7.2 3.2 10.5 0.23 0.52 0.27 0.22 0.53 0.01 0.05
LK-5-12 0.2 1.1 9.3 7.3 2.7 0.5 0.43 0.13 0.87 0.43 13.34 0.01 0.44
LK-5-13 1.1 7.9 10.9 10.2 6.2 28.4 2.66 0.05 0.48 1.12 0.07 0.01 1
LK-5-14 0.5 1.7 13.2 5.5 20.1 25.4 1.79 0.10 0.17 6.32 5.19 0 0.78
LK-5-15 0.1 0.2 8.8 6.2 0.1 0.9 0.06 0.12 0.26 0.06 0.20 0.01 0.04
LK-5-16 0.2 0.4 6 5 5.2 1.6 0.60 0.37 0.14 0.36 3.25 0 0.11
Py3 Erlongkou EL-26-1 0.5 1.8 22.6 1.9 362.6 17.1 0.09 0.06 2.09 0.10 1.49 0.02 0.07
EL-26-2 1.2 14.1 12.2 0.8 54.9 34.2 0.09 0.04 0.84 4.42 0.09 0.05 0.09
EL-26-3 0.2 2.6 10.5 5 78.6 32.5 0.23 0.24 0.47 1.11 0.12 0.01 0.23
EL-26-4 2.3 6.9 23.5 1.7 94.2 19.5 0.09 0.06 3.21 0.34 0.69 0.02 0.06
EL-26-5 3 17 13.6 1.2 104.6 22.1 0.91 0.25 0.12 7.14 0.52 0.22 0.04
EL-26-6 1.1 7.3 29.1 2.6 635.9 16.1 0.37 0.09 3.69 9.08 0.45 0.17 0.22
EL-26-7 6 19 8.1 2.1 4.2 6.4 0.05 0.19 0.79 0.21 0.20 0.03 0.09
EL-26-8 0 0.4 5.2 0.5 256.3 2.6 0.06 0.04 1.07 0.62 0.96 0.05 0.12
EL-26-9 0.5 6 7.7 1.2 19.6 20.5 0.04 0.06 0.1 0.21 1.32 0.02 0.07
EL-26-10 1 8.9 4.4 0.4 314.1 9.3 0.02 0.07 0.32 0.11 0.01 0.29 0.06
EL-26-11 2.7 13.6 4.6 0.8 83.4 20.6 0.04 0.01 0.34 0.33 0.03 0.16 0.04
EL-26-12 0.5 40.7 9.9 1.5 1307 1.1 0.10 0.19 1.02 0.10 0.40 3.65 0.03

