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PII: S0009-2541(20)30320-X
DOI: https://doi.org/10.1016/j.chemgeo.2020.119781
Reference: CHEMGE 119781
Please cite this article as: R. Li, H. Chen, R.R. Large, et al., Ore-forming fluid source of
the orogenic gold deposit: Implications from a combined pyrite texture and geochemistry
study, Chemical Geology (2020), https://doi.org/10.1016/j.chemgeo.2020.119781
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Rucao Lia,b, Huayong Chena,c*, Ross R. Larged, Liandang Zhaoe, Yunhua Liue, Jiangang Jiaoe,
a
Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese
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Academy of Sciences, Guangzhou 510604, China
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School of Earth Sciences and Engineering, Nanjing University, Nanjing 210023, China
c
Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640,
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China
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d
Centre for Ore Deposit and Exploration Science (CODES), University of Tasmania, Private Bag
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e
School of Earth Science and Resources, Chang'an University, Xi'an 710054, China
f
State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese
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*
Corresponding Author: Huayong Chen
Email: huayongchen@gig.ac.cn
Abstract
Interpretation of bulk sulfur isotope data of the orogenic gold deposit is frequently hampered by
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complex zoning in pyrite, which calls for in-situ determination of sulfur isotope composition of sulfide
minerals. The Qiuling gold deposit, located in Qinling orogen, is representative of orogenic type and
selected here to further constrain the source of sulfur (and Au) and test the current popular ore genesis
models for deposits of this type. Detailed backscattered electron imaging (BSE) study is applied to
characterize intragrain texture, and subsequently in-situ sulfur isotope and trace element determination
using secondary ion mass spectrometry (SIMS) and laser ablation-inductively coupled plasma-mass
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spectrometry (LA-ICP-MS) are used to reveal sulfur and metal source and evolution of the ore-forming
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fluid.
Two generations of pyrite, i.e., pre-ore stage (Py1) and ore stage pyrite (Py2), were investigated in
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this study. In most cases, Py1 occurs as pyrite framboids, while Py2 as euhedral grains, in which Py2a
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as anhedral core, Py2b and Py2c as euhedral inner and outer rim, respectively. The δ 34S values of both
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Py1 and Py2 have unusual wide ranges, i.e., a δ34S variation from -31.1 to +106.7‰ for Py1 (average
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+0.8‰) and from -2.7 to +24.1‰ for Py2 (average +13.2). The distribution pattern of δ 34S values in
Py1 is accommodated with Rayleigh fractionation in sulfate-restricted pore water. Modeling results
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show that neither temperature nor oxygen fugacity change could result the variations in δ 34S values of
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Py2, and contribution of both preexisting pyrite and a pulse of ore-forming fluid with δ34S about +14.2‰
may be responsible for the observed variation in Py2. Such fluid may have been sourced from
metamorphism of old strata such as the Neoproterozoic basement. Furthermore, Py2a shows an
intimate relationship with Py1 in its δ34S values, indicating Py1 may have acted as part of sulfur source
Py1 is rich in a suit of element such as Bi, Co, Mn, Ni, Tl and has the lowest As and Au. Py2a is
similar with Py1 but with elevated As and Au. Py2b contains more abundant As and Au compared to
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Py2a. Py2c is rich in As and especially Au, but depleted in other elements compared to Py2a. The
distribution pattern, coupled with sulfur isotope composition, indicates that Py2a was likely formed
with a contribution of trace elements and sulfur from Py1 at the start of hydrothermal process. Py2b
was formed with elevated proportion of contribution from the ore-forming hydrothermal fluid, while
Py2c was formed solely by the ore-forming fluid without a contribution from previous pyrite.
Consequently, the ore-forming fluid in the Qiuling gold deposit was rich in As, Au, Cu and Sb while
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depleted in other metals such as Bi, Co, Mn, Ni and Tl, indicating that the pre-ore framboid pyrite may
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have not contributed any Au and As during mineralization.
