Journal of Geochemical Exploration 218 (2020) 106617

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Journal of Geochemical Exploration

journal homepage: www.elsevier.com/locate/gexplo

Fluid evolution and gold precipitation in the Muping gold deposit (Jiaodong, T
China): Insights from in-situ trace elements and sulfur isotope of sulfides
⁎
Yong-Wen Zhanga,b, Fang-Fang Hua,b,c, Hong-Rui Fana,b,c, , Xuan Liud, Kai Fenga,b, Ya-Chun Caia
a
Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
b
College of Earth Science, University of Chinese Academy of Sciences, Beijing 100049, China
c
Institutions of Earth Science, Chinese Academy of Sciences, Beijing 100029, China
d
GeoRessources Lab, Université de Lorraine, CNRS, CREGU, 54500 Vandoeuvre-lès-Nancy, France

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

Keywords: The Early Cretaceous Muping gold deposit is hosted in the Late Jurassic monzogranite. Crosscutting relations of
Pyrite ore veins implied a presence of multiple fluid pulses, and the mineralization process comprises four miner-
In-situ analysis alization stages. Three generations/types of pyrite (Py1, Py2, and Py3) have been discriminated. Coarse-grained
Sulfur isotope and euhedral Py1 pertains to pyrite-quartz veins. Coarse-fine grained and subhedral Py2 comes from quartz-
Trace element
pyrite veins. Fine-grained and anhedral Py3 is from quartz-polymetallic sulfides veins. Py3 further can be di-
Muping gold deposit
Jiaodong
vided into three sub-types (Py3a, Py3b, and Py3c), in which Py3a did not have a core-rim texture, Py3b is the
core and Py3c is the rim of pyrite with core-rim texture.
Py1 and Py2 contain relatively higher Co (738 and 29 ppm on median) and Ni (30 and 7.6 ppm on median),
but lower As (754 and 15 ppm on median) and Au (median < 0.1 ppm) content. However, Py3 has extremely
low Co and Ni (medians below detection), but elevated As (from 16,290 to 206 ppm on median) and Au (from 36
to 0.4 ppm on median) content. Co and Ni contents of pyrite gradually decreased but As content increased from
Py1 to Py3, implied that the temperature of ore-forming fluids progressively decreases. Extremely higher As
content and high δ34S of Py3c could be associated with an incursion of As-rich and heavy δ34S meteoric water
which has flowed through meta-sedimentary rocks. Sulfur isotopes revealed a gradual decrease from Py1
(+11.6‰) to Py3b (+7.5‰). As for the pyrite with core-rim texture, the sulfur isotope progressively increased
from the core (Py3b, +6.0‰) and the rim (Py3c, +11.8‰). The high δ34S could be derived from the meta-
somatic and fertile lithospheric mantle, and the difference between Py1 and Py2 attributed to suffering from
degassing processes with different condition. Rayleigh fractionation process caused a “reservoir effect” can
explain the inside variations of Py2, while the increase of fO2 caused by phase separation is the main factor
leading to δ34S decrease for Py3. It is the fluid mixture that resulted in the inter-crystalline sulfur isotope var-
iation of pyrite with core-rim texture. Gold and As contents for all types of pyrite plot well below the solubility
limit for gold in arsenian pyrite, indicating that invisible gold occurs as Au1+ in the pyrite lattice. The extent of
invisible gold was incorporated into pyrite depending on the arsenic content, but visible gold mineralization
mainly was controlled by vapor phase escape and fO2 increase which attributed to phase separation.

1. Introduction vein-style, and the Jiaojia-type disseminated-/stockwork-style (Liu

The Jiaodong gold province is the largest gold-producing district in
China, which holds a quarter of the nation's total reserves. The province
is located in the southeastern margin of the North China Craton (NCC),
which is dominated by Precambrian high-grade metamorphosed base-
ment rocks as well as voluminous Mesozoic granitoids (Qiu et al., 2002;
Fan et al., 2003; Tang et al., 2007; Zhu et al., 2015). Gold deposits in
Jiaodong are mainly classified into two styles: the Linglong-type quartz
et al., 1999; Shen et al., 2001; Qiu et al., 2002). Previous researches
based on fluid inclusion analyses suggest that the Jiaodong gold de-
posits formed in a hydrothermal environment with medium-low tem-
perature, low salinity, and hydrogen and oxygen isotope studies reveal
that the ore-forming fluids derived mainly from magmatic sources, and
a small amount of meteoric water involved into the mineralization
process (Fan et al., 2003; Hu et al., 2007; Mao et al., 2008; Wen et al.,
2015; Cai et al., 2018; Xue et al., 2018). However, the dispute of the

⁎
Corresponding author at: Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China.
E-mail address: fanhr@mail.igcas.ac.cn (H.-R. Fan).

https://doi.org/10.1016/j.gexplo.2020.106617
Received 15 January 2020; Received in revised form 20 June 2020; Accepted 4 August 2020
Available online 11 August 2020
0375-6742/ © 2020 Elsevier B.V. All rights reserved.
Y.-W. Zhang, et al.
source and evolution of ore-forming fluids of Jiaodong gold deposits
exists all the while (Fan et al., 2003; Mao et al., 2008; Wen et al., 2015;
Mills et al., 2015a; Zhu et al., 2015; Cai et al., 2018; Feng et al., 2018;
Zhu et al., 2018). Recent researches suggest that there are several fluid
pulses during mineralization stage in the Jiaodong gold deposits (Yang
et al., 2017; Li et al., 2018; Feng et al., 2018). The values of the sulfur
isotope are easily affected and modified by hydrothermal fluids, and
conventional technique cannot achieve grain-scale spatial resolution,
yielding mixed results. The disadvantage hinders sulfur isotope to be
used as a tool which indicating the variation of physiochemical con-
ditions of ore-forming fluids and the mineralization process. The re-
searches on gold precipitation mechanism at Jiaodong mostly empha-
sized fluid-rock interaction, phase separation or mixture of fluids, and
mineralization relationship between gold and other trace elements (Fan
et al., 2003; Hu et al., 2007; Wen et al., 2015; Mills et al., 2015a; Yang
et al., 2016; Cai et al., 2018; Li et al., 2018). Because lacking enough
knowledge of the evolution of ore-forming fluids, how those geological
processes affect physiochemical conditions of the ore-forming fluid
system and gold precipitation remains unattended.
Recently, in-situ coupled trace element and sulfur isotope analyses
on pyrite were applied to epigenetic, hydrothermal gold deposits
(Barker et al., 2009; Peterson and Mavrogenes, 2014; Tanner et al.,
2016). Trace element and sulfur isotope in sulfides can reveal physio-
chemical conditions during mineral deposition, and track changes in
the pH, temperature, redox state, fluid resources and corresponding
geological process such as fluid-rock interaction, phase separation and
fluid mixing (Reich et al., 2005; Hodkiewicz et al., 2009; Morey et al.,
2008; Su et al., 2012; Deditius et al., 2014; Tanner et al., 2016). As yet,
there only has been little attention given to mineral geochemistry of
trace elements and in-situ sulfur isotope in the Jiaodong gold deposit
(Mills et al., 2015a; Yang et al., 2016; Cai et al., 2018; Feng et al., 2018;
Li et al., 2018).
Sulfur isotope values of sulfides at Jiaodong previously analyzed by
conventional (bulk-grains) methods display a broad range from −5.6‰
to 12.8‰, which is not completely consistent with the sulfur isotope
value range of the Mesozoic granites and Precambrian metamorphic
rocks (Mao et al., 2008; Lan et al., 2010; Li et al., 2015). Recently, in-
situ sulfur isotope analysis by SIMS has been applied to Hushan, Hei-
lan'gou, Zhuangzi, and Shangzhuang gold deposits at Jiaodong (Yang
et al., 2017; Cai et al., 2018; Feng et al., 2018; Li et al., 2018). However,
the variations of sulfur isotope in the Jiaodong gold deposit are very
complicated, the too-simple variation pattern of the sulfur isotope (such
as Shangzhaung gold deposit) cannot be used to explain other gold
deposits in the Jiaodong province, or the variation of sulfur isotope
value are too small and it is difficult to establish a relationship with
gold precipitation.
Mills et al. (2015a) firstly proposed that the distinction of gold oc-
currence and precipitation mechanisms among different gold miner-
alization belts in the Jiaodong area. Yang et al. (2016) quantified trace
elements (especially for lattice-bound gold) content in pyrite of the
Xincheng gold deposit. There is a divergence of visible gold that was
interpreted as remobilization from earlier invisible gold in pyrite. Many
researchers have demonstrated that gold deposits at Jiaodong are dif-
ferent from orogenic or Carlin-type gold deposits in tectonic setting,
source of ore-forming fluids, age of metamorphism and mineralization,
mineral assemblages (Groves et al., 1998; Goldfarb et al., 2001, 2007;
Qiu et al., 2002; Fan et al., 2003; Mao et al., 2008; Barker et al., 2009;
Su et al., 2009, 2012; Zhu et al., 2015; Ma et al., 2017; Feng et al., 2018;
Li et al., 2018). Besides, orogenic and Carlin-type gold deposits have an
order of magnitude arsenic content higher than gold deposits at Jiao-
dong, arsenic has facilitation on the incorporation of metals and me-
talloids in pyrite (Reich et al., 2005; Sung et al., 2009; Deditius et al.,
2014; Zhu et al., 2015; Hou et al., 2016; Feng et al., 2018; Li et al.,
2018). Whether arsenic content in ore fluid system is a vital factor in
controlling gold occurrence in the different types of gold deposits or
not, and whether the gold deposits including Muping gold deposit at
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Journal of Geochemical Exploration 218 (2020) 106617
Jiaodong had suffered from gold remobilization process like orogenic
gold deposits due to they all have a bimodal distribution of gold in
pyrite or not are worthy of consideration and investigation.
The Muping gold deposit (with gold reserves of > 50 t gold at a
mean grade of 6 g/t) is hosted by the Wuzhuashan monzogranite which
was emplaced at 160 ± 3 Ma (Hu, 2006). It is a typical quartz-vein
style gold deposit in which the mineralization stage is more explicit
than disseminated- and stockwork-style gold deposit (Fan et al., 2003;
Hu et al., 2007). Additionally, previous research of the Muping gold
deposit suggested that there are zoned pyrites and the content of arsenic
could have a crucial role in gold occurrence (Mills et al., 2015a). In this
contribution, we combine in-situ trace element spot analysis and
mapping, and sulfur isotope analysis to exam the variations in trace
element and sulfur isotope of pyrite in the different mineralization
stages. The results are used to provide insights into the evolution of ore-
forming fluids and gold precipitation. Finally, we highlight the different
occurrence of gold (invisible and visible gold) and the possible genesis
in the Muping gold deposit, attempting to discriminate the distinction
among Jiaodong, orogenic and Carlin-type gold deposits.
2. Regional geology
The Jiaodong peninsula separated from the Luxi Block by the NNE-
trending Tan-Lu fault zone (Fig. 1). The region consists of the Jiaobei
terrain and Sulu ultra-high pressure metamorphic (UHPM) belt (Zheng
et al., 2003). The latter one is formed by northward subduction of the
Yangtze Block during the Triassic (Yang et al., 2005; Xie et al., 2013).
The Jiaobei terrain is predominantly composed of Precambrian base-
ment and Mesozoic granitoids. The basement mainly consists of
Neoarchean TTG (tonalite-trondhjemite-granodiorite) gneisses (Jiao-
dong Group), Paleoproterozoic meta-sedimentary sequences (Fenzishan
and Jinshan Group) with strong overprinting by an ~1.8 Ga amphi-
bolite to granulite facies metamorphism, and the Meso-Neoproterozoic
Penglai Group which consist with slate, quartzite, and limestone (Lu,
1998; Zhai et al., 2000; Tang et al., 2007). The Mesozoic igneous rocks
are mainly divided into (1) the Late Jurassic Linglong-style biotite
granite and Luanjiahe-type monzogranite (160–150 Ma), which were
derived from partial melting of a thickened low crust of the NCC (Yang
et al., 2012); (2) the Early Cretaceous Guojialing-type granodiorite
(130–126 Ma) that was formed by remelting of an Archean lower crust
with addition of mantle components as a response to the Pacific sub-
duction (Yang et al., 2012; Jiang et al., 2016); (3) The latest Early
Cretaceous granitoids, including Sanfoshan, Aishan, Yashan and
Laoshan plutons, consists of monzogranites, syenogranites and quartz
monzonites in the Jiaodong Peninsula. Zircon UePb age data from re-
cent studies showed that these granitoids emplaced at a range of
123–111 Ma, concentrating at 118–113 Ma (Hu, 2006; Goss et al.,
2010; Li et al., 2018). Besides, many mafic to felsic dykes are well
developed in the Jiaodong province and emplaced at 124–87 Ma (Guo
et al., 2004; Yang et al., 2004; Cai et al., 2013).
The distribution of the main gold deposits at Jiaodong is controlled
by northeast to north-northeast (NE/NNE) fault (Qiu et al., 2002;
Goldfarb et al., 2007). Three major mineralization belts have been ca-
tegorized: the Zhaoyuan-Laizhou gold belt, the Qixia-Penglai gold belt,
and the Muping-Rushan gold belt (Fan et al., 2003). The Muping gold
deposit, the second-largest quartz vein-style gold deposit in the Muping-
Rushan belt, is located in the northern zone of this belt. There are other
gold deposits in this gold belt, such as Jinqingding, Jinniushan, Yin-
gezhuang, Hubazhuang, Sanjia and Shicheng gold deposits. All of these
gold deposits are hosted in the Kunyushan complex rocks (Fig. 2),
which consists of Wuzhuashan monzogranite, Washan monzogranite,
Duogushan granodiorite and Sanfoshan monzogranite (Hu, 2006; Lan
et al., 2010). The Washan and Duogushan monzogranite also intruded
at ~160 Ma (Hu, 2006), and the age of Sanfoshan monzogranite is
~112 Ma (Hu, 2006) (Fig. 3a). Exposed rocks in the western area of the
Muping gold deposit are metamorphic rocks of Jinshan Group, which
Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Fig. 1. Geological map of the Jiaodong gold province, showing the distribution of major fault zones, basements, Mesozoic igneous rocks, UHP metamorphic rocks,
and gold deposits. Modified after Fan et al. (2003).

