Contributions to Mineralogy and Petrology (2024) 179:7

https://doi.org/10.1007/s00410-023-02086-w

ORIGINAL PAPER

Implications for metallogenic evolution of the giant Zhenyuan

gold deposit (Yunnan, SW China) from textures and geochemical
compositions of pyrite
Huichao Zhang1,2 · Nigel J. Cook3 · Hongrui Zhang2 · Zengqian Hou2 · Peng Chai2 · Wei Li4 · Sarah Gilbert5

Received: 29 June 2023 / Accepted: 23 November 2023

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023

Abstract
Pyrite, the most common sulfide mineral, is a ubiquitous component of many hydrothermal gold deposits. Geochemical
patterns within the refractory pyrite structure represent a valuable repository of information that can help constrain the
sources of ore-forming materials, and the evolution of ore-forming processes over time. However, there are still a lot of
debates on the mechanisms of physico-chemical processes in ore-forming fluid controlling trace element and sulfur isotope
distributions in pyrite during growth. In our manuscript, we use cutting-edge complementary microanalytical methods to
understand the origin and evolution of zoned gold-bearing pyrite in samples from the largest gold deposit in the Ailaoshan
gold belt, SW China, Zhenyuan (exceeding 100t Au, average grade: 5.3 g/t). Pyrite, arsenopyrite, chalcopyrite, and stibnite
are the most abundant sulfide minerals in most orebodies. Of these, pyrite is dominant and is also the most important host for
gold. Two types of pyrite can be clearly distinguished: framboidal pyrite and hydrothermal pyrite. Gold is most commonly
hosted by hydrothermal pyrite. Framboidal pyrite, mainly hosted by carbonaceous slate, hosts negligible Au, and features low
δ34S values ranging from − 35.0 (± 0.9) to − 25.6 (± 1.0)‰. Hydrothermal pyrite is characterized by complex intra-grain
zoned textures with alternating As-rich and As-poor bands readily recognizable on backscattered electron images. Scanning
electron microscopy and trace-element analyses show that both visible and invisible gold occur only in the As-rich bands.
Compared to the As-poor bands (72.1% of Au concentration data < 1.96 ppm, n = 43), the As-rich bands are characterized
by far higher concentrations of Au (up to 1420 ppm), Cu, Ag, Sb, and Tl, but lower concentrations of Co and Ni. In-situ
sulfur isotope analysis indicates that the δ34S values of As-rich zones range from − 7.3 (± 0.6) to 2.9 (± 0.6)‰ and are
similar to those of As-poor zones (from − 6.9 (± 0.7) to 2.8 (± 0.6)‰), but distinct from the framboidal pyrite. Combined
with published fluid inclusion data and a probable age for the magmatic event associated with mineralization, these data
suggest that magmatic–hydrothermal fluids contributed most ore-forming materials and that periodic boiling led to formation
of the rhythmic As-rich and As-poor bands in pyrite. Our data for pyrite constrain the evolution of ore-forming processes
and provide new insights into the formation of zoned pyrite, with the conclusions having broad implications for analogous
hydrothermal gold deposits worldwide.

Keywords Pyrite · Compositional zoning · Trace-element concentrations · NanoSIMS in-situ sulfur isotopes · Ailaoshan
gold belt

Communicated by Daniela Rubatto.

3
* Hongrui Zhang School of Chemical Engineering, The University
[email protected] of Adelaide, Adelaide, SA 5005, Australia
4
* Zengqian Hou China University of Geosciences, Beijing 100083, China
[email protected] 5
Adelaide Microscopy, The University of Adelaide, Adelaide,
1 SA 5005, Australia
Institute of Marine Geology, College of Oceanography,
Hohai University, Nanjing 210098, China
2
Institute of Geology, Chinese Academy of Geological
Sciences, Beijing 100037, China

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 7 Page 2 of 22 Contributions to Mineralogy and Petrology (2024) 179:7

Introduction 2019a, b; Wang et al. 2020). In the Zhenyuan gold deposit,

hydrothermal pyrites generally show alternating As-rich
Pyrite is a major component of many hydrothermal gold and As-poor zones, which have distinct textural and
deposits and can be a significant host for gold (Maddox compositional characteristics. Zhenyuan pyrite, therefore,
et al. 1998; Williams-Jones et al. 2009; Velásquez et al. represents an exemplary study case to relate the textural
2014; Zhang et al. 2022; Zheng et al. 2022). Previous and compositional record with evolution in physico-
studies suggest that textural relationships, compositions, chemical conditions, ongoing magmatism, faulting, and
and isotopic characteristics of pyrite can provide critical other geological processes.
information on the sources of ore-forming materials In this study, we have addressed the complexity and
and track the compositional evolution of hydrothermal evolution of the pyrite from Zhenyuan in a systematic
systems (Large et al. 2009; Deditius et al. 2014; Tanner investigation of micro-to-nanoscale textures, coupled
et al. 2016; Zhang and Zhu 2016, 2017; LaFlamme et al. with in-situ determination of major, trace element, and
2018a; Li et al. 2020a). Several recent publications sulfur isotopic characteristics. This major deposit, with its
have emphasized that changes in texture, trace-element spectacularly zoned pyrite represents an ideal case to test
endowment, and sulfur isotopic composition of pyrite and refine hypotheses regarding formation of zoned pyrite,
reflect variation of physico-chemical conditions (such with implications for analogous hydrothermal gold deposits
as temperature, pressure, and pH) of ore-forming fluids worldwide.
(Tardani et al. 2017; Li et al. 2021a; Sugiono et al. 2022).
The ratios among certain trace elements and the sulfur Regional and deposit geology
isotope signatures of pyrite have been proposed as tools to
discriminate the evolution of physico-chemical conditions The Ailaoshan tectonic belt, located within the southeastern
(Román et al. 2019; Keith et al. 2022). Nevertheless, the part of the Sanjiang Tethyan Orogen, tectonically connects
mechanisms by which physico-chemical processes control the Yangtze–South China block to the east and the Indochina
trace element and sulfur isotope distributions in pyrite block to the west (Fig. 1a, b; Hou et al. 2007; Deng et al.
during growth, and how these phenomena are preserved 2010; Liu et al. 2015; Wang et al. 2016; Xiao et al. 2017; Xu
in an evolving system, require additional research. et al. 2021). It comprises several regional fault zones, from
Individual pyrite crystals can contain a range of different northeast to southwest, these are the Red River fault, Aila-
texture and compositions, expressed as zoned textures. oshan fault, and Jiujia–Anding fault. All three strike nearly
These pyrites are thus ideal materials to link chemistry NW and dip to NE at 60–80°. The Ailaoshan tectonic belt
and preserved textures to physico-chemical conditions is divided by the Ailaoshan fault into the Proterozoic Aila-
and f luid processes. Each pyrite grain with zoned oshan Group in the east, and the Paleozoic–Mesozoic unit
texture represents a time-resolved record of the complex in the west (Fig. 1b). The Ailaoshan Group mostly consists
processes during precipitation and growth (e.g.,Cook et al. of lower amphibolite to granulite facies metamorphic rocks,
2009; Reich et al. 2013). Many mechanisms have been and the Paleozoic–Mesozoic unit is composed of rocks that
suggested to explain the origin of zoned pyrite, including have undergone regional metamorphism only up to green-
kinetic effects during crystallization, such as growth schist facies (Liu et al. 2015). The Ailaoshan suture zone,
rate and diffusion-limited self-organization processes, located between the high-grade metamorphosed unit and the
and changes in fluid chemical composition caused by low metamorphosed grade unit, formed via Late Permian
fluid–rock reactions, mixing, and boiling (Deditius et al. closure of the Ailaoshan branch of Paleo-Tethyan Ocean
2009; Fougerouse et al. 2016; Tardani et al. 2017; Li et al. (Zhong 1998; Deng et al. 2015).
2018; Wu et al. 2019). These mechanisms are recorded Cenozoic high-potassium alkaline rocks with ages
and readily identified by textures, patterns of trace-element ranging between 41 and 32 Ma, and 28–23 Ma calc–alkaline
distribution, and by measurable variation in isotope magmatic rocks outcrop widely across the Ailaoshan
compositions across discrete zones (Román et al. 2019). tectonic belt (Liang et al. 2007; Liu et al. 2015). Cenozoic
The Ailaoshan gold belt is the most economically lamprophyres with phlogopite Ar–Ar ages of 29.6–36.8 Ma,
important part of the Sanjiang Tethyan metallogenic should also be noted (Chen et al. 2014). In addition, Late
domain (Hou et al. 2007; Zhang and Hou 2015). It hosts Proterozoic and Late Permian–Triassic magmatic rocks have
four large gold deposits, among which Zhenyuan is the been reported in this belt (Qi et al. 2010; Zhang et al. 2011;
largest (Zhang et al. 2014a; Deng et al. 2015; Wang et al. Wang et al. 2012, 2020; Liu et al. 2013, 2014).
2016). Previous research indicates that both magmatism The Ailaoshan gold belt is the region between the
and faulting leading to shearing operated during periods of Jiujia–Anding and Ailaoshan faults, and consists of
mineralization (Zhang et al. 2012; Liu et al. 2015; Li et al. unmetamorphosed or up to greenschist facies metamorphic
Paleozoic–Mesozoic units. The belt hosts numerous gold
Contributions to Mineralogy and Petrology (2024) 179:7 Page 3 of 22 7