This study highlights the importance of detailed texture characterization coupled with relatively
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large data set of in-situ sulfur isotope and trace elements for orogenic gold deposit research, and further
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proves that metamorphic fluids may have significant contribution for Au mineralization in orogenic
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gold deposits.
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Keywords: Orogenic gold deposits; Qiuling; Pyrite; Sulfur isotope; SIMS; Trace element
1. INTRODUCTION
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Orogenic gold deposits are one of the most important Au-bearing deposit types. Although with a
long research history, there has been increased controversy over genesis of these deposits recently
(Goldfarb and Groves, 2015). Even though many parameters of the ore-forming fluid reported to date
are largely consistent with the metamorphic crustal fluid source model, a magmatic-hydrothermal
model is recently coming back into favor (Bath et al., 2013; Lawrence et al., 2013; Spence-Jones et al.,
2018). Magmatic sulfur usually has a δ34S around 0‰ (Seal, 2006) and sulfur derived from
metamorphism of older strata usually have relatively wide range (Goldfarb and Groves, 2015), which
offers a promising tool to test these two models. Besides, sulfur is the complexing agent for Au, thus
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understanding sulfur source may be critical in defining the gold source region(s) (Goldfarb and Groves,
2015; Saunders et al., 2014; Tomkins, 2013). However, interpretation of sulfur isotope data is far from
straightforward because in many orogenic gold deposits, ore stage sulfide grains usually contain
multiple stages of overgrowths, and sulfur isotope data derived using bulk analysis represents a mixed
signal, from which no definite conclusion could be draw. In-situ determination of sulfur isotope
composition, combined with trace element analysis, has been frequently reported recently, and the high
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spatial resolution offers a promising tool to reveal the complex overgrowth history in single grains and
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to trace their sulfur sources in orogenic gold deposit (Large et al., 2009; Li et al., 2014; Sung et al.,
than 100 sediment-hosted gold deposits, in which more than 10 deposits are world-class (Chen and
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Santosh, 2014; Goldfarb et al., 2005; Mao et al., 2002; Zhou et al., 2002). Recently, some deposits
previously thought to be Carlin-type (Zhang et al., 2002) were re-evaluated and suggested to be
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orogenic-type, such as Qiuling gold deposit in the East Qinling orogen (Chen et al., 2015).
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The Qiuling epizonal orogenic deposit (Fig. 1a), located in the East Qinling Orogen (Zhang and
Shen, 1996), is an important gold deposit in this area (Chen et al., 2015). Even though with a long
research history, some key points remain unresolved (Chen et al., 2015; Shen, 1996; Zhang and Shen,
1996). Chen et al. (2015) reported in-situ sulfur isotope of ore stage pyrite, which clusters around
+12.8‰, and claimed that the sulfur should be sourced from the Upper Devonian sub-greenschist
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facies clastic rocks. However, no existing data shows such an S-enriched average sulfur isotope
composition of the Upper Devonian strata in the Qinling orogen. Besides, the sub-greenschist facies
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metamorphism is generally too low to generate metamorphic fluids related to breakdown of pyrite
(Tomkins, 2010). Another aspect remain controversy is the source of gold, with some researchers claim
that gold was sourced from pre-ore stage pyrite (Shen, 1996; Zhang and Shen, 1996) while others claim
that Au (and sulfur) came from ore-forming fluid (Chen et al., 2015). The key to solve this problem
may lie in determination of the Au concentration of the pre-ore stage pyrite, which has failed to do so
in previous research. To illustrate these problems, we applied detailed BSE imaging, EPMA major
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element, SIMS sulfur isotope and LA-ICP-MS trace element analyses on pre-ore stage pyrite (Py1) and
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ore stage pyrite (Py2). Combining all the results, we have shown the As and Au in Py1 is neglectable,
and the S, As, Au, Cu and Sb in ore-forming fluid are mainly sourced from metamorphic fluid released
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from sedimentary pyrite in the Neoproterozoic basement during its transition to pyrrhotite.