Fig. 2. Simplified geological map of the Muping-Rushan gold metallogenic belt. Modified from Zhou et al. (2011).

3
Y.-W. Zhang, et al.
Fig. 3. a Geological map of the Muping gold deposit. b Cross-section (A–B) of ore veins.
consists of plagioclase amphibolite and biotite gneiss. Besides, there are
many dykes in the two sides of the ore body, such as lamprophyre,
gabbro, and diorite porphyrite (Fig. 3a).
3. Deposit geology
The Muping gold deposit has been in production since 1987 and
consists of Denggezhuang and Heiniutai mines. The Heiniutai mine is
located in the Jingniushan fault and Denggezhuang mine controlled by
the western subsidiary faults (Fig. 2). Several gold ore veins have been
discovered (Fig. 3). Ore veins I and II are the major ore bodies. Ore vein
I can be classified I1 and I2. Ore vein I1 dips to northwest at 70–85°, and
it has a length of 2200 m (Fig. 3a) with a thickness of 0.5-1 m. It be-
came thicker where the dip angle of the lode decreased. The grade of
ore vein I1 is 3.0–10.0 g/t with a maximum up to 60 g/t. There is a
positive relationship between gold grade and orebody thickness (Hu
et al., 2007). Ore vein I2 has the same dip direction with I1 and the dip
angles are 30–60°, the thickness of the lode is normally 0.4–1.2 m, and
the grade is averaged at 3.0 g/t with a maximum of 40 g/t. Ore vein II
located on the middle part of the mine, strikes 10° and dips northwest
with a length of 1200 m and the thickness range from 1 to 2 m, the
grade of gold ranges from 0 to 15 g/t (Hu et al., 2007). From the depth
profile, it can be observed that these ore veins are merged with an in-
crease of depth (Fig. 3b).
Hydrothermal alterations, including potassic alteration, sericitiza-
tion, silicification, pyrite-sericite-quartz alteration, are also common in
the Muping gold deposit. The alteration zoning is characterized by
strong pyrite-sericite-quartz adjacent to the vein, grading into sericitic
and potassic (Fig. 4a, c, g). Potassic alteration marks the earliest al-
teration stage and is characterized by the appearance of K-feldspar that
replaces or overgrows primary plagioclase (Fig. 5a) (Cai et al., 2018).
Phyllic alteration is typified by partial or total replacement of biotite by
sericite and transformation of plagioclase to sericite (Fig. 5b).
4. Ore mineralogy
Major ore minerals include native gold, pyrite, chalcopyrite, galena,
sphalerite, magnetite, pyrrhotite, and arsenopyrite. Main gangue mi-
nerals consist of quartz, calcite, siderite, potassium feldspar, and ser-
icite, with minor barite (Figs. 5, 6).
Field, optical and scanning electron microscopy (SEM)
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Journal of Geochemical Exploration 218 (2020) 106617
investigations revealed four mineralization stages and three types of
pyrite at Muping: i.e. Stage I was defined by pyrite-quartz veins, which
are dominated by milky white quartz and subordinate coarse-grained,
euhedral to subhedral pyrite (Py1) (Figs. 4a, c, g; 5c); Stage II is defined
by quartz-pyrite veins, which are characterized by smoky quartz and
abundant subhedral pyrite (Py2) with minor visible gold and chalco-
pyrite occurring as inclusions. Sericitolite or beresitization occurs inside
or on both sides of the ore vein (Figs. 4d, g; 5d); Stage III is defined as
quartz-polymetallic sulfides veins, which are characterized by smoky
quartz and various sulfides. These veins cut through the quartz-pyrite
vein (Fig. 4e) and there are obvious quartz vug and geodes suggesting
open space (Fig. 4h, i). Pyrite (Py3) in this stage can be divided into
three sub-types (Py3a, Py3b, and Py3c) according to the texture of
pyrite. Py3a consists of tiny pyrite grains that corroded pyrrhotite and
dense disseminated pyrite with amounts of chalcopyrite, visible gold,
sphalerite and galena depositing in fractures, grain boundaries or oc-
curring as inclusions (Fig. 5e–i). Py3b and Py3c can be discriminated by
means of field emission scanning electron microscope (FE-SEM), to-
gether making up the pyrite with core-rim texture (Fig. 6e–i). The Py3b
is the core of the pyrite, there are amounts of fractures and corroded
pores filling with sphalerite, galena, arsenopyrite, and visible gold. In
contrast, Py3c that rarely has mineral inclusions, fractures and dis-
solved pores is the rim of the pyrite (Fig. 8a–b). In addition, some
magnetite corroded Py3a can be observed in the thin section (Fig. 5f–g).
It is worth noting that there is minor barite which is existing with
siderite filling in fractures of pyrite and matrix (Fig. 6b–c). (4) Stage IV
is defined by quartz-calcite veins, which crosscut all other vein types
and have pyrite relic of the previous mineralization stage (Fig. 4g).
The paragenetic sequence of the aforementioned minerals in the
mineralization stage is illustrated in Fig. 7.
5. Sampling and analytical methods
Most ores were collected from underground tunnels of the Muping
gold deposit and minor ore samples were collected from ore heap. All
mineralization stage ores were made into the thin section for electronic
microscopic observation and in-situ elemental and sulfur isotopic ana-
lyses.
Y.-W. Zhang, et al.
Fig. 4. Photographs show field and hand specimen characteristics. (a) Pyrite-quartz vein and sericite alteration. (b) Auriferous pyrite vein paralleling to the mafic
dyke. (c) Pyrite-sericite rock existed in two sides of the pyrite-quartz vein with geode. (d) Quartz-pyrite vein. (e) Quartz-sulfide vein crosscutting quartz-pyrite vein.
(f) Siderite veinlet crosscutting pre-stage pyrite and pyrrhotite. (g) Crosscutting relations of different stage ore veins. (h) Quartz geode existed in pyrrhotite-pyrite
vein. (i) Sphalerite and core-rim textural pyrite coexisted with quartz vug and geode.
5.1. Major elements spot analysis and mapping of pyrite
Major element compositions of representative pyrite were collected
on a JEOL JXA-8100 electron microprobe, at the Institute of Geology
and Geophysics, Chinese Academy of Sciences (IGGCAS) with a focused
beam diameter of 5 μm, an accelerating voltage of 20 kV and a beam
current of 10 nA. Calibration standards used were pyrite for S and Fe,
chalcopyrite for Cu, galena for Pb, and alloy or pure metal for As, Co,
Ni, Ag and Au. The detection limits for each element were As
(231 ppm), Fe (111 ppm), S (99 ppm), Pb (598 ppm), Cu (210 ppm), Zn
(226 ppm), Co (112 ppm), Ni (120 ppm), Ag (253 ppm) and Au
(614 ppm). Major elements in pyrite were analyzed by EMPA to be used
for calibration information of the LA-ICP-MS analyses described below.
Pyrite with core-rim texture was chosen to qualitatively map com-
positional variation (Fe, S, As, Au) using EPMA and NanoSIMS map-
ping. High-resolution EMPA maps were collected using a Cameca
SXFiveFE electron microprobe, with 20 kV acceleration voltage, 100 nA
beam current, 250–300 ms dwell time per spot and minimum beam size
of 1–2 μm. Elements and X-ray lines used for analyses are Fe (Kα), S
(Kα), As (Lα), and Au (Lα) in each area (Feng et al., 2018). High-re-
solution NanoSIMS maps were performed using a Cameca NanoSIMS
50 L instrument at IGGCAS. Samples were polished and coated with C
for conductivity at high voltage. A Cs+ beam current of ~7–10 pA with
a diameter of 250 nm was rastered across the sample surface. Before
image acquiring, the selected area (50 × 50 μm2) was sputtered with a
high intensity of 1 nA for ~2 min to remove the coating and to stabilize
the yield of the secondary ions. Images with a resolution of 256 × 256
pixels, were recorded from the secondary ions 34S, 80Se, 63Cu32S,
75
As32S, 197Au, 208Pb32S, simultaneously. Peaks were calibrated using
arsenopyrite for AsS, chalcopyrite for CuS, galena for PbS, FeSe2 for Se,
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Journal of Geochemical Exploration 218 (2020) 106617
and metallic Au.
5.2. LA-ICP-MS trace elements analysis of pyrite
Trace element analysis of minerals was conducted with a LA-ICP-MS
at the Wuhan Sample Solution Analytical Technology Co. Ltd. Wuhan,
China. Detailed operating conditions for the laser ablation system and
the ICP-MS instrument and data reduction are the same as described by
Zong et al. (2017). Laser sampling was performed using a GeolasPro
laser ablation system that consists of a COMPexPro 102 ArF excimer
laser (wavelength of 193 nm and maximum energy of 200 mJ) and a
MicroLas optical system. 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 (Hu et al., 2015). The spot size
and frequency of the laser were set to 33 μm and 5 Hz in this study,
respectively. Each analysis incorporated a background acquisition of
approximately 20–30 s followed by 50 s of data acquisition from the
sample. An Excel-based software ICPMSDataCal was used to perform
off-line selection and integration of background and analyzed signals,
time-drift correction and quantitative calibration for trace element
analysis (Liu et al., 2008). All analyses were quantified against USGS
synthetic MASS-1 standard (Wilson et al., 2002), following the proce-
dure of Longerich et al. (1996) and using Fe as the internal standard,
and the Fe contents were quantified by EMP analyses. The detection
limit for all measured trace elements was 0.01–0.001 ppm. The stan-
dard MASS-1 was compared to published values to ensure reasonable
homogeneity in the standards for the elements analyzed. Average va-
lues and standard deviations of elements can be found in Table S1.
Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Fig. 5. Photomicrographs of the minerals in alteration and mineralization stages. (a) Potassic altered wallrocks characterized by plagioclase partly replaced by K-
feldspar. (b) Phyllic alteration, typified by biotite and plagioclase partly replaced by sericite. (c) Coarse-grained euhedral and subhedral pyrite in pyrite-quartz vein.
(d) Subhedral and fractured pyrite, rarely coexisting with native inclusion. (e–f) Siderite and fine-grained pyrite dissolved pyrrhotite. (f–g) Siderite and magnetite
dissolved fine-grained pyrite of stage III with or without chalcopyrite. (h) Chalcopyrite filled in fractures of pyrite of stage III with native gold. (i) Native gold filled in
the fracture or dissolved pore of pyrite of stage III. Mineral abbreviations: Qtz, quartz; Pl, Plagioclase; Kfs, K-feldspar; Bi, Biotite; Ser, Sericite; Py, pyrite; Sd, siderite;
Po, pyrrhotite; Mt., magnetite; Ccp, chalcopyrite; Au, native gold.