Fig. 1  a Simplified geological map showing the Indian–Eurasian collision zone. b Tectonic map of the Ailaoshan gold belt, SW China. Loca-
tions of the Cenozoic gold deposits are indicated. Modified from Deng et al. (2015) and Liu et al. (2015)

deposits, including Zhenyuan (> 100 t Au), Mojiang rocks (Li et al. 2013a). Lamprophyre dikes with phlogopite
40
(> 30 t Au), Chang’an (> 30 t Au), and Daping (> 60 t Au) Ar–39Ar ages of 34–31 Ma are also widely exposed in the
(Ge et al. 2007; Sun et al. 2009; Yang et al. 2010, 2021; Laowangzhai and Donggualin mines (Wang et al. 2001; Gan
Deng et al. 2010; Li et al. 2019a). Zhenyuan, in the northern and Huang 2017).
part of the belt, is by far the largest deposit among these, The Laowangzhai orefield is controlled by NW and NE-
with a current resource (measured and indicated) exceeding striking faults. The main orebody clusters seen in the Laow-
100 t Au at an average grade of 5.3 g/t (Shi et al. 2012; angzhai mine (labeled as III, IV, and V on Supplemental Fig.
Li et al. 2020b; Wang et al. 2022). The two largest deposit S1) are strictly controlled by the F14, F19, and F7 faults,
orebody clusters making up the deposit are Laowangzhai respectively (Zhang et al. 2012). In the open pit of Laow-
(4.16 Mt @ 5.29 g/t Au) and Donggualin (8.82 Mt @ angzhai mine (orebody cluster V), the main exposed rocks
5.10 g/t Au) (Supplemental Fig. S1; Yang et al. 2010). are Early Carboniferous carbonaceous slate and quartz sand-
The strata exposed in the Zhenyuan deposit are mostly the stone, which are intruded by Late Permian quartz porphyry
Upper Devonian Kudumu, Lower Carboniferous Suoshan, and Eocene lamprophyre (Fig. 2a). Orebodies are generally
and Upper Triassic Yiwanshui Formations (Supplemental located at the contacts between quartz porphyry, carbona-
Fig. S1). Ultramafic–mafic rocks, in faulted contact with ceous slate, and quartz sandstone (Fig. 2a–d). Representa-
the aforementioned metasedimentary rocks, include olivine tive ore samples from the open pit and underground mining
pyroxenite, harzburgite, and basalt (Ren et al. 1995). Late areas of orebodies III, IV, and V were investigated (see sam-
Permian felsic intrusions (zircon U–Pb ages 255–247 Ma) ple locations and types in Supplemental Figs. S2a and S3).
intrude both the metasedimentary units and ultramafic–mafic These samples cover mineralized quartz porphyry (Fig. 2c),
 7 Page 4 of 22 Contributions to Mineralogy and Petrology (2024) 179:7

Fig. 2  Occurrence of orebodies and ore samples in the Zhenyuan between the quartz sandstone and carbonaceous slate; e samples from
gold deposit. a Open pit mining area in Laowangzhai mine with the orebody hosted by quartz porphyry in Donggualin mine; f quartz
orebodies located between the quartz porphyry and carbonaceous porphyry ores with disseminated pyrites; g lamprophyre-hosted ores
slate; b, c pyrite generally occurs in the contact zone between the with disseminated pyrites
quartz porphyry and carbonaceous slate; d pyrite in the contact zone

carbonaceous slate, and quartz sandstone (Fig. 2d), and con- Analytical methods
tain disseminated pyrite and minor quartz–pyrite veinlets
(Supplemental Fig. S3). Three main orebody clusters (SI, Ore textures, pyrite major and trace element, and sulfur
SII, SIII) are identified in the Donggualin mine (Supple- isotope compositions were analyzed in this study. The
mental Fig. S1), in which NW-striking faults control the scanning electron microscope (SEM) used (FEI Quanta
distribution and occurrence of orebody clusters. Ores hosted 650 FEG, Peking University) is equipped with an energy-
by quartz porphyry (1543 m level, Fig. 2e, f), lamprophyre dispersive spectrometer (EDS), allowing backscattered
(1563 m level, Fig. 2g), and carbonaceous slate (1753 m and electron (BSE) imaging of mineral morphologies and
1673 m level) from orebody SI, SII, and SIII were sampled qualitative compositional data.
(see sample locations and types in Supplemental Figs. S2b To investigate the physical form of gold in Au-rich
and S4). These ores all contain abundant finely disseminated pyrite, solid solution or nanoparticles, transmission electron
pyrite. microscopy (TEM) analysis was conducted. Fragments from
As- and Au-rich pyrite for TEM analysis were extracted
Contributions to Mineralogy and Petrology (2024) 179:7 Page 5 of 22 7