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2. GEOLOGICAL BACKGROUND
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The roughly NWW-striking Triassic Qinling orogen extends for about 2,500 km across central
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China (Fig. 1a), and was formed by continental collision of the Yangtze and North China cratons in the
Middle-Late Triassic (Dong et al., 2011). The Qinling orogen records a complex, multistage orogenic
history involving prolonged subduction and closure of the Shangdan and Mianlue oceans from middle
Paleozoic to early Mesozoic (Dong et al., 2013; Dong et al., 2011; Meng and Zhang, 1999).
Traditionally, the Qinling orogen was divided into the North Qinling and South Qinling belts (Fig. 1a),
which are separated by the Paleozoic Shangdan suture (Dong et al., 2011; Ratschbacher et al., 2003).
The northern domain is characterized by extensive exposures of Devonian flysch sequences that
have been subjected to greenschist facies metamorphism (Mao et al., 2002; Mattauer et al., 1985), and
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the southern domain is bounded by the Triassic Songpan-Ganzi basin to the southwest and separated
lengthwise by the Zhouqu-Chengxian-Huixian fault (Fig. 1a). The South Qinling belt is underlain by
Paleo- to Mesoproterozoic basement metamorphic complex, composed of paragneiss and marble that
were overlain by low-K tholeiite to calc-alkaline and alkaline basalts with arc signatures (Chen et al.,
2015). Neoproterozoic basement presents both in the west and east domain of the Qinling orogen, and
in the east domain is represented by Yaolinghe Group (Dong and Santosh, 2016; Ling et al., 2008).
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Neoproterozoic basement in the Qinling orogen is generally metamorphosed to greenschist facies, but
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amphibolite facies metamorphism is also reported in Yaolinghe Group (east Qinling orogen) (Zhang et
al., 1995). Above the metamorphic complex are the Cambrian to Triassic marine sedimentary rocks (up
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to 12,000 km in thickness). The Cambrian rocks contain a distinctive sequence of sediments composed
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of pyritic black shale, black chert and carbonate rock with a maximum thickness of 1000 m (Chen et al.,
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2015; Wang and Li, 1991). Silurian to Devonian rocks are dominated by a flysch sequence consisting
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of meta-graywacke, slate, phyllite, and carbonate which is indicative of significant subsidence and
rapid sedimentation (Zhang et al., 1997b). There are many gold deposits present in the South Qinling
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belt (Fig. 1a), and most of which are hosted in Devonian rocks composed of carbonate, siliciclastic and
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argillaceous rocks with a total thickness of ca. 3000 ~ 8000 m that were deposited in several growth
fault-bounded basins (Liu et al., 1990). The Devonian sequence is conformably overlain by
Carboniferous to Triassic rocks consisting of shallow marine limestone with minor amounts of
siliciclastic sedimentary rocks and, locally, coal (Ma et al., 2004; Ma et al., 2007).
The Paleozoic and Triassic sedimentary rocks were intensely deformed during the Qinling
orogeny, and along with this, numerous regional northwestern striking folds and thrust faults were also
produced (Fig. 1a). These faults are the first control on the distribution of the gold deposits in this area
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(Chen and Santosh, 2014; Mao et al., 2002). The Qinling orogen has been broadly divided into the East
and West Qinling orogens by the Baocheng railway (Zhang et al., 1995) and the Qiuling gold deposit is
A large number of granitoid intrusions are present to the south of the Shangdan suture, which were
emplaced during closure of the Mianlue Ocean and subsequent collision of the Yangtze and North
China cratons (Qin et al., 2009). The emplacement ages range from 239 ~ 200 Ma, which indicates
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emplacement of the granitoid intrusions in both syn-collision and post-collision environments (Dong et
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al., 2011; Qin et al., 2009; Wang et al., 2011; Zhang et al., 2008). Syn-collisional intrusions were
emplaced at about 239 ~ 217 Ma, while post-collisional intrusions were mostly emplaced at about 217
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~ 200 Ma (Dong et al., 2011; Qin et al., 2009; Wang et al., 2011; Zhang et al., 2008).