5.3. Sulfur isotope analysis of pyrite and other sulfides
Sulfur isotope analysis was carried out in-situ on sulfides from
standard polished thin sections using a Nu Plasma II MC-ICP-MS, which
was equipped with a Resonetics-S155 193 nm excimer ArF laser abla-
tion system at the GPMR, China University of Geosciences (Wuhan).
During the experiment, the diameter of the laser beam was 33 μm with
a laser repetition rate of 10 or 6 Hz according to the thickness of the
thin section. The fast “washout” time of 25 s allows a high sample
throughput and the ablation process was set to last for 40 s. Standard-
sample bracketing (SSB) was used to determine the δ34S values of
samples throughout the MC-ICPMS analytical sessions. WS-1 was used
as in-house pyrite calibrated standard in this study which is natural
pyrite collected from Wenshan polymetallic skarn deposit, Yunnan
Province, China, and all sulfides are calibrated by WS-1 because no
obvious matrix effect has been observed (Zhu et al., 2016). The δ34S
values for WS-1 natural pyrite were determined to be 0.9‰ using the
isotope ratio mass spectrometer, as well as 1.1 ± 0.2‰ by SIMS at the
Chinese Academy of Geochemistry, Guangzhou (Zhu et al., 2016,
2017). Detailed analytical conditions and procedures are provided in
Zhu et al. (2016, 2017). The true sulfur isotope ratio was calculated by
correction for instrumental mass bias by linear interpolation between
the biases calculated from two neighboring standard analyses. The ex-
ternal precision is 0.4‰ (2SD) in this study which is consisting of the
external precision is 0.15–0.45% (2SD) with an accuracy of 0.15‰ for
δ34S according to long-term laboratory study.
Additionally, Py3b and Py3c have variable element composition
which was detected by LA-ICPMS spot analysis and NanoSIMS ele-
mentals mapping. The width of the rim of pyrite with core-rim texture
is relatively narrow, NanoSIMS has a higher spatial resolution which
can analyze sulfur isotope variation that was hidden or weaken when
we using a lower spatial resolution instrument such as LA-MC-ICP-MS
and investigate the correlation between sulfur isotope values variation
and trace element distribution. Sulfur isotope analysis of the pyrite with
core-rim texture was performed using a Cameca NanoSIMS 50 L in-
strument at IGGCAS. Samples were polished and coated with C for
conductivity at high voltage. A Cs+ beam current of ~7–10 pA with a
diameter of 250 nm was rastered across the sample surface. Before
sulfur isotope analyzing, each area of 20 × 20 μm2 was firstly pre-
sputtered with a primary beam of ~1 nA for ~2 min to remove the
coating and to stabilize the yield of the secondary ions. Ion images of
each pre-sputtered region were acquired and the interesting grains were
selected for analysis. The instrument then automatically analyzed all
the selected grains by rastering the primary beam over each pre-set area
(e.g. 2 × 2 μm2) of the grains. The total counting time for each analysis
was 150 s, consisting of 300 cycles of 0.5 s. Detailed analytical condi-
tions and procedures are provided by Zhang et al. (2014). Pyrite of
Balmat, CAR 123 pyrite are certified international standards with the

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Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Fig. 6. Photomicrographs and BSE images of sulfides in the main metallogenic stage. (a) Arsenopyrite filled in fracture of pyrite and pyrrhotite. (b–c) Siderite and
barite filled in fracture of pyrite or contained fine-grained pyrite inclusions. (d) Arsenopyrite filled in dissolved pores of pyrite. (e–g) Reflected light and BSE images
of core-rim textural pyrite coexisting with sphalerite and galena. (h–i) Native gold filled in fracture of core-rim textural pyrite. Mineral abbreviations: Asp, ar-
senopyrite; Py, pyrite; Sd, siderite; Po, pyrrhotite; Bar, barite; Sp, sphalerite; Gn, galena; Au, native gold.

recommended δ34S VCDT values. The other sulfide minerals (the pyrites
PY-1117 and CS01) are working reference samples. The analytical lat-
eral resolution was < 2 × 2 μm2 and the external reproducibility was
better than 0.5‰ (1SD) for δ34S.
6. Results
6.1. Trace element compositions and correlations in pyrite
A total of 82 LA-ICP-MS spot analyses were conducted, which in-
cluded 5 spots on Py1, 27 spots on Py2, 32 spots on Py3a, 6 spots on
Py3b and 12 spots on Py3c. These spots analyses were designed to re-
cord the concentration of invisible gold and other lattice-bound trace
elements in pyrite, so it is important to avoid visible gold grain when
we design analysis spot, but some minerals inclusion below the surface
are unavoidable, which may explain some of the outliers. Absolute
concentrations (ppm) of selected trace elements are reported in Table 1
and Table S2, and the enrichment regularity of trace elements in dif-
ferent types of pyrite are illustrated in Fig. 9. Au, As, Ag, Sb, Te, Co, Ni,
Cu, Zn, Pb and Bi showed meaningful variations, but Se, was con-
sistently below detection.
The gold content in Py1 is below the detection limit, other elements
such as Ag, Sb, Cu, Zn, Pb, Bi and Se are also below the detection limit.
The contents of Te (median below detection) are very low, but Py1 has
the highest Co (738 ppm on median) and Ni (30 ppm on median)
concentration compared to pyrites of a subsequent generation.
The gold content in Py2 is also low, ranging from below detection to
1 ppm, and the median value is 0.1 ppm. Other elements have in-
homogeneous distribution, Py2 has elevated and highly variable arsenic
content (from below detection to 2126 ppm, 754 ppm on median).
Elevated trace elements compared to Py1 include Ag (from below de-
tection to 10 ppm, 0.02 ppm on median), Cu (from below detection to
550 ppm, 0.1 ppm on median), Pb (below detection to 109 ppm,
0.2 ppm on median), Bi (from below detection to 53 ppm, 0.2 ppm on
median). Compared to Py1, Py2 is depleted in Co (from below detection
to 587 ppm, 29 ppm on median) and Ni (from below detection to
211 ppm, 7.6 ppm on median).
Py3a has a high and variable gold concentration ranging from below
detection to 21 ppm with a median value of 0.7 ppm compared to Py1
and Py2. The arsenic content varies from below detection to
10,016 ppm with a median value of 1089 ppm. Py3a is depleted in Co
(from below detection to 48 ppm, median value below detection) and
Ni content was detected only in two analyses (1.5 ppm and 48 ppm).
Py3b has relatively low gold (0.1–1.2 ppm, 0.4 ppm on median) and
arsenic (32–2539 ppm, 206 ppm on median) concentration but Py3c
has the highest gold (6.8–136 ppm, 36 ppm on median) and arsenic
(6857–18,641 ppm, 16,290 ppm on median) concentration compared
to other generation pyrites. Other elements such as Ag, Sb, Te, Cu, Zn
and Pb that are in Py3b and Py3c have significant variability. Py3b has
the highest Ag (32–2539 ppm), Sb (13–68 ppm), Te (from below

7
Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Fig. 7. Paragenetic sequence for representative hydrothermal minerals of the Muping gold deposit. The width of the solid lines denotes the relative abundance of
minerals.

detection to 111 ppm), Cu (46–1521 ppm), Zn (304–3129 ppm) and Pb
(302–10,790 ppm) concentrations compared to other pyrite genera-
tions. By contrast, Py3c has relatively low Ag (0.04–9 ppm), Sb (from
below detection to 2 ppm), Te (from below detection to 9 ppm), Cu
(5.3–237 ppm) and Pb (from below detection to 8 ppm) concentration.
Py3b and Py3c are extremely depleted in Co and Ni (median values
below detection). Overall, Py1 is enriched in Co and Ni, Py3b is en-
riched in Ag, Sb, Te, Cu, Zn and Pb, Py3c is enriched in Au and As. Py2
and Py3a have no obvious trace elements enrichment in comparison
with other generations (Fig. 9).