in-situ using the focused ion beam (FIB) technique at the grain. 115In was corrected for isobaric interference from
115
Institute of Geology and Geophysics, Chinese Academy of Sn using the measured 118Sn and assuming natural
Sciences (IGG–CAS). The FIB cutting was conducted with a isotopic abundance. Minimum detection limits depend
Zeiss Auriga Compact dual beam instrument equipped with on spot size, which governs ablated mineral volume.
an Omniprobe AutoProbe 200 micromanipulator. Ion beam Average minimum detection limits for trace elements in
conditions for the final thinning and polishing were 5–30 kV pyrite (in ppm) are Co (0.28 ± 0.17), Ni (1.43 ± 0.82),
with beam currents of 50 pA to 2 nA. The FIB section Cu (5.76 ± 3.84), As (11.83 ± 5.82), Ag (1.33 ± 0.72),
was thinned to ~ 100 nm. Bright-field (BF) imaging was Sb (0.43 ± 0.22), Au (0.31 ± 0.62), Tl (0.11 ± 0.05),
performed using a JEOL JEM-2100 microscope operated at Pb (0.61 ± 0.49), and Bi (0.15 ± 0.07) (Supplemental
200 kV, and with the electron beam generated from a LaB6 Table S2).
gun. Chemical compositions were acquired using the built-in LA–ICP–MS mapping of pyrite was conducted by
Oxford X-max 80 energy-dispersive X-ray spectrometer ablating sets of parallel lines scanned across an area of the
(EDXS). Details of TEM methodologies are given by Tang sample using beam sizes ranging from 8 to 15 μm depending
et al. (2023). on grain size, at a laser frequency of 10 Hz. The speed of the
Quantitative compositional data (Supplemental line scans was the same as the spot size used (e.g., 8 µm/s
Table S1) were obtained using a JEOL JXA-8230 electron for an 8 µm beam size). Re-deposition during mapping was
probe microanalyser (EPMA) at the Chinese Academy of minimized by pre-ablating each line prior to data collection.
Geological Sciences, Beijing. Elements and X-ray lines Identical raster lines were made on the MASS-1 reference
used were Fe (Kα), As (Lα), S (Kα), Pb (Mα), Ni (Kα), Ag material at the start and end of each mapping run to correct
(Lα), Cu (Kα), Zn (Kα), Co (Kα), Sb (Lα), and Au (Lα). For for instrument drift. All data reduction was performed using
sulfide minerals, operating conditions were an accelerating Iolite, an open-source software package for processing
voltage of 20 kV, beam current of 10 nA, and an electron ICP–MS data, as an add-in for the data analysis program
beam approximately 1 μm in diameter. Count times were Igor developed by WaveMetrics (Paton et al. 2011).
10 s on peak, 5 s on low background position and 5 s on high Sulfur isotope analysis of pyrite was performed using
background position for each element. Natural and synthetic a Cameca nanoscale secondary ion mass spectrometry
mineral standards of chalcopyrite, pyrite, sphalerite, galena, (NanoSIMS) 50L at IGG–CAS. Samples were polished
CoNiAs, and native silver, antimony and gold were used and carbon-coated for conductivity at high voltage. A ­Cs+
for calibration. The ZAF correction method, consisting beam current of ~7–10 pA with a diameter of 250 nm was
of atomic number correction (Z), absorption correction rastered across the sample surface. Before image acquisition,
(A), and fluorescence correction (F), was applied for the selected area was sputtered with a high intensity beam
standardization. Average minimum detection limits (mdl) of 1 nA for 2 min to remove the coating and to implant
of elements in sulfide minerals are as follows (in ppm): Fe enough ­Cs+ into the sample surface to stabilize the yield of
(176), As (232), S (71), Ni (152), Co (153), Pb (413), Sb the secondary ions. Areas 2×2 μm in size were selected for
(131), Zn (184), Cu (160), Ag (119), and Au (146). spot analyses of the 34S/32S ratio each time with an electron
Each sample for trace element analysis and element multiplier for the 34S− signal and a Faraday cup for the 32S−.
mapping of sulfide minerals was prepared as a 1-inch- The standard material (PY-1117) was used to correct for
diameter polished block. These polished blocks were instrumental mass fractionation. The reproducibility of δ34S
analyzed using a 213 nm, Q-switched, Nd: YAG NWR213 measurements on the PY-1117 pyrite is 0.55‰ during the
laser ablation system (Elemental Lasers), coupled to an analytical session (Supplemental Table S3). The uncertainty
Agilent 7900 Quadrupole ICP–MS instrument (Adelaide on single spot analyses (­ SEsample) were estimated by the
Microscopy, University of Adelaide, Australia). following formula
√ (Hao et al. 2023):
LA–ICP–MS analysis of pyrite was performed in spot SEsample = SESpot 2 + SDstandard 2 + SDref . 2
mode using a laser beam diameter of 10 to 25 μm, a SE sample is estimated as the square sum of the
repetition rate of 5 Hz, and laser energy of 4.0 to 5.5 J/ reproducibility of δ 34 S measurements on t he
cm 2. Total acquisition time for each analysis was 70 s corresponding pyrite standard of PY-1117 (­ SD standard),
(30 s background measurement followed by 40 s of sample the internal precision of each spot on the sample (­ SEspot)
ablation). Calibration for LA–ICP–MS spot analysis was and the uncertainty of the reference values of the PY-1117
performed using USGS sulfide reference material MASS-1 standard ­(SDref.), which are determined by stable isotope
(Wilson et al. 2002). Monitored isotopes included 34S, mass spectrometry with δ34SV-CDT value of 0.3 ± 0.1‰,
55
Mn, 57Fe, 59Co, 60Ni, 63Cu, 66Zn, 69 Ga, 75As, 77Se, 95Mo, which can be found in Zhang et al. (2014b) and Hao et al.
107
Ag, 111Cd, 115In, 118Sn, 121Sb, 125Te, 197Au, 201Hg, 205Tl, (2023). Detailed analytical conditions are identical to
208
Pb, and 209Bi. 57Fe served for internal calibration, using those described by Zhang et al. (2014b).
measured wt.% data from EPMA of the same or similar
 7 Page 6 of 22 Contributions to Mineralogy and Petrology (2024) 179:7