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2.2. Geology of the Qiuling gold deposit
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The Qiuling deposit, which is assigned to be an epizonal orogenic gold deposit (Chen et al., 2015),
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is located in the south belt of the East Qinling orogen (Fig. 1a). The strata present at Qiuling are, from
old to young, the Upper Devonian Lengshuihe and Nanyangshan formations, the Lower Carboniferous
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Yuanjiagou Formation of and Middle Carboniferous Sixiakou Formation (Zhao and Feng, 2002). Gold
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ore bodies are hosted in the Upper Devonian Nanyangshan and Lower Carboniferous Yuanjiagou
formations (Fig. 1b, Shen, 1996; Zhang and Shen, 1996). The Nanyangshan formation consists of
micrite, clastic limestone, silty limestone and calcareous siltstone, while the Yuanjiagou formation
consists of micrite, bioclastic limestone, sandy limestone with argillaceous clastic rock interlayers
(Zhao and Feng, 2002). Thin chert beds increase when approaching the Yuanjiagou formation, which is
usually used as boundary line between the two formations. No or very low-grade metamorphism is
observed in both formations. The Devonian and Carboniferous sedimentary rocks were deformed
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during formation of the Qinling orogen, which resulted in the formation of a number of faults and folds
involving the Paleozoic sequence (Zhang et al., 2000; Zhang and Shen, 1996; Zhang et al., 2002). The
faults occur mostly along a northwestern or nearly east-western strike and were overprinted by NE- to
NNE-striking faults (Fig. 1b). The NWW-striking Qiuling anticline is the principle structural feature in
this deposit (Fig. 1b). Gold ore bodies are mainly controlled by the NWW-striking transpressional
faults. No igneous rocks are present in the deposit area (Shen, 1996).
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Five ore bodies were identified at the Qiuling gold deposit, i.e., 301, 302, 303, 304 and 308 (Fig.
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1b), in which 301 and 304 are the two main ore bodies. The ore bodies have a proven reserve of 50 t Au
Zhang and Shen, 1996). Other minor sulfides are sphalerite, chalcopyrite and galena (Zhang and Shen,
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1996). Gangue minerals associated with ore minerals mainly include quartz, calcite and sericite. The
decarbonation is observed. Researchers reported clastic hosts to gold mineralization in local parts of
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this deposit (Zhang et al., 1997a). The age of Qiuling deposit, determined using Ar/39Ar
geochronology of ore stage sericite, is suggested to be 232.7 ± 6.9 Ma (Zhao et al., 2001), synchronous
with formation of the Qinling orogen (Dong and Santosh, 2016; Dong et al., 2011) and similar to other
orogenic gold deposit in this region (Mao et al., 2002; Zeng et al., 2013).
A total of 22 samples, 19 from 301 and 304 ore bodies and 3 from host rocks, were collected in
this study, whose lithologies are mainly micrite and clastic limestone and silty limestone. The thick
sections of the samples were first examined using microscope, and then BSE imaging to characterize
internal textures and discriminate different stages of pyrite, i.e. pre-ore stage (Py1) and ore stage Py2.
Of all the samples, 7 of them have Py2, 20 have Py1, and 5 of them contain both Py1 and Py2. The
areas of interest were cut off using a microdrill and mounted into epoxy of 25.4 mm in diameter. The
mounts were carefully polished with a 1 μm diamond paste, and then washed several times using
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ethanol and de-ionized water. All mounts were heated in an oven for 3 h at 40oC. Before SIMS analysis,
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all mounts were coated by a gold layer with a thickness of 30 nm. Representative samples with
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relatively large grain size and wide zonation were selected for LA-ICP-MS analysis.
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3.2. In-situ SIMS sulfur isotope analysis
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The SIMS analysis was conducted on a Cameca IMS1280-HR at the Guangzhou Institute of
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follows: Selected sulfide samples were mounted onto 25 mm diameter epoxy and polished. A primary
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Cs+ ion beam (~2.0 nA current and 20 keV total impact energy) was focused at the sample surface
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with a spot diameter of 15 μm. 20 s pre-sputtering was applied to remove the Au coating, and a
normal-incidence electron gun used for charge compensation. The mass resolving power was set at
~5000 to avoid isobaric interferences. NMR field sensor was applied to stabilize the magnetic field. 32S,
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S and 34S were measured simultaneously by the multi-collection system and the total analysis time for
one spot is about 4 minutes. More details can be found in (Li et al., 2019).