Table 1
Summarized laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analyses of different generations of pyrite.
Au As Ag Sb Te Co Ni Cu Zn Pb Bi Se

Py1 (n = 5)
Median b.d. 15.10 b.d. b.d. b.d. 738.26 29.82 b.d. b.d. b.d. b.d. b.d.
Min b.d. b.d. b.d. b.d. b.d. 0.51 b.d. b.d. b.d. b.d. b.d. b.d.
Max b.d. 50.68 b.d. b.d. 1.38 3662.25 295.52 b.d. b.d. 0.03 b.d. b.d.

Py2 (n = 27)
Median 0.10 753.65 0.02 b.d. 0.83 28.80 7.64 0.12 b.d. 0.19 0.20 b.d.
Min b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d.
Max 0.96 2126.28 10.47 2.87 23.23 586.66 211.32 550.20 8.72 108.64 52.70 b.d.

Py3a (n = 32)
Median 0.69 1089.30 0.19 0.20 0.62 b.d. b.d. 3.20 b.d. 2.39 0.02 b.d.
Min b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d.
Max 21.28 10,016.16 13.47 7.35 18.48 47.77 48.40 171.90 22.91 52.57 12.96 b.d.

Py3b (n = 6)
Median 0.39 206.24 15.22 46.31 0.60 b.d. b.d. 219.53 1271.57 837.62 b.d. b.d.
Min 0.05 32.36 9.91 12.50 b.d. b.d. b.d. 46.14 303.57 302.14 b.d. b.d.
Max 1.16 2538.63 68.38 67.53 111.22 3.48 5.41 1520.95 3128.57 10,789.09 b.d. b.d.

Py3c (n = 12)
Median 35.77 16,289.69 0.26 0.24 0.14 b.d. b.d. 48.97 b.d. 1.31 b.d. b.d.
Min 6.79 6856.55 0.04 b.d. b.d. b.d. b.d. 5.28 b.d. 0.26 b.d. b.d.
Max 136.31 18,640.57 8.93 1.99 9.17 4.62 0.84 236.66 697.98 8.10 b.d. b.d.

8
Y.-W. Zhang, et al.
Gold and As in all pyrite generations plot way below the solubility
limit for gold in arsenian pyrite (Reich et al., 2005), indicating that gold
occurs as Au1+ in the pyrite lattice (Fig. 10). Correlations between Au
and other trace elements in pyrites are shown in Fig. 11. All data higher
than the detection limit are used for calculating the correlation coeffi-
cients. Gold and Ag generally show a relatively significant correlation
in Py3b (correlation coefficient rAu，Ag = 0.68), gold and Pb have
higher correlation in Py2 and Py3b (correlation coefficients are 0.74
and 0.89, respectively) (Fig. 11a–b). There is no significant correlation
between Ag and Sb, excepting Py3c (Fig. 11c). Silver and Te generally
show some degree of correlation in Py2 and Py3b (correlation coeffi-
cients are 0.63 and 0.88, respectively) (Fig. 11d). Silver and Pb show a
slightly strong correlation in Py2, Py3b and Py3c (correlation coeffi-
cients are 0.85, 0.66 and 0.79, respectively), excepting Py3a (Fig. 11e).
The correlation between Zn and Cu is similar to that between Ag and Pb
(Fig. 11f), but the degree of correlation is higher (correlation coeffi-
cients are 0.95, 0.75 and 0.89, respectively). From the NieAs and
CoeAs correlation diagram, we recognize that in general the con-
centration of Co and Ni gradually decreased from the early miner-
alization to the main mineralization stage, but the concentration of
arsenic has a contrary tendency (Fig. 11g–h).
6.2. Sulfur isotopes of pyrite and other sulfides
A total of 89 in-situ MC-LA-ICPMS sulfur isotope compositions were
determined (7 in chalcopyrite, 7 in galena, 13 in sphalerite, 5 in pyr-
rhotite, 4 arsenopyrite, 4 in Py1, 20 in Py2, 9 in Py3a, 9 in Py3b, 11 in
Py3c). The sulfur isotope results are shown in Table 2 and Fig. 12a. A
total of 18 NanoSIMS sulfur isotope compositions were determined, in
which 4 analysis spots on Py3b that is Au- and 34S-deficient and 14
analysis spots on Py3c that is Au- and 34S-enriched. The sulfur isotope
data by NanoSIMS are shown in Table 3 and Figs. 8, 12b.
For in-situ LA-MC-ICPMS sulfur isotope analysis, the δ34S values for
Py1 range from +11.4‰ to +11.8‰; the δ34S values for Py2 (+7.1‰
to +9.6‰) are lower than Py1; Py3a has a similar composition with
Py2 (+7.7‰ to +9.0‰); Py3b has the lowest δ34S values, which range
from +7.3‰ to +7.9‰; The δ34S values for Py3c increased slightly
compared to Py3b, which range from +8.0‰ to +9.2‰; The δ34S
values for chalcopyrite range from +4.6‰ to +6.1‰; the δ34S values
for galena range from +2.2‰ to +3.0‰; the δ34S values for sphalerite
range from +5.5‰ to +7.9‰; the δ34S values for pyrrhotite range
from +7.7‰ to +7.8‰, and the δ34S values for arsenopyrite range
from +8.1‰ to +8.7‰.
Fig. 12b shows that Py3c is distinctly enriched in δ34S (+7.5‰ to
+11.8‰) relative to Py3b (+6.0‰ to +6.4‰). Otherwise, we can
recognize that the δ34S value gradually increased from inner rim (near
the core) to outer rim (away from the core), and the variation trend of
sulfur isotope wasn't affected by arsenic concentration which shows
slight degree change based on element mapping of arsenic. The δ34S
values of Py3b determined by LA-MC-ICP-MS and NanoSIMS are
slightly different (+7.5‰ and +6.2‰), which is likely due to errors
caused by different analysis methods and/or sulfur isotope slightly in-
homogeneous distribution in Py3b. Besides, the different δ34S values of
Py3c caused by the size of the beam spot of different analysis methods is
the most likely, because the δ34S value gradually increased from inner
rim to outer rim but the beam spot of LA-MC-ICP-MS is too big for
discriminating sulfur isotope variation precisely.
7. Discussion
7.1. Trace elements incorporation in pyrite
Py1 has the highest Co and Ni concentrations among all pyrite
generations but contains no Au and minor As. Co and Ni gradually
decreased while As and also Au increased from the early mineralization
stage to the main mineralization stages, especially for Py3c. Cobalt and
9
Journal of Geochemical Exploration 218 (2020) 106617
nickel are typical mantle-derived elements, especially for basic magma
(Loftus-Hills and Solomon, 1967; Rajabpour et al., 2017). Up to 9 wt%
Co can be included in pyrite at temperatures of 400 °C, and at higher
temperatures (> 700 °C) a complete solid solution between FeS2-CoS2
can occur (Clark et al., 2004). Arsenic is transported in hydrothermal
fluids mainly as As(III), and As(OH)3(aq) is the dominant As(III) species
in aqueous hydrothermal fluids up to at least 300 °C (Pokrovski et al.,
2002). Arsenic tends to become enriched near the sub-surface and in
sedimentary and sedimentary-volcanic rocks. Its solubility in pyrite
decreases with increasing temperature, and pyrite can host up to ~6 wt
% of arsenic in solid solution (Tauson, 1999; Pokrovski et al., 2002;
Reich et al., 2006). Relatively high temperature is favorable for sub-
stitution of Fe by Co and Ni while low temperature facilitates sub-
stitution of S by As (Migdisov et al., 2011; Deditius et al., 2014).
Moreover, it has been shown that cooling may have a dramatic effect on
the destabilization of Co-chloride complexes in hydrothermal fluids.
Specifically, a reduction of temperature from 300 to 200 °C can lead to
a decrease in Co solubility by up to two orders of magnitude (Migdisov
et al., 2011). The Co concentration of ore-forming fluid will gradually
decrease with temperature decreasing. This can explain the increase
while decreasing tends for As and CoeNi, respectively, due to a general
decrease in the fluid inclusion temperatures (Hu et al., 2007; Xue et al.,
2018).
Román et al. (2019) pointed out that pyrite formed during vigorous
boiling is characterized by relatively high concentrations of As, Cu, Pb,
Ag and Au and lower concentrations of Co and Ni compared to pyrite
formed under different conditions. Moreover, these anhedral to eu-
hedral pyrite grains display zones with a porous texture and abundant
mineral and micro- to nano-inclusions. In contrast, pyrite formed under
steadier physic-chemical condition (such as non-boiling condition) are
euhedral and pristine crystals with scarce pores and minerals inclu-
sions, these pyrites are characterized by a higher concentration of Co
and Ni, and relatively low concentrations of As, Cu, Pb, Ag and Au
(Román et al., 2019). These consist of texture and trace elements in
pyrite of the Muping gold deposit. The Py3b has amounts of fractures
and corroded pores filling with sphalerite, galena, arsenopyrite and
visible gold. Additionally, we can realize that lots of sub-micro sulfide
inclusions precipitated when Py3b was forming (Figs. 6e, 8a and 13e).
In contrast, Py3c rarely has mineral inclusions, fractures and corroded
pores (Figs. 6f, 8b and 13f). Py3b has the highest Ag, Sb, Te, Cu, Zn and
Pb concentrations compared to other pyrite generations and these trace
elements also have a relatively significant correlation (Figs. 9, 11). All
of these facts suggest that Py3b formed under highly fluctuating con-
ditions, which could be caused by fluid immiscibility or boiling process.
It consists of previous fluid inclusion results from the Muping gold
deposit (Hu et al., 2007; Xue et al., 2018).
In a single mineralization stage (Py3b and Py3c), minor temperature
changes exist, so it could not be a factor for the sharp increase in ar-
senic. Instead, we propose that a mixture of two different geochemical
feature hydrothermal fluids play an important role in forming the pyrite
with core-rim texture. Extensive oxygen and hydrogen isotopic studies
have shown that ore-forming fluids of the Muping and other early
Cretaceous gold deposits in the eastern NCC were mainly derived from
magmatic sources with the incorporation of meteoric waters (Hu, 2006;
Zhu et al., 2015; Cai et al., 2018). Arsenic commonly enriched in meta-
sedimentary rocks relative to granitoids in Jiaodong (Ding et al., 1997),
and the former also has a higher sulfur isotope value (Huang, 1994;
Zhang and Chen, 1999; Li et al., 2004). It is inferred that ore-forming
fluids of the Muping gold deposit were initially derived from magmatic
sources (Hu, 2006), and then evolved toward mixing of magmatic fluids
with an As-rich and heavy δ34S (Py3c) meteoric water which has flowed
through meta-sedimentary rocks (such as Jinshan Group) (Fig. 8). An-
other interesting phenomenon is that increase of sulfur isotope value
from the inner rim (near the core) to outer rim (away from the core)
was not affected by the oscillations of arsenic (Fig. 8c, e). Previous
research suggested that oscillatory zoning or fine-scale trace element
Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Table 2
Sulfur isotopic compositions of sulfides analyzed by LA-MC-ICP-MS at the Muping gold deposit.
Analysis no. Sample Mineralogy 34
S/32S δ34S(V-CDT)‰ Operation parameters