activity in the Getang gold deposit. It is possible that some structurally
bound gold formed during the main ore stage was remobilized and
exsolved to form gold nanoparticles in response to subsequent hydro-
thermal event.
6.2. Source of sulfur
6.2.1. Py0
The Py0 grains display significant enrichment in 32S, with a wide
range of negative δ34S values from −38.4 to −4.0‰. Such low and
variable δ34S values indicate the derivation of sulfur by bacterial re-
duction of marine sulfate (BSR) during sedimentation and diagenesis in
a setting with sufficient reach of sulfate from the overlying water
column to approximate an open system (Ohmoto and Rye, 1979; Seal,
2006). This is corroborated by the framboidal texture of Py0 and the
abundance of organic matter in the Longtan Formation.
Py0 commonly forms framboids and nodules consisting of discrete
euhedral microcrystallites (Fig. 7A–C), which are typical of syngenetic
or diagenetic origin (Wilkin et al., 1996; Gregory et al., 2014). The
Longtan Formation in the Getang district contains several layers of
anthracite, and the argillite also contains elevated concentration of
organic matter (up to 23 vol%, Zhuang et al., 2000). The geochemical
studies further suggested that the argillite and shale of the Longtan
Formation was deposited in a reduced sedimentary environment of
shallow sea (Huang et al., 2012). In this circumstance sulfate-reducing
bacteria are active owing to the sufficient supply of organic matter
(Machel et al., 1995; Seal 2006). Since the sulfate-reducing bacteria
preferentially metabolize 32S relative to 34S (Ohmoto and Rye, 1979),
the δ34S of the residual S reservoir increases during the reaction pro-
gress. Previous studies have demonstrated that the δ34S values of
marine sulfate during Permian and Triassic time are of +10 to +15‰
(Holser and Kaplan, 1966; Claypool et al., 1980), and the fractionation
of δ34S values between sulfate and precipitated pyrite associated with
BSR typically ranges from 15 to 71‰ in marine settings (Canfield and
Teske, 1996). Combined with the negative δ34S values of Py0, it can be
concluded that the sulfur of Py0 was produced during the early to
middle period of BSR.
6.2.2. Py1
The δ34S values of Py1 predominantly vary from +9.7 to +17.7‰
(except one analysis of +3.8‰, Sample GT-17-3), which are basically
within the range of Permian and Triassic marine sulfate of +10 to
+15‰ as described above (Holser and Kaplan, 1966; Claypool et al.,
1980). One may interpret the sulfur isotopic signatures of Py1 in terms
of H2S generated by BSR in a system becoming close to SO42−. How-
ever, the fluid inclusion microthermometry of coexisting quartz sug-
gests that the temperature of hydrothermal fluids in the Getang gold
deposit vary from 185 to 240 °C with an average of 215 °C (Dong et al.,
2011), which rules out any significant role for microbial activity in the
genesis of Py1. The sulfur isotopic compositions of Py1 differ sub-
stantially from those of Py0, precluding the possibility that the sulfur in
Py1 was derived from dissolution or transformation of diagnetic Py0 in
the sedimentary rocks, although such mechanisms have been docu-
mented in other gold deposits in the southwestern Guizhou Province
(Hu et al., 2002; Peng et al., 2014).
A possible source of sulfur for the 34S-enriched Py1 would be ori-
ginated from complete thermochemical or inorganic reduction of the
Permian – Triassic sulfate in a closed system. In such cases, the resultant
H2S and metal sulfides are expected to have nearly the same δ34S values
as the parent sulfate. This process can happen in compressive depres-
sion basins or during the burial history of the sediments (Hu et al.,
2002).
6.2.3. Py2 & Py3
Py2 and Py3 yield comparable δ34S values of +1.9 to +8.4‰, with
a mean of +3.8‰ and +6.0‰, respectively. The sulfur isotopic
compositions of Py2 and Py3 are significantly different from those of
Py0 and Py1 (Table 3; Fig. 12), indicating that they precipitated from
different fluids.
The relatively narrow range and slightly positive δ34S values of Py2

12
X. Hu et al. Ore Geology Reviews 99 (2018) 1–16

Fig. 10. Time-resolved LA-ICP-MS output graphs for different types of pyrites from the Getang gold deposit. Py0 is characterized by high concentrations of trace
elements such as As, Ni, Cu, Pb, Zn, and Mo (A–B). Py1 has higher contents of As, Ni, and Cu (C–D). Py2 displays higher contents of Au, but lacks most trace elements
(E–F). Py3 contains minor amounts of As, Cu, and Ni (G–H). Spikes in the plots indicate micro-inclusions within pyrite.

and Py3 suggest that sulfur was most likely sourced from a deep-seated
reservoir, either metamorphic or magmatic (Ohmoto and Rye, 1979).
Considering that the δ34S values of Py2 and Py3 can be obtained by
homogenisation of Py0 and Py1, one may interpret the S-isotope sig-
nature by the metamorphic model. However, since no notable meta-
morphism is observed in the sedimentary strata of southwestern
Guizhou Province, metamorphic-derived fluid is a less likely source for
the sulfur. Alternatively, a magmatic sulfur source may account for the
predominant sulfur budget of Py2 and Py3, despite the fact that no
igneous intrusions are outcropped in the vicinity of the Getang gold
deposit. The usual estimate of δ34S values for magmatic sulfur are be-
tween 0 to +5.0‰ (Ohmoto and Rye, 1979; Ishihara and Sasaki, 1989),
which are slightly lower than the δ34S values of Py3 and one analysis of
Py2 (Sample GT-17-14, δ34S = 8.4), indicating that magmatic sulfur
alone might cannot generate the δ34S range for Py2 and Py3. This im-
plies that a small amount of marine sulfate-sulfur with high δ34S values
may be incorporated during the formation of Py2 and Py3. The parti-
cipation of marine sulfate could occur by assimilation or partial melting
of sulfate-bearing rocks during the ascending and emplacement of
granitic magmas (Seal, 2006), or by fluid-rock interaction (Santosh and