Data reduction was similar to that described in (Li et al., 2019), and the primary pyrite standards
used in this study is UWPy-1 (Ushikubo et al., 2014). The isotope ratio is expressed in relation to the
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(Seal, 2006). At the SIMS laboratory at GIG-CAS, we adopt the protocol that reproducibility is
calculated as the standard deviation (SD) of the entirety of analyses on the reference material over the
course of an analytical session. The reproducibility of δ34S was better than 0.2‰ in most cases and 0.8‰
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BSE imaging, major element determination and elemental mapping were applied to reveal internal
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texture and chemistry variation of the pyrite grain. All analyses were performed using a JEOL
JXA-8230 electron probe micro-analyzer (EPMA) at the Shandong Analysis Center of China
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Metallurgical Geology Bureau. The parameters were an accelerating voltage of 15 kV for BSE imaging
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and changed to 20 kV for quantitative determination and elemental mapping of major elements. Other
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parameters include a probe current of 20 nA and a beam size of 1 μm. The step size for elemental
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mapping was 1 μm, and the dwell time was set to be 100 ms for each point.
Elemental mapping and quantitative determination by LA-ICP-MS was conducted at the Tuoyan
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in-situ Analysis Lab (Guangzhou, China), using a 193 nm ArF Excimer Laser Ablation system (NWR
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193) coupled with a Thermal Fisher iCAP RQ, a dual concentric injector (DCI) plasma torch integrated
with the two-volume ablation cell for the LA-ICP-MS mapping. Detailed analytical procedures were
described as follows: the ablation site is determined using spot and line scanning pattern for
quantitative determination and mapping respectively. The raster image is made up of evenly-spaced
individual line stack together in time order. The laser log which including the laser on and off, the line
spatial location and the sample information is suggested to preserve for further data reduction. The
external element standard of NIST 610, MASS-1 and GE8 was suggested to add in beginning and end
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of the total scan line matrix of samples. In this study, the laser frequency set to 100 Hz, and the laser
scan speed was 6 µm/s, the scan speed should be larger than the d𝑥/duty time, which is 2 µm/0.354 s =
5.64 µm/s, the laser spot sets as 5 µm with no space between lines.
The ICP-MS was set to time-resolved method and automatically triggered by laser, the elements
of Ag, As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb and Tl were collected at each duty cycle, with the dwell time
set to be 6 ms for each element. This gave a duty time of 0.354 second. The estimated time taken for
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sample mapping and standards were automatically calculated in the laser software, and set a longer
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time than the calculation time as collection time in the ICP-MS.
After the data acquisition, data reduction was performed using the software Iolite (version 3.73)
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(Hellstrom et al., 2008; Paton et al., 2011), an add-in run within Igor Pro (version 6.37, WaveMetrics).
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Mass bias and instrument drift were carefully corrected by setting a linear fit with a selected standard
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calibrating of mapping run, and NIST 610 was used as the standard. Subsequently, the raw data were
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calibrated with the internal standard the average Fe value of the whole map. After crunching the data,
the Iolite software can perform quantitative mapping by stacking the continuous line in time order, and
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4. RESULTS
Three major generations of pyrite were identified at the Qiuling gold deposit, i.e., pre-ore stage,
ore stage and post-ore stage pyrite (Chen et al., 2015). Since, no post-ore stage quartz-pyrite vein is
observed in this study, and the aim of this study is to illustrate the relationship between Py1 and Py2
and ore-forming fluid evolution, so only Py1 and Py2 were carefully studied.
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Py1 is randomly distributed in the sedimentary rocks of the Nanyangshan and Yuanjiagou
formations. Py1 mainly occurs as pyrite framboids (Fig. 2a) and locally as euhedral pyrite crystal (Fig.