1 16MP065-1 Py1 4.94E-02 11.4 33um,10 Hz,50%T

2 16MP065-2 Py1 4.95E-02 11.7 33um,10 Hz,50%T
3 16MP065-3 Py1 4.95E-02 11.8 33um,10 Hz,50%T
4 16MP065-4 Py1 4.94E-02 11.5 33um,10 Hz,50%T
5 16MP025-01 Py2 4.93E-02 8.3 33um,6 Hz,50%T
6 16MP025-02 Py2 4.93E-02 9.1 33um,6 Hz,50%T
7 16MP025-03 Py2 4.92E-02 7.1 33um,6 Hz,50%T
8 16MP025-04 Py2 4.92E-02 7.1 33um,6 Hz,50%T
9 16MP025-05 Py2 4.92E-02 7.1 33um,6 Hz,50%T
10 16MP025-06 Py2 4.93E-02 8.9 33um,6 Hz,50%T
11 16MP025-07 Py2 4.93E-02 9.0 33um,6 Hz,50%T
12 16MP025-08 Py2 4.93E-02 9.2 33um,6 Hz,50%T
13 16MP025-09 Py2 4.93E-02 9.5 33um,6 Hz,50%T
14 16MP040-1 Py2 4.93E-02 8.4 33um,10 Hz,50%T
15 16MP040-2 Py2 4.93E-02 8.8 33um,10 Hz,50%T
16 16MP040-3 Py2 4.93E-02 8.3 33um,10 Hz,50%T
17 16MP040-4 Py2 4.93E-02 8.9 33um,10 Hz,50%T
18 16MP040-5 Py2 4.93E-02 8.1 33um,10 Hz,50%T
19 16MP048-1 Py2 4.93E-02 9.3 33um,10 Hz,50%T
20 16MP048-2 Py2 4.93E-02 9.2 33um,10 Hz,50%T
21 16MP048-3 Py2 4.93E-02 8.7 33um,10 Hz,50%T
22 16MP079-5 Py2 4.94E-02 9.6 33um,10 Hz,50%T
23 16MP079-6 Py2 4.94E-02 9.6 33um,10 Hz,50%T
24 16MP079-7 Py2 4.93E-02 8.9 33um,10 Hz,50%T
25 16MP002-6 Py3a 4.93E-02 7.9 33um,10 Hz,50%T
26 16MP002-7 Py3a 4.93E-02 7.8 33um,10 Hz,50%T
27 16MP002-8 Py3a 4.93E-02 7.7 33um,10 Hz,50%T
28 16MP44-19 Py3a 4.93E-02 9.0 33um,10 Hz,50%T
29 16MP44-20 Py3a 4.93E-02 8.9 33um,10 Hz,50%T
30 16MP44-21 Py3a 4.93E-02 8.8 33um,10 Hz,50%T
31 16MP44-22 Py3a 4.93E-02 8.2 33um,10 Hz,50%T
32 16MP079-13 Py3a 4.93E-02 8.1 33um,10 Hz,50%T
33 16MP079-14 Py3a 4.93E-02 8.1 33um,10 Hz,50%T
34 16MP070-8 Py3b-core 4.93E-02 7.9 33um,10 Hz,50%T
35 16MP070-9 Py3b-core 4.92E-02 7.5 33um,10 Hz,50%T
36 16MP070-2 Py3b-core 4.92E-02 7.6 33um,10 Hz,50%T
37 16MP070-4 Py3b-core 4.92E-02 7.8 33um,10 Hz,50%T
38 16MP070-1-5 Py3b-core 4.92E-02 7.4 33um,10 Hz,50%T
39 16MP070-1-6 Py3b-core 4.92E-02 7.3 33um,10 Hz,50%T
40 16MP070-1-7 Py3b-core 4.92E-02 7.4 33um,10 Hz,50%T
41 16MP070-1-8 Py3b-core 4.92E-02 7.3 33um,10 Hz,50%T
42 16MP070-1-9 Py3b-core 4.92E-02 7.4 33um,10 Hz,50%T
43 16MP070-1 Py3c-rim 4.93E-02 9.2 33um,10 Hz,50%T
44 16MP070-3 Py3c-rim 4.93E-02 8.0 33um,10 Hz,50%T
45 16MP070-5 Py3c-rim 4.93E-02 9.3 33um,10 Hz,50%T
46 16MP070-6 Py3c-rim 4.93E-02 8.1 33um,10 Hz,50%T
47 16MP070-7 Py3c-rim 4.93E-02 8.6 33um,10 Hz,50%T
48 16MP070-1-1 Py3c-rim 4.93E-02 9.0 33um,10 Hz,50%T
49 16MP070-1-2 Py3c-rim 4.93E-02 8.6 33um,10 Hz,50%T
50 16MP070-1-3 Py3c-rim 4.93E-02 8.7 33um,10 Hz,50%T
51 16MP070-1-4 Py3c-rim 4.93E-02 8.7 33um,10 Hz,50%T
52 16MP070-1-10 Py3c-rim 4.93E-02 8.1 33um,10 Hz,50%T
53 16MP070-1-11 Py3c-rim 4.93E-02 8.2 33um,10 Hz,50%T
54 16MP070-10 Sp 4.92E-02 7.4 33um,10 Hz,50%T
55 16MP070-11 Sp 4.92E-02 7.7 33um,10 Hz,50%T
56 16MP070-16 Sp 4.92E-02 7.3 33um,10 Hz,50%T
57 16MP070-17 Sp 4.92E-02 7.3 33um,10 Hz,50%T
58 16MP070-18 Sp 4.92E-02 7.2 33um,10 Hz,50%T
59 16MP070-28 Sp 4.93E-02 7.9 33um,10 Hz,50%T
60 16MP070-1-12 Sp 4.92E-02 7.1 33um,10 Hz,50%T
61 16MP070-1-13 Sp 4.92E-02 6.8 33um,10 Hz,50%T
62 16MP070-1-14 Sp 4.92E-02 6.8 33um,10 Hz,50%T
63 16MP070-1-15 Sp 4.92E-02 7.1 33um,10 Hz,50%T
64 16MP044-12 Sp 4.92E-02 5.5 33um,10 Hz,50%T
65 16MP044-13 Sp 4.92E-02 6.1 33um,10 Hz,50%T
66 16MP044-14 Sp 4.92E-02 5.8 33um,10 Hz,50%T
67 16MP070-12 Gn 4.90E-02 2.9 33um,10 Hz,50%T
68 16MP070-13 Gn 4.90E-02 2.6 33um,10 Hz,50%T
69 16MP070-14 Gn 4.90E-02 2.8 33um,10 Hz,50%T
70 16MP070-15 Gn 4.90E-02 3.0 33um,10 Hz,50%T
71 16MP44-2 Gn 4.90E-02 2.2 33um,10 Hz,50%T
72 16MP044-3 Gn 4.90E-02 2.8 33um,10 Hz,50%T
73 16M0P44-5 Gn 4.90E-02 2.4 33um,10 Hz,50%T
74 16MP002-3 Ccp 4.92E-02 5.9 33um,10 Hz,50%T
(continued on next page)

10
Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Table 2 (continued)