Results (Fig. 4i). Disseminated sulfide minerals and quartz–pyrite

veinlets are crosscut by later calcite–quartz–stibnite–pyrite
Textural characterization of pyrite veinlets, in which pyrite shows no zoned texture and no
micro-inclusions of gold were observed.
Orebodies with different host rocks from the Laowang-
zhai and Donggualin mines all share similar sulfide assem-
blages that include pyrite, arsenopyrite, chalcopyrite, and Pyrite major and trace‑element composition
stibnite. Pyrite, the most abundant sulfide, can be broadly
subdivided into framboidal pyrite and hydrothermal pyrite. Major element compositional datasets for pyrite
Framboidal pyrite occurs only in the carboniferous slate, (Supplemental Table S1) reveal that framboidal pyrite
where it displays a texture of microscopic spheroidal to from the carboniferous slate is generally poor in As (< 0.11
sub-spheroidal pyrite clusters ranging from 5 to 60 μm in wt.%), Ni (< 0.07 wt.%), and Co (0.07–0.13 wt.%). No other
size. Framboidal pyrite is preferentially concentrated in trace or minor components are present at concentrations
black bands where it coexists with irregular carbonaceous measurable by EPMA. Trace-element concentration data
material oriented nearly parallel to bedding (Fig. 3a, b). for framboidal pyrite were obtained by LA–ICP–MS.
Framboidal pyrite may also occur as inclusions within Time-resolved LA–ICP–MS depth profiles were checked
carbonaceous material (Fig. 3c, d). Spheroidal fram- and display reasonably smooth signals across the integrated
boids commonly consist of cubic microcrystals of pyrite count range for most elements (Supplemental Fig. S5).
cemented by later pyrite (Fig. 3e, f). Hydrothermal pyrite All depth profiles with obvious peak signals indicative of
commonly encloses framboidal pyrite, inferring formation inclusions were not processed further. Trace-element data for
of framboidal pyrite prior to hydrothermal activity. framboidal pyrite are summarized in Supplemental Table S2.
Hydrothermal pyrite in ores, including disseminated Framboidal pyrite from carboniferous slate contains
sulfide minerals and quartz–pyrite veinlets, hosted by limited concentrations of Co (Median value 28.7 ppm), Ni
different host rocks from Laowangzhai and Donggualin (171 ppm), Ag (5.15 ppm), Cu (46.4 ppm), As (174 ppm),
mines, commonly displays euhedral to subhedral mor- Sb (27.0 ppm), Tl (0.28 ppm), Pb (85.6 ppm), and Bi
phology, and diameters ranging from 50 to 400 μm. It (0.62 ppm). Concentrations of Au are generally < mdl.
generally shows complex internal structure, with a yellow Most hydrothermal pyrite grains in ores from the Laow-
core in reflected light enclosed by a recognizably pink angzhai and Donggualin mines hosted by different types
overgrowth. This overgrowth is, in turn, surrounded by a of wall-rocks share similar compositional characteristics.
further yellow overgrowth, and finally rimmed by an idi- The As contents of hydrothermal pyrite with zoned textures
omorphic pink overgrowth (Fig. 4a). These intricate zoned vary significantly, consistent with the different colors vis-
textures can be clearly recognized as alternating dark and ible under the microscope and strong brightness variation on
bright zones on BSE images (Fig. 4b). The dark zone cor- BSE images (Fig. 4a, b). EPMA data indicate pyrite cores
responds to As-poor pyrite, whereas the bright zone is are commonly As-poor (< 1.56 wt.%), whereas the over-
As-rich. The As-poor zone is usually corroded by the As- growths contain far higher As (7.61 to 14.63 wt.%; Fig. 5a,
rich overgrowth (Fig. 4b, c, f). Arsenopyrite, mostly rep- b; Supplemental Table S1). A zone between the As-rich and
resented by euhedral to subhedral crystals, only occurs as As-poor zones contains intermediate As contents (1.95 to
inclusions within As-rich pyrite (Fig. 4b, c), but may also 6.38 wt.%; Fig. 5b-–d; Supplemental Table S1). The nega-
form an overgrowth on the whole pyrite (Fig. 4d). Occa- tive correlation between As and S (Fig. 5c) suggests that As
sionally, pyrite is overgrown by arsenopyrite, which is, in is likely incorporated by substitution for S (Palenik et al.
turn, surrounded by another pyrite overgrowth (Fig. 4e). 2004; Deditius et al. 2008). Substitution of S by As can also
Similarly, stibnite and chalcostibite only occur as inclu- be verified by EDS mapping, which shows the bright zone in
sions in As-rich zones of pyrite (Fig. 4c, g). Relative to BSE images is rich in As and relatively poor in S (Fig. 6a–c).
the As-rich zone, the As-poor zone of pyrite contains Arsenic-poor and As-rich zones both contain measurable Co
more inclusions of quartz and monazite (Fig. 4f). Previous and Ni, but the As-poor zone contains more Co and Ni than
research at Zhenyuan did not observe much native gold, the As-rich zone (Fig. 5d). In contrast, the Fe contents of
leading researchers to consider that most Au was invisible the two zones are similar (Fig. 6d), suggesting that Fe does
or refractory in nature. Our higher magnification imaging, not participate in the substitution. To better understand the
however, enabled identification of sub-micron grains of occurrence of Au, a fragment of an As-rich zone in pyrite
native gold within the As-rich zone of pyrite (Fig. 4h). It was extracted for TEM analysis using the FIB extraction-
is noteworthy that several disseminated pyrite grains are lifting technique (Fig. 6a, e). TEM imaging revealed sev-
surrounded by pressure shadows filled with oriented quartz eral nanoscale grains of chalcopyrite and stibnite within the
Contributions to Mineralogy and Petrology (2024) 179:7 Page 7 of 22 7

Fig. 3  Photomicrographs of framboidal pyrites from carbonaceous sions; e, f framboidal pyrite commonly consists of microcrystals of
slate. a, b Framboidal pyrite is preferentially concentrated in black pyrite, which were cemented by later pyrites. Mineral abbreviations:
bands; c framboidal pyrite coexists with irregular carbonaceous mate- CM carbonaceous material, Py pyrite
rial; d framboidal pyrites occur in the carbonaceous material as inclu-
 7 Page 8 of 22 Contributions to Mineralogy and Petrology (2024) 179:7

Fig. 4  Photomicrographs of hydrothermal pyrites with zoned texture. phyre (BSE); g chalcostibite also only occurs in the As-rich zone of
a Pyrite displays complex internal texture and is enclosed by arseno- pyrite hosted by lamprophyre (BSE); h sub-micron grains of native
pyrite (reflected light); b alternating As-rich and As-poor bands in gold within the As-rich zone of pyrite (BSE); i pyrite grain sur-
pyrite hosted by quartz porphyry (BSE); c arsenopyrite and stibnite rounded by pressure shadows filled with oriented quartz. Mineral
only occur in the As-rich zone of pyrite (BSE); d pyrite with zoned abbreviations: As-Py As-rich pyrite, Apy arsenopyrite, Au native gold,
texture enclosed by arsenopyrite (BSE); e As-rich zones of pyrite Cct chalcostibite, Mon monazite, Py pyrite, Qz quartz, Stb stibnite
coexist with arsenopyrite (BSE); f zoned pyrite hosted by lampro-

bright zone, but no nanoscale grains of native gold or other In addition, Ni distributions commonly resemble those of
Au-bearing phases could be identified (Fig. 6f, g). Co and that these two elements are concentrated in As-
LA–ICP–MS trace-element mapping was conducted on poor zones (Fig. 7h, i). Several pyrite grains show dark
zoned hydrothermal pyrite. Results reveal that the As-rich As-poor cores, bright As-rich mantles, and dark As-poor
and As-poor zones in pyrite contain distinct trace-element rims on BSE images (Fig. 8a). In the center of an As-poor
contents (Fig. 7; Supplemental Fig. S6). In general, the core, an area is replaced by later fluid along the fracture
inner and outermost As-rich zones are the richest in both (Fig. 8a); therefore, the composition of this area cannot
Au and Cu (Fig. 7b–d). Antimony, Tl, and Ag are prefer- represent the composition of As-poor core. Apart from
entially enriched at the outermost As-rich zones, whereas this area, our mapping shows that the As-rich mantles are
the inner As-rich zones contain these elements at concen- commonly enriched in Cu, Au, Ag, Sb, and Tl relative to
trations comparable with the As-poor zones (Fig. 7e, g). the cores (Fig. 8b–g). These As-rich mantles can be further
Contributions to Mineralogy and Petrology (2024) 179:7 Page 9 of 22 7