13
X. Hu et al. Ore Geology Reviews 99 (2018) 1–16

Table 3 Masuda, 1991). In summary, the sulfur of Py2 and Py3 was mainly
LA-MC-ICP-MS in situ S isotope compositions of different generations of pyrites sourced from magmatic sulfur with minor input of reduced marine
from the Getang gold deposit (‰). sulfate.
Pyrite Ore block Analysis no. 34
S/32S 2σ δ34S (‰)
6.3. Implication for ore genesis
Py0 Kesa KS-24-1 0.047622 0.000006 −21.6
KS-24-2 0.047616 0.000008 −21.8
Although different genetic models involving sedimentary, meta-
KS-24-3 0.047754 0.000008 −18.9
KS-24-4 0.047728 0.000003 −19.5 morphic, and magmatic systems have been proposed for the SHDG
KS-24-5 0.047675 0.000014 −20.6 deposits in southwestern Guizhou Province, the genesis of the Getang
KS-37-1 0.047434 0.000006 −25.5 gold deposit has been seldom discussed owing to the lack of isotopic
KS-37-2 0.047621 0.000017 −21.7
and other evidences. The distinct difference of δ34S values between
KS-37-3 0.047456 0.000003 −25.1
KS-37-4 0.047293 0.000005 −28.4
main ore-stage pyrite (Py2, +1.9 to +8.4‰) and diagenetic pyrite
KS-37-5 0.046808 0.000005 −38.4 (Py0, −38.4 to −4.0‰) rules out any possibility that the ore-related
Erlongkou EL-37-1 0.047955 0.000003 −8.2 sulfur was derived from sediments. The metamorphic model can also be
EL-37-3 0.048134 0.000007 −4.0 excluded by the absence of regional metamorphism. The change in δ34S
EL-37-5 0.047971 0.000004 −7.4
values through time probably reflects a change from an early sedi-
EL-37-7 0.048091 0.000005 −5.0
EL-37-9 0.047955 0.000004 −7.8 mentary to a later magmatic source for the sulfur. Similar results were
Py1 Getang GT-14-1 0.049113 0.000004 15.7 also obtained by sensitive high-resolution ion microprobe analyses of
GT-14-2 0.049115 0.000006 15.8 different varieties of pyrite from the Huijiabao ore field in southwestern
GT-14-3 0.049210 0.000003 17.7
Guizhou Province (Hou et al., 2016). The oxygen and hydrogen isotope
GT-14-4 0.049070 0.000006 14.8
GT-14-5 0.049081 0.000003 15.1
compositions of the ore-related quartz veins from the Getang gold de-
GT-14-6 0.049493 0.000003 16.7 posit have been reported by Zhu et al. (1997) and Huang et al. (2012).
GT-14-7 0.049336 0.000003 13.5 The δD(H2O) and calculated δ18O(H2O) values range from −95.9 to
GT-17-1 0.048930 0.000008 11.7 −32.3‰ and −1.3 to 2.7‰, respectively. In the δD versus δ18O dia-
GT-17-2 0.048834 0.000007 9.7
gram, these data plot close to the magmatic water box (Zhu et al.,
GT-17-3 0.048536 0.000005 3.8
GT-17-4 0.048970 0.000004 12.8 1997), also indicating a predominant magmatic origin for the miner-
GT-17-5 0.048903 0.000003 11.4 alizing fluids.
GT-17-6 0.049176 0.000003 10.2 The potential importance of magmatic fluids has long been dis-
GT-17-7 0.049379 0.000003 14.4 counted because of the paucity of igneous intrusions in southwestern
Py2 Getang GT-17-2 0.048572 0.000003 4.3
GT-17-4 0.048575 0.000004 4.4
Guizhou. However, recent gravity and magnetic surveys have re-
GT-17-6 0.048555 0.000004 4.2 cognized a number of probable buried intrusions in this district (Wang
GT-17-8 0.048546 0.000005 4.0 et al., 2009; Jin et al., 2016; Luo et al., 2016), which are spatially as-
GT-17-10 0.048596 0.000003 5.0 sociated with the pre-existing SHDG deposits, including the Getang gold
GT-17-12 0.048866 0.000003 3.9
deposit. In addition, plenty of granites and granite-related hydro-
GT-17-14 0.049084 0.000004 8.4
Erlongkou EL-37-2 0.048474 0.000003 2.5 thermal W, Sn, Mo, and Pb-Zn deposits have been discovered in the
EL-37-4 0.048423 0.000003 1.9 eastern and western edge of the Youjiang Basin, reflecting frequent
EL-37-6 0.048430 0.000003 2.1 granitic magmatism within the crust. The lack of igneous intrusions in
EL-37-8 0.048443 0.000003 2.3 southwestern Guizhou may be attributed to the relatively shallow de-
EL-37-10 0.048436 0.000003 2.2
Py3 Erlongkou EL-26-1 0.048623 0.000003 5.3
nudation depth in this area, which has been corroborated by evaluation
EL-26-2 0.048673 0.000003 6.4 of regional geochemical data (Luo et al., 2016). In summary, we favor
EL-26-3 0.048661 0.000003 6.2 that the Getang gold deposit and some other SHDG deposits in south-
EL-26-4 0.048662 0.000003 6.2 western Guizhou are distal products of deep magmatic hydrothermal
systems, from which Au and the mineralizing fluids were derived.
Likewise, the magmatic-hydrothermal origin for SHDG or Carlin-style
gold deposits in Nevada have also been proposed by many researchers
in recent years (Kesler et al., 2005; Muntean et al., 2011; Large et al.,
2016).