Analysis no. Sample Mineralogy 34

S/32S δ34S(V-CDT)‰ Operation parameters

75 16MP002-4 Ccp 4.91E-02 4.6 33um,10 Hz,50%T

76 16MP44-1-4 Ccp 4.91E-02 5.4 33um,10 Hz,50%T
77 16MP44-15 Ccp 4.91E-02 5.3 33um,10 Hz,50%T
78 16MP44-16 Ccp 4.92E-02 6.1 33um,10 Hz,50%T
79 16MP44-17 Ccp 4.92E-02 5.7 33um,10 Hz,50%T
80 16MP44-18 Ccp 4.92E-02 6.0 33um,10 Hz,50%T
81 16MP079-8 Po 4.93E-02 7.7 33um,10 Hz,50%T
82 16MP079-9 Po 4.93E-02 7.8 33um,10 Hz,50%T
83 16MP079-10 Po 4.93E-02 7.8 33um,10 Hz,50%T
84 16MP079-11 Po 4.93E-02 7.8 33um,10 Hz,50%T
85 16MP079-12 Po 4.93E-02 8.2 33um,10 Hz,50%T
86 16MP079-1 Apy 4.93E-02 8.1 33um,10 Hz,50%T
87 16MP079-2 Apy 4.93E-02 8.7 33um,10 Hz,50%T
88 16MP079-3 Apy 4.93E-02 8.5 33um,10 Hz,50%T
89 16MP079-4 Apy 4.93E-02 8.4 33um,10 Hz,50%T

chemistry variation which could be caused by extrinsic changes in fluid
composition, pressure or temperature of the parent hydrothermal
system, as well as changes in mineral growth rate (Barker and Cox,
2011; Reich et al., 2013; Peterson and Mavrogenes, 2014; Fougerouse
et al., 2016b; Li et al., 2018). And Growth zone in sulfide minerals has
been demonstrated to be caused by several separated mineralization
stages during different hydrothermal event, such as pyrite in Carlin-
type system (Barker et al., 2009). Moreover, crystallography also can
control the differential uptake of trace elements during a single hy-
drothermal event (Chouinard et al., 2005). The arsenic concentration in
the “near-surface” region of the pyrite and competition between crystal
growth (trapping surface enriched element) and ion migration in the
near-surface region (which attempts to rid the crystal lattice of im-
purities) can explain the content variation in the rim of pyrite in the
Muping gold deposit (Watson, 1996, 2004), but during mixing of two
end-members, the extrinsic effects of geological controls such as fluid
composition and temperature also cannot be excluded.
7.2. Sulfur isotope fractionation and its controlling factors
Sulfur isotope values of pyrites from different mineralization stages
are shown in Figs. 13, 14. These data displayed a gradual depletion in
δ34S from Py1 to Py3b (from +11.6‰ to +7.5‰) but gradually in-
creased from core to rim for the pyrite with core-rim texture (From
+6.0‰ to +11.8‰). There exist different factors that caused sulfur
isotope variation during different mineralization stage: (1) isotopic
composition of the parental fluid, (2) temperature, (3) the dissolved
sulfur species, pH and fO2 at the mineralization stage, and (4) relative
amount of the mineral deposited from the fluids (Zheng and Hoefs,
1993).
Py1 (δ34S: 11.6‰) is more enriched in 34S than Py2 (8.6‰). There
is no obvious evidence suggested oxygen fugacity has a variation which
resulted in sulfur isotope variation in these two mineralization stages.
Some other factors such as temperature are not significant because the
temperature change between stage I and stage II is not so dramatic
(approximately < 50 °C) (Hu et al., 2007; Xue et al., 2018). This can
only induce a Δpy-H2S value of 1.0 and 1.2 at 350 °C and 300 °C, re-
spectively (Rye and Ohmoto, 1974; Ohmoto and Rye, 1979). The
average δ34S values of pyrite from Linglong biotite granite and mafic-
intermediate dykes are 7.3‰ and 6.9‰ (Huang, 1994; Li et al., 2004),
and the δ34S of pyrite from Jinshan Group are 9.3‰ to 9.8‰ (Zhang
and Chen, 1999). Intense metasomatic NCC lithospheric mantle may
have high oxygen fugacity and enriched δ34S value, then, degassing of
mantle wedge will increase the heavy S of the residual fluid (Ionov
et al., 1992; Zhu et al., 2015). So, the difference of sulfur isotope values
between Py1 and Py2 would attribute to the two ore-forming stages
suffered from different condition of degassing processes (Fiege et al.,
2014). Muping is a quartz-vein type gold deposit that is controlled by
steeply dipping dilational structures (Hu et al., 2007; Wen et al., 2015;
Fan et al., 2016; Xue et al., 2018), the δ34S of pyrite mainly controlled
by the fluid-dominated process (Hodkiewicz et al., 2009), stage I is
under conditions of greater rock buffering than later-stage fluids. The
early ore-forming fluids were likely affected by different sulfur sources,
for instance, the Jinshan Group has higher values of δ34S.
The distinction of sulfur isotope values between Py2 and Py3a is not
obvious. The fact implied sulfur source didn't have an obvious change,

Table 3
NanoSIMS sulfur isotope values of pyrite with core-rim texture.
Analysis no. Generation 32
S(cps) 34
S/32S ± SE (%) δ34S‰ (VCDT) ± SE‰

16MP070-1 Py3-rim 4.15E+08 4.46E-02 2.38E-02 11.8 0.37

16MP070-2 Py3-rim 4.09E+08 4.46E-02 2.40E-02 11.5 0.37
16MP070-3 Py3-rim 4.40E+08 4.45E-02 2.31E-02 10.6 0.36
16MP070-4 Py3-rim 4.38E+08 4.45E-02 2.31E-02 10.8 0.36
16MP070-5 Py3-rim 4.36E+08 4.45E-02 2.32E-02 10.6 0.36
16MP070-6 Py3-rim 4.40E+08 4.45E-02 2.31E-02 10.4 0.36
16MP070-7 Py3-rim 4.51E+08 4.45E-02 2.28E-02 10.7 0.36
16MP070-8 Py3-rim 4.54E+08 4.45E-02 2.27E-02 10.0 0.36
16MP070-9 Py3-rim 4.61E+08 4.45E-02 2.26E-02 9.7 0.35
16MP070-10 Py3-rim 4.74E+08 4.45E-02 2.23E-02 9.4 0.35
16MP070-11 Py3-rim 4.32E+08 4.44E-02 2.33E-02 8.6 0.36
16MP070-12 Py3-rim 4.37E+08 4.44E-02 2.32E-02 8.8 0.36
16MP070-13 Py3-rim 4.29E+08 4.44E-02 2.34E-02 7.5 0.36
16MP070-14 Py3-rim 4.34E+08 4.44E-02 2.33E-02 7.9 0.36
16MP070-15 Py3-core 4.45E+08 4.43E-02 2.30E-02 6.0 0.36
16MP070-16 Py3-core 4.43E+08 4.43E-02 2.31E-02 6.2 0.36
16MP070-17 Py3-core 4.45E+08 4.43E-02 2.30E-02 6.4 0.36
16MP070-18 Py3-core 4.58E+08 4.43E-02 2.27E-02 6.3 0.36

11
Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Fig. 8. Elements mapping and sulfur isotope values of core-rim textural pyrite. (a–b) Reflected light and BSE photos of core-rim textural pyrite. (c–d) EMP elements
mapping showed an obvious distinction of arsenic content between the rim and core of core-rim textural pyrite but didn't show a difference in gold content which is
restricted by the detection limit. (e–f) NanoSIMS elements mapping of a target region in Fig. 8c, arsenic and gold showed a coupled mineralization relationship
between the rim and core of core-rim textural pyrite. Moreover, the numbers aside from the square which represented the size (2 × 2 μm2) of analysis zone by
NanoSIMS are sulfur isotope values.

but the internal variations in Py2 and Py3a can be discriminated
against. The δ34S values of Py2 and Py3a range from 7.1‰ to 9.6‰ and
7.7‰ to 9.0‰, respectively. In a single mineralization stage such as
stage II, the fluid system can be viewed as closed, even though we think
ore-forming fluids of different mineralization stages cannot comprise a
unified and closed fluid system according to the crosscutting relation-
ship of ore veins and geochemical characteristic of different generation
pyrites. In this situation, the Rayleigh fractionation process could cause
a “reservoir effect” that already has been illustrated by Zheng and Hoefs
(1993). As is mentioned above, the isotope fractionation factor between
pyrite and hydrogen sulfide is 1.2 at 300 °C (Ohmoto and Rye, 1979),
pyrite precipitation resulted in a decrease in the δ34S value of the re-
sidual hydrothermal fluids. Consequently, later pyrite precipitated from
the fluids will have a slightly lower sulfur isotope value.
Py3b from the polymetallic sulfide stage shows the lowest sulfur
isotope value. During this mineralization stage, a lot of sulfides, such as
pyrrhotite, sphalerite, chalcopyrite, galena precipitated form hydro-
thermal fluid system. The isotope fractionation factor of these sulfides is
lower than H2S, especially for galena the isotope fractionation factor is
−3.8 at 300 °C (Ohmoto, 1972). Sulfides precipitation process should
result in an increase in the δ34S values of residual fluids, which con-
trasts with the present observation. We speculate the oxygen fugacity