Fig. 5  Chemical compositions of representative framboidal and ing zones (Donggualin mine, BSE); c As vs. S variation in framboi-
hydrothermal pyrite (EPMA data). a Hydrothermal pyrite and arse- dal and hydrothermal pyrite; d As vs. Co + Ni variation in framboidal
nopyrite with As contents on corresponding zones (Laowangzhai and hydrothermal pyrite. Mineral abbreviations: Apy arsenopyrite, Py
mine, BSE); b hydrothermal pyrite with As contents on correspond- pyrite

divided into two parts: an inner mantle and an outer man- and As-rich zones of pyrite have distinctly different trace-
tle, separated from one another by a thin As-poor band element concentrations (Fig. 9).
(Fig. 8a). Arsenopyrite only occurs in the As-rich outer Arsenic-poor zones (< 15,000 ppm) contain only a
mantle, which has higher As concentrations than the inner small amount of Au with most data < 1.96 ppm (72.1%,
mantle (Fig. 8a). In contrast, Co and Ni display marked n = 43), whereas Au concentrations can attain up to as
enrichment in the As-poor core, whereas the mantles con- much as 1420 ppm in the As-rich zones and most data
tain almost no Co or Ni (Fig. 8h, i). are > 1.91 ppm (65.0%, n = 80) (Fig. 9a; Supplemental
Quantitative trace-element concentration data for Table S2). Copper concentrations in As-rich zones range
hydrothermal pyrite were obtained by LA–ICP–MS in over several orders of magnitude from < mdl to 2080 ppm
spot analysis mode. Trace-element data are summarized in with most values > 100 ppm (78.8%, n = 80), but the As-poor
Supplemental Table S2. As a whole, hydrothermal pyrite zones of pyrites usually contain lesser Cu with most
from ores hosted by quartz porphyry, lamprophyre, quartz values < 100 ppm (74.4%, n = 43; Fig. 9b; Supplemental
sandstone, and carbonaceous slate, all have similar trace- Table S2). Silver concentrations can reach up to as much
element concentrations including Au. Our spot analyses as 46.1 ppm with most values > 1 ppm (57.5%, n = 80) in
verify the results from mapping that the As-poor zones As-rich zones (Supplemental Table S2), whereas the Ag
 7 Page 10 of 22 Contributions to Mineralogy and Petrology (2024) 179:7

Fig. 6  EDS maps and TEM photomicrographs of hydrothermal bright zone using FIB technique for TEM analysis, bright-field
pyrite. a Hydrothermal pyrite with zoned texture, BSE; b, c bright image; f, g sub-micron chalcopyrite and stibnite grains were identi-
zone is richer in As and poorer in S than the dark zone; d iron is fied under the TEM, bright-field image. Mineral abbreviations: Py
evenly distributed across both zones; e Sample extracted from the pyrite, Ccp chalcopyrite, Stb stibnite

concentrations in As-poor zones are commonly < 1 ppm Laowangzhai mine are slightly higher than those from
(62.8%, n = 43). Concentrations of Tl and Sb generally Donggualin mine. The δ 34S values of As-poor pyrite
display a positive correlation with As (Fig. 9c). The Tl zones from Donggualin mine have a range from − 6.9
and Sb concentrations in As-rich zones range from 0.14 (± 0.7) to 2.8 (± 0.6)‰ (n = 21), and the δ 34S values of
to 39.0 ppm (n = 80) and from 13.5 to 1900 ppm (n = 80), As-rich zones are − 7.3 (± 0.6) to 2.0 (± 0.6) ‰ (n = 15)
respectively (Fig. 9c, Supplemental Fig. S6g; Supplemental (Figs. 10, 11a–d). The δ34S values of As-poor pyrite zones
Table S2). However, the Tl and Sb concentrations in As-poor from Laowangzhai mine are − 3.6 (± 0.6) to 2.6 (± 0.6)‰
zones range from < mdl to 7.05 ppm (n = 43) and from 0.45 (n = 12), and the δ34S values of As-rich zones range from
to 397 ppm (n = 43), respectively. A similar relationship is − 3.6 (± 0.6) to 2.9 (± 0.6)‰ (n = 11; Figs. 10, 11e–f).
observed between Co and Ni (Fig. 9d). Like the mapping, The sulfur isotopic compositions of framboidal pyrite
trace-element spot analysis shows that Co and Ni have from carboniferous slate are marked by extremely low δ34S
distribution trends that are distinct from other elements. values ranging from − 35.0 (± 0.9) to − 25.6 (± 1.0)‰
Cobalt concentrations in the As-poor zones of pyrite (n = 6, Fig. 10). The carboniferous slate also contains
range from < mdl to 1940 ppm with most data > 116 ppm several hydrothermal pyrite grains, which show a restricted
(55.8%, n = 43) and Ni concentrations range from < mdl to range of δ34S values from − 1.5 (± 0.7) to 3.9 (± 0.7)‰
2850 ppm with most data > 108 ppm (70.0%, n = 43). The (Fig. 10). These hydrothermal pyrite grains commonly
Co and Ni concentrations in As-rich zones vary from < mdl enclose framboidal pyrite, with irregular boundaries
to 1940 ppm (with most data < 116 ppm, 88.8%, n = 80) and between the two types (Supplemental Fig. S7a, b),
from < mdl to 1460 ppm (with most data < 108 ppm, 66.2%, suggestive of replacement of framboids by hydrothermal
n = 80), respectively (Supplemental Table S2). In general, pyrite. The pyrite grains, located between the framboidal
the As-rich zones of hydrothermal pyrite appear relatively pyrite and hydrothermal pyrite (Supplemental Fig. S7c–f),
enriched in Au, Cu, Ag, Sb, and Tl, whereas Co and Ni are yield δ 34S values ranging from − 13.4 (± 0.6) to − 9.7
preferentially concentrated in the As-poor zones. (± 0.6) ‰ (Fig. 10; Supplemental Fig. S7e), midway
between the δ 34 S values of adjacent framboidal and
Sulfur isotope analysis hydrothermal pyrite (Fig. 10; Supplemental Fig. S7d, f).

In-situ NanoSIMS sulfur isotope data for pyrite are tab-

ulated in Supplemental Table S3 and plotted in Fig. 10.
In general, δ 34 S values for hydrothermal pyrite from
Contributions to Mineralogy and Petrology (2024) 179:7 Page 11 of 22 7

Fig. 7  LA–ICP–MS element maps of a representative pyrite grain with zoned texture from Laowangzhai mine. Scales in ppm

Discussion solubility saturation line for Au on a plot of Au vs. As (Reich

et al. 2005). Conventionally, this was considered to infer
Occurrence of gold that invisible Au occurs structurally bound rather than as
nanoparticles, even if recent evidence (Ehrig et al. 2023)
Although previous research pointed to invisible Au as the suggests this need not always be the case. Such a conclusion
main form of Au in the Zhenyuan deposit and implied this is consistent with the fact that no native gold nanoparticles
must be in solid solution within sulfide minerals (Li et al. were observed during TEM imaging of As-rich pyrite.
2019a, b), we have observed very fine-grained (~ 1 μm) EPMA data and EDS mapping suggest that As is probably
inclusions of native gold exclusively within As-rich pyrite incorporated into pyrite via substitution for S (Figs. 5c,
(Fig. 4h). Our LA–ICP–MS mapping shows that As-rich 6b–d), an interpretation consistent with the conclusion
zones also contain significant concentrations of invisible that pyrite containing substituted As is formed at reduced
Au. In most hydrothermal gold deposits, invisible Au can be conditions such as in orogenic gold deposits hosted by
subdivided into nanoscale particles of gold-bearing minerals sediments (Qian et al. 2013; Stepanov et al. 2021).
(most often native gold) and Au within solid solution (Cook A close relationship between Au and As is observed in
et al. 2009; Deditius et al. 2014). As shown in Fig. 9a, As-bearing pyrite from many types of hydrothermal gold
concentrations of invisible Au in pyrite all plot below the deposits (e.g.,Simon et al. 1999; Morey et al. 2008; Large
 7 Page 12 of 22 Contributions to Mineralogy and Petrology (2024) 179:7