7. Conclusions

The Getang sediment-hosted disseminated gold deposit contains

four generations of pyrite (Py0, Py1, Py2, and Py3), which show distinct
textural, chemical, and S isotopic characteristics.

1. Py2 contains the highest concentrations of Au, indicating its for-

mation during the main stage of gold mineralization. Most of the
gold is structurally bound in pyrite as Au+, with a small fraction of
them present as nanoparticles (Au0).
2. The sulfur of Py0 was derived by bacterial sulfate reduction. The
sulfur of Py1 was sourced from complete thermochemical reduction
of marine sulfate. The sulfur of Py2 and Py3 was mainly originated
from magmatic sulfur with minor contribution of reduced marine
Fig. 11. Au contents (ppm) in different types of pyrites from the Getang gold sulfate.
deposit.

14
X. Hu et al.
Fig. 12. Histograms of S isotope compositions for different types of pyrites from
the Getang gold deposit.
3. The Au and the mineralizing fluids in the Getang gold deposit were
derived from concealed granitic intrusions. The gold mineralization
in Getang was a distal manifestation of deep magmatic hydro-
thermal systems.
Acknowledgments
We are grateful to the No. 105 and No. 117 geological teams in
Guizhou Province for geologic guidance during field investigations.
Hang Li and Yongjie Jin are thanked for their help during sample
preparation. Ming Zhou is thanked for his assistance during LA-ICP-MS
analyses. The study benefited from discussion with Prof. Zonggui Zhou
and Dr. Diwei Luo. Constructive reviews by Profs. Franco Pirajno, Nuo
Li, and two anonymous reviewers have substantially improved the
manuscript. This research was financially supported by the Natural
Science Foundation of China (Grant Nos. 41602070) and the
Fundamental Research Funds for the Central Universities, China
University of Geosciences (CUG160831).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.oregeorev.2018.05.020.
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