12
Y.-W. Zhang, et al.
Fig. 9. Comparative box plot of trace element concentration in three types of pyrites. Co and Ni are enriched in py1; Ag, Sb, Te, Cu, Zn and Pb are enriched in py3b;
Au and As are enriched in py3c. Boxes represent the interquartile range (data between 25th and 75th percentiles), with top and bottom lines extending 1.5 times the
interquartile range toward the maximum and minimum, respectively.
may have a more important role in changing the sulfur isotope com-
position of sulfides, relative to sulfur isotope fractionation between
different minerals. The unexpected result attribute to the oxygen fu-
gacity of fluid gradually increased during sulfide deposition. The
change of ore-forming fluid redox state can be defined by the change of
mineral assemblage (Figs. 6e–g; 7b–c), in which pyrrhotite firstly was
corroded and crosscut by fine-grained pyrite (Py3a), then the Py3a was
corroded by magnetite, finally, barite coexisted with siderite filling in
the fractures of pyrite. So, we presumed that the hydrothermal fluid of
stage III evolved from a relatively reduced state to a relatively oxidized
state. Only a small amount of barite but no hematite occurred during
the late stage of mineralization implied that the redox state of hydro-
thermal fluid was buffered by the assemblage of pyrite and magnetite.
Sulfur isotope research from some other gold deposits in Jiaodong also
suggested that it is the increased oxygen fugacity resulted in the de-
crease of pyrite sulfur isotope value (Yang et al., 2017; Cai et al., 2018;
Feng et al., 2018).
Previous fluid inclusions research of the Muping gold deposit sug-
gested that fluid immiscibility occurred during the gold mineralization
stage, due to a dramatic decrease in pressure and temperature (Hu
et al., 2007; Xue et al., 2018). It also consists of the texture and trace
elements research of pyrite from the Muping gold deposit. Phase se-
paration resulted in the escape of volatile from fluid and/or forming a
low density “vapor” phase separated from high-density ore-forming
fluid phase (Pichavant et al., 1982; Drummond and Ohmoto, 1985;
Diamond, 1990). Open boiling is synonymous with perfect fractional, or
Rayleigh distillation. As for the sulfur isotope system, this process
subordinated to mass-dependent fractional distillation, the lighter 32S
will enter the vapor phase while the heavier 34S remains in the residual
fluids, resulting in an increase of δ34S value. But Mckibben and Eldridge
(1990) showed that the kinetic process always caused an increase in the
oxidation state of the residual fluid due to involving loss of aqueous H2
13
Journal of Geochemical Exploration 218 (2020) 106617
and H2S to the vapor phase. Accompanying with an increase in an
oxidation state of the residual fluid, preferential oxidation of 34S in H2S
(H234S + 4H2O = 34SO4−2 + 2H+ + 4H2) also occurred, such an
effect would result in a gradual decrease in the δ34S of the residual H2S,
so that δ34S of pyrite precipitated from the residual fluid will also de-
crease. Calculating through the model of Rayleigh distillation, removal
of H2S via oxidation to SO4−2 will yield residual aqueous H2S that is
depleted by 3 per mil at 10% removal, 9 per mil at 25% removal
(Mckibben and Eldridge, 1990). Even though these different sulfur
isotope fractional distillation factors (sulfides precipitation and increase
of fO2) have multiple and opposite effects on the δ34S of pyrite, the
increase of fO2 and preferential oxidation of H2S dominantly controlled
the variation of δ34S values of pyrite in the epithermal system (Ohmoto,
1972; Drummond and Ohmoto, 1985; Mckibben and Eldridge, 1990).
The tradeoff between different factors and immiscibility only occurred
in part samples of Muping gold deposit is responsible for the slightly
decreasing trend for sulfur isotope value from Py3a to Py3b, and it is
consistent with the presence of only minor amounts of barite but no
hematite, which suggested that the redox state of hydrothermal fluid
did not cross the boundary between magnetite and hematite (Fig. 14).
As for pyrite with core-rim texture (Py3b and Py3c), the sulfur
isotope values have a significant increase in δ34S from 6.0‰ to 11.8‰
from core and rim. The variation trend is interpreted as a result of a
process that the original magmatic-hydrothermal with light δ34S value
mixed with a heavy δ34S value meteoric water. Therefore, we suggest
that the variation of δ34S value which gradually increased from inner
rim (near the core) to outer rim (away from the core) recorded the
process that the proportion of meteoric water progressively increased in
the ore-forming fluids (Figs. 8e and 12b). The model of a fluid mixture
requires producing a continuum of δ34S value from the core to the rim
(Peterson and Mavrogenes, 2014), and the near linear trend of sulfur
isotope value in pyrite with core-rim texture consist with the various
Y.-W. Zhang, et al.
proportion mixture between two end-members of the sulfur isotope.
Sulfur isotope thermometry calculations for pyrite -galena or -sphalerite
yield anomalously low or high temperatures (Δpy3b-Gn = 4.7‰, Δpy3c-
Gn = 5.9‰, calculating temperatures approximately are 190 °C and
145 °C; Δpy3b-Sp = 0.6‰, Δpy3c-Sp = 1.5‰, calculating temperatures
approximately are 434 °C and 174 °C) (Ohmoto and Rye, 1979), even
the order of isotope enrichment reversed between part pyrites with
core-rim texture and sphalerites (Table 2), which all indicate a sulfur
isotope disequilibrium among these pairs of sulfide. Rapid cooling and
variable oxidation condition are the most possible reasons that caused
the sulfur isotopic disequilibrium in the Muping gold deposit, and co-
incidentally, the two geological effects all could be caused by fluid
mixture (Ohmoto and Rye, 1979; Rajabpour et al., 2017). The mixing
process also can be supported by the arsenic content variation between
Py3b and Py3c and it occurred in most of the gold deposits of Jiaodong
area according to HeO isotopes data (Hu, 2006; Zhu et al., 2015; Cai
et al., 2018). From the above discussion about sulfur isotope values
variation, we can conclude that although HS− is the dominate species
that forms complexation with gold in near-neutral and alkaline fluid
over a wide range of sulfur concentration and temperature (Pokrovski
et al., 2009; Williams-Jones et al., 2009), the value of δ34S∑ can re-
present the origin of hydrothermal fluid even the origin of gold, but the
sulfur isotope values of pyrite are not always equal to the value of δ34S∑
of hydrothermal fluids. Except for the source of sulfur, the physio-
chemical condition of fluids also has a significant effect on the sulfur
composition of pyrite.
7.3. Occurrence of gold and implications for precipitation mechanism
The occurrence of gold in different types of gold deposits existing
obvious distinction, the different occurrence of gold recorded the gold
saturation state in the hydrothermal fluid and subsequent dissolution-
reprecipitation or metamorphic recrystallization history (Chouinard
et al., 2005; Reich et al., 2005; Su et al., 2008; Cook et al., 2009; Hou
et al., 2016; Fougerouse et al., 2016a,b; Li et al., 2016). Parameters
controlling gold transportation and precipitation in hydrothermal fluid
include temperature, salinity, acidity, oxygen, and sulfur fugacities
(Pokrovski et al., 2014). In response, processes leading to a change in
these parameters are considered Au precipitation mechanisms, for in-
stance fluid-rock interaction, fluid immiscible, boiling and fluid mixture
or flash vaporization (Böhlke, 1989; Diamond, 1990; Fan et al., 2003;
Weatherley and Henley, 2013; Yang et al., 2016; Cai et al., 2018). All of
these processes would result in the instability of gold complexes. A
large number of studies show that Au (HS)− 2 is the dominant gold
14
Journal of Geochemical Exploration 218 (2020) 106617
Fig. 10. AueAs plot from Muping gold deposit data
according to Reich et al. (2005). The dashed line
represents the gold solid solution limit in arsenian
pyrite valid for As concentrations above 0.002 mol
%. All data below the dashed line indicating the in-
visible gold in the Muping gold deposit occurred as
solid solution gold in pyrite. Overall, the invisible
gold content is controlled by the arsenic content of
pyrite, the rim of core-rim textural pyrite dominated
the proportion of total invisible gold content in the
Muping gold deposit.
species in near-neutral and alkaline fluid over a wide range of sulfur
concentration and temperature (Pokrovski et al., 2009; Williams-Jones
et al., 2009), but gold has different occurrence in host minerals of
different type gold deposits, there are just some factors resulting in
these difference.
Mills et al. (2015a) proposed that invisible gold which formed in
syn-pyrite is the main occurrence in the Muping-Rushan gold belt. The
visible gold which formed in post-pyrite is most of the gold endowment
for the Zhaoyuan-Laizhou gold belt and was interpreted as re-
mobilization from earlier invisible gold in pyrite (Mills et al., 2015a).
However, extremely low invisible gold content in all types of pyrite
from the Xincheng gold deposit indicated that no significant component
of the gold ores can be formed by mobilization of gold out of previous
pyrites (Yang et al., 2016). This study on the Muping gold deposit is
also inconsistent with that of Mills et al. (2015a). The Muping deposit
has a bimodal distribution of gold in pyrite that is characteristic of an
orogenic gold deposit. Visible gold is dominantly hosted as inclusion or
in fractures in Py3 (Figs. 5h-i; 6h–i), part visible gold occurs as mineral
inclusion in Py2 (Fig. 5d) or chalcopyrite (Fig. 5h). From Py2 to Py3
(Py3a, Py3b, and Py3c), invisible gold mineralization always exists.
Py3c has the highest invisible gold content (the highest value is
136.31 ppm), and Py3a has relatively higher but inhomogeneous gold
content comparing to Py2 and Py3b (Fig. 9 and Table 1). Visible gold
from the orogenic gold deposit is interpreted as being remobilized from
previous gold-bearing pyrite during tectonic deformation, dissolution
or recrystallization of pyrite (Morey et al., 2008; Cook et al., 2009,
2013; Sung et al., 2009; Velasquez et al., 2014; Fougerouse et al.,
2016a). Gold remobilization from invisible gold of previous pyrites is
not likely for the Muping gold deposit, since extremely high arsenic
content pyrite (Py3c) which has enough invisible gold content is only
found in late mineralization stage when visible gold has precipitated or
was precipitating.
Previous research about visible gold precipitation mechanism in the
Jiaodong area was focused on geological processes such as fluid-rock
interaction, phase separation or fluid mixing (Fan et al., 2003; Hu et al.,
2007; Wen et al., 2015; Yang et al., 2016; Cai et al., 2018). Li et al.
(2013) studied hydrothermal alteration in the Sanshandao Au deposit
in order to define the physiochemical condition of ore fluid system.
Their results suggested that a decrease in fO2 was probably one of the
controlling factors for the precipitation of gold. But recent research
found that the fO2 could increase instead of decrease during the main
mineralization stage based on mineral assemblages and sulfur isotope
(Mills et al., 2015b; Yang et al., 2017; Cai et al., 2018). It is consistent
with the fact that the host rocks are main Mesozoic granitoids and
Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Fig. 11. Binary plots of (a) Au vs. Ag, (b) Au vs. Pb, (c) Au vs. Te, (d) Ag vs. Sb, (e) Ag vs. Pb, (f) Zn vs. Cu, (g) Ni vs. As, (h) Co vs. As, and (i) Bi vs. Pb, in different
pyrite types. All data above the minimum detection limit (mdl) are shown. Correlation coefficients for trace element pairs in the five pyrite types are shown (top left)
in each figure (part correlation coefficients didn't calculate due to lacking enough data or obvious correlation). The r1, r2, r3a, r3b and r3c are correlation coefficients
for py1, py2, py3a, py3b and py3c, respectively.

merely Precambrian metamorphic rocks, there is not enough reductant
such as organic-rich sediments in the Carlin-type gold deposit to de-
crease the redox state of ore fluid system (Su et al., 2009). Fluid in-
clusion research implied phase separation are common in the quartz-
vein style gold deposits at Jiaodong. Phase separation occurred at
Muping deposit (Hu et al., 2007; Xue et al., 2018) resulted in an in-
crease in fO2 and pH, then the redox state of ore fluid system changed
from buffering by pyrrhotite and pyrite to buffering by pyrite and
magnetite. The occurrence of barite implied that the sulfur species
evolved from H2S to SO42−. HS− is the main complex for gold, vapor
phase escaped and increase of fO2 during phase separation process
resulted in a dramatic decrease in the concentration of HS−, leading to
Au precipitation. Fig. 14 displays Au solubility contours suggesting that
oxidation is an excellent trigger for gold precipitation compared with
the reduction process (Roberts, 1987; Hodkiewicz et al., 2009;
Williams-Jones et al., 2009). Moreover, sulfides precipitation can fur-
ther reduce the HS− concentration and thus effect on gold solubility.
We can realize that lots of sulfide inclusions and sub-micro visible gold
precipitated when Py3b was forming. Accompanying visible gold mi-
neralization caused by phase separation, closely related elements such
as Ag, Sb, Te, Cu, Zn, and Pb simultaneously precipitated (Figs. 6f, 8b
and 13e).