Fig. 8  LA–ICP–MS element maps of a representative pyrite grain with zoned texture from Donggualin mine. Scales in ppm

et al. 2009). Previous studies emphasized that Au was likely inferring that As content in pyrite is an important influence
incorporated into As-bearing pyrite by chemisorption and on Au content. Considering the stable form and absence
electrochemical accumulation onto pyrite surfaces during of obvious porosity in the As-rich zones, we attribute
crystal growth (Möller and Kersten 1994; Fleet and Mumin the enrichment to Au incorporation into As-enriched Fe
1997). Kusebauch et al. (2019) proposed that enrichment in crystallographic sites via coupled Au–As redox reactions
As leads to high partition coefficient for Au (adsorption and as proposed by Pokrovski et al. (2021). We do not, however,
incorporation) between pyrite and fluid, thus resulting in the rule out a role for surface sorption and mineral growth rate
high Au concentrations measured in As-rich pyrite. Besides, as contributors to incorporation of Au (Li et al. 2018; Wu
a decrease in pyrite volume (generating porosity) during et al. 2019).
progressive enrichment of As in pyrite may also enhance
Au sequestration (Xing et al. 2019). More recently, Stepanov A contribution from framboidal pyrite
et al. (2021) have suggested that the role of metastability
in Au enrichment in the pyrite–arsenopyrite system must Host rocks are important metal sources in many
also be considered, and Pokrovski et al. (2021) have hydrothermal gold systems (e.g., orogenic gold deposits),
demonstrated how coupled Au–As redox reactions control where the ore-forming fluids are metamorphic fluids and/
gold incorporation in As-bearing pyrite. In the Zhenyuan or meteoric water (Powell et al. 1991; Phillips and Powell
gold deposit, invisible Au mainly occurs in As-rich zones, 2009). Altered mafic rocks are considered as an ideal source
Contributions to Mineralogy and Petrology (2024) 179:7 Page 13 of 22 7

Fig. 9  Trace-element plots of framboidal pyrites and hydrothermal pyrites from Zhenyuan gold deposit. See text for additional explanation

Fig. 10  Sulfur isotopic values of different types of pyrites from the Zhenyuan gold deposit
7 Page 14 of 22 Contributions to Mineralogy and Petrology (2024) 179:7
 Contributions to Mineralogy and Petrology (2024) 179:7 Page 15 of 22 7

◂Fig. 11  a–d Sulfur isotopic values of As-rich and As-poor zones of framboidal and hydrothermal pyrite (Fig. 10; Supplemental
hydrothermal pyrite from Donggualin mine; e, f Sulfur isotopic val- Fig. S7c–f), indicating that the sulfur for this type of pyrite
ues of hydrothermal pyrite from Laowangzhai mine
indeed comes from a mixture of two distinct sulfur sources.
These texture and sulfur isotopic data indicate that reaction
because of their higher Au concentrations (Bierlein and between ore-forming fluid and framboidal pyrite must have
Pisarevsky 2008; Wilson et al. 2013; Pitcairn et al. 2015). occurred and framboidal pyrite, to some extent, could have
Thermodynamic calculations show that carbonaceous contributed to the evolution of ore fluids.
sedimentary rocks can also generate Au-rich fluids during
prograde metamorphic dehydration reactions (Tomkins Zoning in pyrite
2010, 2013). Sedimentary environments are commonly
favorable for formation of framboidal pyrite (Love Previous research (Peterson and Mavrogenes 2014; Wu
1971; Wilkin and Barnes 1997), resulting from a rate of et al. 2019; Sugiono et al. 2022) suggests that alternating
crystallization that is much slower than the nucleation rate As-rich and As-poor zones in pyrite can be induced by:
(Wilkin and Barnes 1997; Ohfuji and Rickard 2005). Prior (1) kinetic effects during crystallization including growth
studies have shown that bacterial sulfate reduction (BSR) rate and diffusion-limited self-organization processes; (2)
could result in the framboidal pyrite having very low δ34S changes in fluid chemical composition caused by fluid–rock
values, approximately 40–60‰ less than contemporary reactions and mixing; and (3) fault-valve controlled boiling.
seawater sulfate in an open-SO42− ocean environment The rate of crystal growth indeed impacts on trace-element
(Ohmoto and Rye 1979; Jiang and Ling 2004; Zhao et al. concentrations and the substitution of those trace elements
2018). Published LA–ICP–MS data reveal that framboidal in sulfide minerals (Barker and Cox 2011; Fougerouse et al.
pyrite in carbonaceous sedimentary rocks is generally 2016). However, continuous crystallization with different
rich in Au, Ag, and other metals, and may represent a growth rates should not result in a corrosion texture between
potential source for hydrothermal gold deposits (Gregory two zones, like that observed in Zhenyuan pyrite (Fig. 4b,
et al. 2016). Gold-rich framboidal pyrite can transform c, e–f). Diffusion-limited self-organization processes during
into Au-poor pyrrhotite during prograde metamorphism, crystallization were invoked to explain the sub-micron to
releasing Au into the ore-forming fluid (Large et al. 2009, atomic-scale zoned distribution of Au, As, and Cu (Wu et al.
2011; Tomkins 2010; Thomas et al. 2011). Studies of several 2019). However, the widths of individual zones in pyrite
other hydrothermal gold deposits have shown, however, that range from a few microns to several tens of microns, and
framboidal pyrite often hosts lower concentrations of Au there is evidence of corrosion texture between the As-rich
than (later) hydrothermal pyrites and, therefore, could not and As-poor zones (Fig. 4b, c, e–f). Therefore, kinetic effects
have been a source for gold mineralization (Li et al. 2014; during pyrite crystallization, by themselves, cannot explain
Wang and Zhu 2015), unless the framboids recrystallized formation of zoning in pyrite. However, the ultra-fine
after release of Au. oscillatory zonation in pyrite at the micron to sub-micron
Since the wall rocks of framboidal pyrite (Lower scale (Fig. 5a, b) may result from local kinetics.
Carboniferous carbonaceous slate) deposited in an open Several researchers (e.g.,Deditius et al. 2009; Tardani
ocean setting (Zhong 1998; Deng et al. 2015). It seems et al. 2017) have suggested that concentric micron-scale
the low δ 34S values of framboidal pyrite in Zhenyuan trace-element zoning in pyrite may form in response to
deposit presumably result from BSR processes in an changes in fluid chemical composition. However, changes in
open-SO42− ocean environment (Ohmoto and Rye 1979; fluid chemical composition caused by fluid–rock reactions,
Zhao et al. 2018). The framboidal pyrite with low δ34S value sustained fluid mixing, or mineral precipitation, generally
in Zhenyuan deposit contain very little Au concentration, form different zones in which the compositions should vary
but we cannot exclude a metal contribution from framboidal gradually (Peterson and Mavrogenes 2014), rather than the
pyrite in rocks either distal to the deposit or present at greater discrete trace-element concentrations we observe in adjacent
crustal depths. Because the Au content of most sedimentary zones within the Zhenyuan samples.
pyrite only has a median of 16 ppb (Gregory et al. 2015), As mentioned above, kinetic effects during pyrite
yet sedimentary pyrite is still considered to be an important crystallization, sustained mineral precipitation, changes in
source of Au for orogenic gold deposits. Relict framboidal fluid chemical composition caused by fluid–rock reactions
pyrite clearly occurs as inclusion within hydrothermal pyrite cannot result in the occurrence of alternating As-rich
in carbonaceous slate in the Zhenyuan deposit. Framboidal and As-poor zones of pyrites. The cyclic nature of the
pyrite is shown to be replaced by hydrothermal pyrite As-rich and As-poor zones, and their sharp textural and
(Supplemental Fig. S7a, b). Furthermore, pyrite grains compositional boundaries is reflective of repeated and
located between the framboidal pyrite and hydrothermal sudden variations in physico-chemical conditions, leading
pyrite, have δ34S values mid-way between those of adjacent to the suggestion that a fault-valve cycle environment is a
 7 Page 16 of 22 Contributions to Mineralogy and Petrology (2024) 179:7