2b). The pyrite framboids are mostly < 10 μm in diameter, with rare cases can be as large as 50 μm or
larger (Fig. 2a). The pyrite framboids in pre-ore stage generally occur as cluster of dark individual
euhedral crystal in BSE images (Fig. 2a). These small individual crystals usually have a size less than 2
μm and are frequently observed to be surrounded by bright overgrowth (Fig. 2a), which could belong to
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late Py2 (see below). Euhedral pyrite of pre-ore stage usually has a size similar with pyrite framboids
(Fig. 2b), and in rare cases can be larger than 100 μm.
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Py2 was formed in the main mineralization stage, in which gold was introduced. Py2 mainly has a
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size of 100 ~ 200 μm, usually associated with arsenopyrite (Fig. 2c). According to BSE imaging results,
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Py2 was divided into three sub-stages in this study, i.e., Py2a, Py2b and Py2c (Fig. 2c). Py2a occurs as
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dark anhedral core; Py2b as bright euhedral overgrowth on Py2a and Py2c as clear euhedral
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overgrowth on Py2b with brightness between Py2a and Py2b in BSE images (Figs. 2c, d). It is obvious
that Py2a has been partially replaced by Py2b, which is not observed between Py2b and Py2c (Figs. 2c,
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d). In most cases, Py2 is associated with arsenopyrite (Fig. 2c), but in samples distal to the main ore
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body, little or no arsenopyrite observed (Fig. 2d). In most of our samples, Py2a act as core of zoned
pyrite in ore stage (Fig. 2c), and in rare cases Py1 can also act as core of zoned Py2 (Fig. 2d). Py1
usually has the darkest brightness in BSE images, and has much more voids when there are Py2
overgrowths (Fig. 2d), which can be used as a criterion to distinguish Py2a from Py1.
δ34S values of Py1 has a range > 130‰ (-31.1 ~ 106.7‰, average at +0.8‰, Fig. 3). The δ34S
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values of Py2 has a range of 26.8‰ (-2.7 ~ 24.1‰, average at +13.2‰, Fig. 3). The average δ34S
values for Py2a, Py2b and Py2c are +11.4‰, +13.4‰ and +14.9‰, respectively. Substantial variation
is observed from Py2a to Py2c (Figs. 4a-g), and both decreasing and increasing trends in δ34S values
are observed from Py2a to Py2c (Figs. 4a, d). The variation of δ34S in a single grain is as high as 10.6‰
(Fig. 4a). Such variation is large between Py2a and Py2b (Figs. 4a-b) and small between Py2b and P2c
(Figs. 4d-e), however, most variations of δ34S from Py2a to Py2c tend to focus in the range of +9 ~ +15‰
(Fig. 5). In addition, δ34S values of Py2a show an intimate relationship with Py1 (Fig. 6a) from the
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same sample, but less so between Py2b and Py1 (Fig. 6b). More details can be found in Appendix S2.
than that of Py1, which can be as high as 8.31 wt% (Table. 1). Sulfur concentration in Py1 is
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considerably higher than that in Py2, reversed with As, indicating possible substitution between As and
S in pyrite (Figs. 7a-c). Arsenic concentration in Py2a varies widely, with some analysis below
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detection limit of EMPA (Table.1, Figs. 7d-f), and others as high as 7.67 wt% (Table. 1). Arsenic
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concentration in Py2b and Py2c varies from 4.02 to 8.31wt% and 2.43 to 5.67 wt%, respectively. Co
and Ni concentrations in Py1 are slightly higher than that of Py2, but no significant difference was
observed in Co/Ni ratios between Py1 and Py2, both of which have consistent Co/Ni ratios mostly <2
(Table. 1).