15
Y.-W. Zhang, et al.
Fig. 12. The δ34S of different types of pyrite and coexisting sulfides analyzed by LA-MC-ICP-MS. b The δ34S of pyrite with core-rim texture analyzed by NanoSIMS.
Rim-1, rim-2 and rim-3 are different regions that represented the distances among rims and core becomes farther.
Gold and As data of all generation pyrites are below the maximum
gold solubility in arsenian pyrite (Fig. 10), which was used to infer gold
occurrence in pyrite and ore fluid whether or not saturated to native Au
(Reich et al., 2005). Accordingly, we suggest that invisible gold at
Muping occurs as a solid solution (Au+) in the pyrite lattice. This is also
confirmed by LA-ICPMS time-resolved spectra showing that the profile
of gold is flat basically without spikes caused by nanoparticles gold or
sub-micro gold inclusions (Fig. 13). But the Au3+ was not taken into
consideration because the known gold chemistry both in solid and so-
lution implies that the only stable Au oxidation state at hydrothermal
conditions is Au+, and Au3+ was incorporated into pyrite few has been
reported and there was no spectroscopic confirmation (Chouinard et al.,
2005; Deditius et al., 2014).
Zhu et al. (2015) pointed out gold deposits in the Jiaodong area is a
unique type of gold deposit, different from orogenic and Calin-types.
One of the major differences is that it contains much less arsenic than
the latter two types of gold deposit (Mills et al., 2015a; Yang et al.,
2016; Feng et al., 2018; Li et al., 2018). Different from previous re-
search results, excepting relatively low arsenic content in Py1, Py2,
Py3a, and Py3b, we found that Py3c has extremely high arsenic content
which can up to ~2 wt%. So many literature have discussed the cou-
pling of gold and arsenic in different types of gold deposits (Simon
et al., 1999; Reich et al., 2005; Morey et al., 2008; Cook et al., 2009,
2013; Deditius et al., 2014; Feng et al., 2018; Li et al., 2018). Au-
bearing fluids in the Carlin system were undersaturated concerning
native Au during precipitation of arsenic pyrite that was confirmed by
quantitative LA-ICP-MS analysis of fluid inclusion (Su et al., 2012;
Deditius et al., 2014). Au can be incorporated into pyrite via chemi-
sorption gold complexes, such as Au(HS)2−, on As-rich, Fe-depleted
active growth surface of arsenian pyrite or incorporated into vacancies,
defects and octahedral site of pyrite (Fleet and Mumin, 1997; Palenik
et al., 2004; Cepedal et al., 2008; Mikhlin et al., 2011). Arsenic in-
corporation will also change the semiconducting properties of pyrite (n-
type to p-type) and dissolution of arsenian pyrite resulted in pyrite
surface becoming locally reduced, these processes can facilitate Au
complexes incorporation and deposition (Möller and Kersten, 1994;
Pokrovski et al., 2002). Density functional (DFT) calculations of posi-
tion and correlation between Au and As in pyrite showed a decrease in
the formation energy of Au-bearing pyrite with an increase in As con-
centration (Chen et al., 2013). Above all factors are in favor of pyrite
absorbing invisible gold.
According to the above discussion, we can conclude that there are
two different gold occurrences in the Muping gold deposit. Invisible
gold mineralization always happened, and the invisible gold content in
pyrite was controlled by arsenic content in the hydrothermal fluid and
16
Journal of Geochemical Exploration 218 (2020) 106617
the process did not require gold saturation in the ore fluid. The pre-
cipitation mechanism is similar to the Carlin-type gold deposit, which
arsenic has crucial facilitation for gold was absorbing into pyrite.
Visible gold mineralization mainly was controlled by fO2 increase due
to phase separation. Through breaking the complex, the process caused
the solubility of gold to decrease and the saturation or supersaturation
for gold. The effect that amounts of sulfides precipitation and mixture
between magmatic-hydrothermal fluid and meteoric water on the so-
lubility also cannot be ignored. The surface of pyrite has amounts of
vacancies and defects due to incorporating much trace elements, it is
energetically easier for heterogeneous nucleation that gold precipitated
on the surface of arsenian pyrite, and the dissolution of arsenian pyrite
resulted in pyrite surface becoming locally reduced, which can facilitate
Au reduction and deposition (Pokrovski et al., 2002; Mills et al.,
2015a). Compared to invisible gold which formed syn-pyrite occurred
as solid solution or nanoparticles in the inner of arsenian pyrite, in
which gold incorporated and precipitated accompanying with the
growth of pyrite, visible gold which formed post-pyrite mainly de-
posited on the interface between pyrite and ore fluid, once gold nu-
cleated on the surface of the previous pyrite, new gold will tend to
precipitate on existing gold crystal nucleus which was not effectively
separated from ore fluid system. Thus, we presumed that invisible and
visible gold in the Muping gold deposit has a difference in the pre-
cipitation time, and the main precipitation process of visible gold
should occur after Py3a, but invisible gold deposition always occurred
although Py3c occupied the main portion.
Although recent researches proposed that the fluid of gold deposits
in Jiaodong area and Carlin-type gold in Nevada are derived from
magmatic-hydrothermal fluids that were associated with plate sub-
duction and decratonization (Richards, 2011; Zhu et al., 2015), there is
remarkable distinction on the gold occurrence and style of gold mi-
neralization between these two types of gold deposit. High arsenic
content and lacking dramatic change on physiochemical condition in
the ore fluid system resulted in gold precipitating at unsaturation or
nearly saturation in the Calin-type gold deposit, fluid-rock interaction
and facilitate incorporation by arsenic led to gold occurring as a solid
solution or nanoparticles in arsenian pyrite or arsenopyrite (Simon
et al., 1999; Reich et al., 2005; Su et al., 2008, 2012; Deditius et al.,
2014). In contrast, gold deposits at Jiaodong have relatively low arsenic
content and the ore bodies are controlled by fracture systems. In the
Muping gold deposit, dramatic changes in physiochemical conditions
caused by phase separation and/or fluid mixture resulted in gold so-
lubility steeply decreasing and becoming saturation or super-saturation,
arsenic can't efficiently scavenge dissolved gold complex thus occurred
visible gold mineralization.
Y.-W. Zhang, et al. Journal of Geochemical Exploration 218 (2020) 106617

Fig. 13. Representative LA-ICPMS time-resolved spectra for three pyrite types at Muping. (a) Py1; note the relatively high counts of Co and Ni, low counts of As, and
no counts of other metal elements including Au. (b) Py2; relatively high counts of As compared to Py1 and very low counts of Au and Bi. Note out of integration
interval, there are some Zn, Cu and Au signal spikes which might represent the micro-inclusions of Zn-Cu-Au compounds. (c–d) Py3a; note two figures all have high
counts of As, but the counts of Au are differently indicting the invisible gold contents in Py3a are inhomogeneous and the Py3a might suffer from invisible gold
remobilization process or arsenic-bearing fluid metasomatic process. (e) Py3b; The extremely high counts of Cu, Pb, Zn, Ag and Sb, relatively low counts of Au. Note
the profiles for Zn, Cu, Pb and Au unstable which represented the micro-inclusions or sub-micro-inclusions of sphalerite, chalcopyrite, galena and native gold
occurred. And the profiles for Ag and Sb are mostly parallel to the profile of Fe showed that these elements dominantly occurred as a solid solution. (d) Py3c; The
highest counts of As and Au compared to other types of pyrite, and the profiles for these elements are mostly parallel implied that Au occurred as a solid solution in
pyrite. The counts of other elements such as Cu, Zn, Ag, Sb, and Pb are relatively low or didn't exist.

8. Conclusion in the intercrystalline sulfur isotope variation of pyrite with core-rim

Three generations/types of pyrite have been identified in the
Muping gold deposit. The variations of the sulfur isotope of pyrite are
the result of multiple fluid pulses in an open system. Sulfur sources and
physiochemical conditions played a different role in determining sulfur
isotope value of pyrite. It is fluid mixing of hydrothermal fluid resulted
texture, and the fluid mixture process can also be perfectly reflected and
recorded by trace elements composition of the pyrite. The rim of pyrite
with core-rim texture has the highest invisible gold content with the
highest arsenic content, consisting of the dominated invisible gold mi-
neralization event in the Muping gold deposit. The invisible gold con-
tent in pyrite was controlled by arsenic content in the hydrothermal

17
Y.-W. Zhang, et al.
Fig. 14. The plot of oxygen fugacity (log fO2) against pH showing gold solu-
bility contours (0.01, 0.1, 1.0 and 10.0 ppm) for gold–bisulphide complexes,
modified from Roberts (1987). The solubility of gold increases with fO2 up to
the boundary between the fields of reduced and oxidized sulfur. At higher
oxygen fugacity, sulphate is the dominant species, and, with the decrease in the
activity of the reduced sulfur species, the solubility of gold decreases markedly
(see arrow). Therefore, oxidation of fluids is an efficient mechanism for the
precipitation of gold. Isotopic contours are drawn as H2S values. They were
drawn assuming mNa+ = 1, mK+ = 0.1 and mCa2+ = 0.01 and total
δ34S = 0‰ (Hodkiewicz et al., 2009).
fluid, but phase separation is the main mechanism resulting in visible
gold precipitation. Models for remobilization of invisible gold are not
applicable in the Muping gold deposit.
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.gexplo.2020.106617.
Declaration of competing interest
We declare that we have no financial and personal relationships
with other people or organizations that can inappropriately influence
our work, there is no professional or other personal interest of any
nature or kind in any product, service and/or company that could be
construed as influencing the position presented in, or the review of, the
manuscript entitled “Fluid evolution and gold precipitation in the
Muping gold deposit (Jiaodong, China): insights from in-situ trace ele-
ments and sulfur isotope of sulfides”.
Acknowledgments
Drs. Xin Yan, Qian Mao, Jianchao Zhang, Jialong Hao, and Kuidong
Zhao are thanked for their technical support in running the FSEM,
EPMA, NanoSIMS, and MC-LA-ICPMS, respectively. We thank
Shuguang Ren and Mingguang Lv for their helps in sampling. Dr.
Tingguang Lan is appreciated for his thoughtful comments and con-
structive suggestions. We are grateful to two anonymous reviewers for
their constructive feedback that helped to improve an earlier draft of
the manuscript, and associate editor Prof. Stefano Albanese for valuable
suggestions and efficient editorial handling. This study was financially
supported by the National Key Research and Development Program
(No. 2016YFC0600105) and National Natural Science Foundation of
China (41772080).
18
Journal of Geochemical Exploration 218 (2020) 106617
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