likely candidate for formation of these pyrite grains (Toda complexes (Au(HS)2−) in medium- to low-temperature,
et al. 2002; Peterson and Mavrogenes 2014). Fault-valve weakly acidic to neutral ore-forming systems (Seward
controlled boiling can trigger sharp physico-chemical 1973; Stefánsson and Seward 2004; Williams-Jones et al.
changes of fluids including cooling and cause an increase 2009; Pokrovski et al. 2014). For native gold, a decrease
in pH and fO2 because of the loss of H ­ 2O, ­H2S, ­CO2 and of ­H2S content coupled with precipitation of As-rich pyrite
other volatiles to the vapor phase (Drummond and Ohmoto would drive destabilization of Au bisulfide complexes
1985; Williams-Jones et al. 2009). Therefore, pyrites formed and promote Au deposition in As-rich pyrite (Zhang and
under boiling and non-boiling conditions will have different Zhu 2016; Kusebauch et al. 2019; Sugiono et al. 2022).
textural and compositional characteristics. In general, the corrosion texture, abundant inclusions
The As-poor zones in the pyrite cores formed during including arsenopyrite and stibnite, and chemical features
the earliest fluid event in Zhenyuan. These As-poor zones of the As-rich pyrite zones are indicative of growth in an
generally preserve phosphate and silicate inclusions environment of intermittent boiling (Velásquez et al. 2014;
(Fig. 4f), and are depleted in chalcophile elements yet rich in Sugiono et al. 2022).
Co and Ni (Figs. 7, 8; Supplemental Table S2). In contrast,
the As-rich zones are rich in Au, Cu, Ag, Sb, and Tl but Potential sulfur sources
depleted in Co and Ni. High concentrations of Co and Ni
in pyrite have been correlated with higher temperature in Gold is mainly transported as bisulfide complexes at
previous studies (Large and Maslennikov 2020; Liu et al. conditions like those at which Zhenyuan was formed
2021), because high temperature is in favour of substitution (Williams-Jones et al. 2009; Pokrovski et al. 2014).
of Fe by Co and Ni, and relatively low temperature facilitates Therefore, the source of Au can be reliably constrained
substitution of S by As in hydrothermal pyrite (Migdisov by investigating the source of sulfur. Pyrite is the most
et al. 2011; Deditius et al. 2014). Besides, Ni generally important Au-bearing sulfide in orogenic gold deposits,
has higher solubility in fluids at higher fO2 conditions. In meaning that the sulfur isotope signatures of pyrite should
contrast, Ni tends to enter pyrite at lower fO2 conditions provide direct insights into sulfur source and evolution
(Fougerouse et al. 2016; Sugiono et al. 2022). As a result, of gold mineralization (Barker et al. 2009; Hou et al.
a fO2 increase can lead to the lower Ni concentrations in 2016; LaFlamme et al. 2018b). Previous studies suggest
pyrite. As we know boiling would trigger a temperature that different stages of pyrite and different bands within
reduction and fO2 increasing, the observed decreasing of Co individual zoned pyrite may have drastically variable δ34S
and Ni contents from As-poor zones to As-rich zones can be values in some hydrothermal deposits (Chen et al. 2015;
interpreted by boiling (Li et al. 2022; Sugiono et al. 2022). Zhao et al. 2016), revealing contributions come from
After formation of As-poor zones, boiling induced by distinct sources or from physico-chemical changes in the
subsequent episodes of faulting triggered precipitation of ore-forming system.
new As-rich zones. This was accompanied by formation of Hydrothermal pyrite from quartz porphyry, lamprophyre,
pressure shadows surrounding the pyrite crystals (Fig. 4i). quartz sandstone, and carbonaceous slate ores from the
Boiling can also be confirmed by published fluid inclusion Laowangzhai and Donggualin mines all display zoned
studies (Zhao 2014; Li et al. 2021b) showing the coexistence textures, with alternating As-rich and As-poor pyrite zones.
of ­CO2-rich fluid inclusions, C
­ O2–H2O fluid inclusions, and All have a restricted range of δ34S values from − 7.3 (± 0.6)
aqueous fluid inclusions in the auriferous quartz veinlets to 2.9 (± 0.6) ‰ with most data concentrated between − 4
with similar homogenization temperature. Arsenic, Au, and and 4‰ (89.6%, n = 58) (Fig. 10; Supplemental Table S3).
Cu exhibit high partitioning coefficients between liquid and The abundance of sulfide minerals and absence of sulfates
vapor phase at temperatures below 300 °C (Kouzmanov and indicate that ­H2S was the dominant form of sulfur in the ore-
Pokrovski 2012 and references therein). Cooling and loss forming fluid. Given the temperature range (160–190 °C),
of water and other volatiles triggered by boiling would lead low fO 2, and near-neutral pH (Ren et al. 1995; Mao
to extensive saturation of metallic elements (e.g., As, Au, et al. 2003; Liang et al. 2011), the bulk sulfur isotopic
and Cu) in liquid phase and consequently to higher levels composition in ore-forming fluid at Zhenyuan should be
of trace-element incorporation in pyrite (Velásquez et al. comparable with the measured pyrite sulfur isotopic value
2014). For instance, As(OH)3 is the dominant As-bearing (Ohmoto 1972). The δ34S values of hydrothermal pyrites
species in natural hydrothermal systems, over a wide range from Zhenyuan resemble those from Chang’an (− 6.2 to
of temperature and fluid densities (Pokrovski et al. 2002; 7.1‰) gold deposit elsewhere in the Ailaoshan gold belt
Perfetti et al. 2008). Cooling can significantly decrease (Li et al. 2013b; Yang et al. 2021). Pyrites from the adjacent
As solubility and lead to precipitation of arsenopyrite and Tongchang (1.0–1.5‰) and Habo (− 1.9–2.7 ‰) porphyry
As-rich pyrite (Velásquez et al. 2014; Xing et al. 2019). Cu–Au deposits also share similar δ34S values (Xu et al.
Importantly, Au is primarily transported as bisulfide 2014; Meng et al. 2016). These sulfur isotope signatures,
Contributions to Mineralogy and Petrology (2024) 179:7 Page 17 of 22 7

from deposits across the Ailaoshan district, resemble that of Magmatism strongly enhanced hydrothermal fluid activity
magmatic sulfur (0 ± 5‰; Ohmoto and Rye 1979). across the region. Related magmatic–hydrothermal fluids
Commonly, sulfur from sedimentary rocks provides a triggered formation of porphyry Cu–Au deposits, including
much wider range of isotopic values in sulfide minerals than Tongchang and Habo, and some of these likely evolved
we report for hydrothermal pyrites from Zhenyuan (Chang into Au-bearing ore-forming fluids that subsequently
et al. 2008; Chen et al. 2015; Xie et al. 2018). In addition, migrated. Generally, regional fluid flow and emplacement
the rocks hosting ore were unaffected by medium- or high- of gold deposits are focused and controlled by regional-
grade metamorphism. Therefore, these relatively narrow scale shear zones (Seltmann et al. 2011). Gold-bearing
range of sulfur isotopic data (most concentrated between fluids migrated upward along subsidiary shear zones in the
− 4 and 4‰, 89.6%, n = 58) indicate that magmatic sulfur Zhenyuan region. Shearing along the Ailaoshan gold belt
is the most plausible source for sulfur in Zhenyuan pyrite. was initiated at 30 Ma and lasted until 22 Ma (Zhang and
Apart from the δ 34S values, the close relationship Schärer 1999; Cao et al. 2012; Tang et al. 2013; Liu et al.
between ore-forming age of Zhenyuan deposit and adjacent 2015), concordant with an Oligocene age of ore-formation
igneous rocks can also support that sulfur is derived from a as mentioned above.
magmatic source. The Oligocene epoch was interpreted as Arsenic-poor zones in pyrite cores with high Co and
the main phase of gold mineralization at Zhenyuan based on Ni concentrations formed during the earliest fluid event.
paleomagnetic data and the Ar–Ar age of altered phlogopite Arsenic, Cu, Au, Ag, Sb, and Tl were undersaturated in the
(Wang et al. 2001; Deng et al. 2015; Gao et al. 2018). This fluid. With progressive strain (evidenced by the occurrence
age, which we infer to be that of ore formation, is in good of pressure shadows; Fig. 4i), fluid pressure increased and
agreement with that of the high-K alkaline and calc–alkaline exceeded lithostatic pressure, generating hydraulic fractures
magmatic rocks in the Ailaoshan tectonic belt (Liang et al. and resulting in a sudden drop of fluid pressure, triggering
2007; Liu et al. 2015). Moreover, published δ18OH2O and boiling of ore-forming fluid, at least locally (Zhao 2014; Li
δ13CCO2 data for fluid inclusions in auriferous quartz veinlets et al. 2021b; Fig. 12). Boiling led to oversaturation of As,
(He and Hu 1997; Liang et al. 2011) and He–Ar isotopic Cu, Au, Ag, Sb, and Tl, and precipitation of As-rich bands,
data from pyrite (Bi 1998) also suggest that ore-forming overgrowing As-poor pyrite cores. With fluid replenishment,
fluids for Zhenyuan are mainly derived from a magmatic physico-chemical conditions did not favor boiling and pre-
reservoir. cipitation of As-poor pyrite bands began again overgrowing
Boiling can lead to an increase of fluid pH and fO2, the As-rich zones. Continuous deformation induced boiling
resulting in the precipitation of pyrite with lower δ34S values of ore-forming fluids once again. As a result, As-rich pyrite
(Ohmoto 1972; Drummond and Ohmoto 1985; Palin and bands again overgrew the As-poor pyrite bands. Repetition
Xu 2000; Peterson and Mavrogenes 2014; Sugiono et al. of such a process produced the conspicuous rhythmic zoning
2022). However, the δ34S values of individual As-rich described and illustrated (Fig. 12).
pyrite zones from Donggualin mine and Laowangzhai
mine (− 7.3 ± 0.6 to 2.9 ± 0.6 ‰) are similar to those of
the corresponding As-poor pyrite zones (− 6.9 ± 0.7 to Conclusions and implications
2.8 ± 0.6 ‰; Supplemental Table S3), thus indicating that
any shift in δ34S values between the two zones is negligible. Ores from the Zhenyuan deposit are altered host rocks
Small δ34S shifts caused by boiling have been reported from containing disseminated pyrite and arsenopyrite, and
other hydrothermal gold deposits (Velásquez et al. 2014; quartz–pyrite veinlets. Pyrite in the altered host rocks and
Li et al. 2018; Hu et al. 2020). Limited, localized boiling quartz–pyrite veinlets displays complex internal textures,
events are likely unable to significantly modify the bulk clearly recognizable as alternating As-poor and As-rich
sulfur isotopic composition of the parent fluid (Tanner et al. zones. Arsenopyrite and stibnite only coexist with As-rich
2016). Alternatively, boiling cannot cause obvious increase pyrite, whereas As-poor pyrite contains inclusions of
of fluid fO2, which was buffered by reaction between fluid quartz and monazite. Visible and invisible Au both only
and carbonaceous slate. Hence, the δ34S values of As-rich occur in the As-rich zones. LA–ICP–MS mapping and spot
and As-poor pyrite are similar. analysis reveal that the As-rich pyrite zones contain greater
concentrations of Au, Cu, Ag, Sb, Tl, and lesser Co and Ni
Genesis of the Zhenyuan gold deposit than the As-poor zones. In-situ NanoSIMS sulfur isotope
analysis indicates that the δ34S values of As-rich zones
Large-scale igneous activity occurred in the Ailaoshan (− 7.3 ± 0.6 to 2.9 ± 0.6‰) are similar to those of As-poor
region due to post-collisional lithospheric extension zones (− 6.9 ± 0.7 to 2.8 ± 0.6‰), but nevertheless distinct
involving mantle processes during the Oligocene (Liang from framboidal pyrite (− 35.0 ± 0.9 to − 25.6 ± 1.0‰).
et al. 2007; Hou and Cook 2009; Liu et al. 2015). Ore-forming fluids were mainly magmatic–hydrothermal
 7 Page 18 of 22 Contributions to Mineralogy and Petrology (2024) 179:7

ores elsewhere, even if perhaps not always as spectacular as

those documented here. The textural information encoded in
pyrite, especially when coupled with robust trace-element
datasets and in-situ sulfur isotope signatures, can be widely
utilized to provide valuable insights into the evolution of
ore-forming processes.

Supplementary Information The online version contains supplemen-

tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 00410-0​ 23-0​ 2086-w.

Acknowledgements This research was supported by the National

Key Research and Development Project of China (2022YFF0800903,
2023YFC2907105), the National Natural Science Foundation of
China (41802113, 42273073 and 42261144669), and the Fundamental
Research Fund for the Central Universities (2019B08214). Discussions
with Prof. Jun Deng and Prof. Qingfei Wang improved the quality of
this paper. We thank Hengyong Lei, Qing Peng, and Yanbin Sun for
their support in the field. Xiaodan Chen kindly assisted with EPMA
operation. Lixin Gu and Xu Tang helped with FIB/TEM experiments
and Jialong Hao provided assistance during NanoSIMS analysis. This
work has greatly benefited from insightful and thorough comments
from two anonymous reviewers and Associate Editor Daniela Rubatto.

Data availability The data of the study are available in the

supplementary material (Tables S1, S2, and S3).

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