The pyrite grains with obvious texture and major element zonation were further characterized in
their trace element by LA-ICP-MS. Some spots of Py1 have very high As concentration, which is in
sharp contrast with EMPA results. The high As concentration in Py1 detected by LA-ICP-MS should
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result from contamination by As-rich pyrite of Py2 (Fig. 7a). Therefore, we suggest the spots with As
concentration higher than 1700 ppm (the highest As concentration determined by EMPA, Tab. 1) is not
Trace element concentration in Py1 and Py2 are highly variable (Fig. 8). Generally, Py1 is rich in
a suit of trace elements such as Bi, Co, Mn, Ni and Tl, which is also observed in Py2a (Fig. 8). Trace
element concentrations decrease from Py2a to Py2c in Bi, Co, Mn, Ni and Tl, and vice versa in As, Au
Cu and Sb (Fig. 8). Co/Ni ratios in both Py1 and Py2 are all ≤1 (Fig. 9), which is consistent with EMPA
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results (Tab. 1). LA-ICP-MS mapping results show that Py2a is rich in a suit of trace elements, such as
Ag, Bi, Pb, Sb and Tl, and depleted in As and Au comparing with Py2b and Py2c (Figs. 10a-m). Py2b
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has similar element assemblage with Py2a, but higher As (Figs. 10b, e), while Py2c is depleted in all
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trace elements presented in Py2a but rich in As and Au (Figs. 10e-f). Similar distribution pattern of the
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5. DISCUSSION
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Pyrite formed in the ocean is one of the most important sinks for sulfur and arsenic in the sulfur
cycle (Canfield, 2001; Large et al., 2014), and the sulfur of sedimentary pyrite mainly comes from
reduction of seawater sulfate by sulfate-reducing bacteria (SRB, Ohmoto and Goldhaber, 1997; Rickard
Theoretically, pyrite framboids can be formed both in the water column (syngenetic) and pore
water (diagenetic) (Raiswell and Berner, 1985). Syngenetic framboids usually have smaller size
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compared with diagenetic ones, which may result from limited growth time within the water column
(Rickard, 2019). According to statistical investigation (Rickard, 2019), framboids with diameter > 11
µm are more likely to be diagenetic. Besides, euhedral pyrite is generally accepted to have formed in
sediments (diagenetic) (Lin et al., 2016; Taylor and Macquaker, 2011). To meet the analytical
requirements during SIMS analysis in this study, only framboids > 20 µm were selected. So, both the
framboids and euhedral pyrite in this study should mainly be diagenetic, in which sulfate-limited
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condition could happen.
The fractionation in sulfur isotopes between sulfate and pyrite is usually thought to be about 45‰
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when the system is open with respect to seawater sulfate (Canfield, 2001; Ohmoto and Goldhaber,
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1997; Seal, 2006). But recent research has revealed that a sulfur isotope fractionation as high as 66‰
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between seawater sulfate and product pyrite can be achieved by sulfate-reducing bacteria without
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disproportionation process (Sim et al., 2011). According to the carbonate associated sulfate study, the
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average δ34S value of the global seawater at Devonian-Carboniferous boundary is around +23‰ (Wu et
al., 2014). If the fractionation between starting seawater sulfate and product pyrite is in a range of 45‰
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~ 66‰, the product pyrite should have δ34S value as low as -43‰ ~ -22‰, which is generally
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consistent with the most negative δ34S value of Qiuling Py1 (-31.1‰, Fig. 3), which indicates a
sulfate-unlimited open system (e.g., shallow sediments). The less negative δ34S values (-19.3‰ in
Appendix S2) may have formed in partially closed system (e.g., deep sediments) which is slightly
sulfate-limited. The most positive δ34S value of Py1 is +106.7‰, much higher than coeval seawater
sulfate (Wu et al., 2014), indicating a sulfate-limited system in which Rayleigh fractionation would
happen (Canfield, 2001; Canfield et al., 2010; Luo et al., 2010; Ohmoto and Goldhaber, 1997).
Modeling result indicates that consumption of seawater sulfate in confined pore water over 90% could
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result in pyrite with δ34S value up to +106.7‰ (Fig. 12a). The skewed δ34S distribution pattern in
which the frequency decreases when approaching higher δ 34S values is also perfectly consistent with
Actually, it is not easy to discriminate Py1 and Py2a when they occur in different grains. But two
criteria can be used to discriminate them occurring in one grain, i.e., Py1 is darker and contains much
of
more voids in BSE image than Py2a (Figs. 4b, c). The systematic changes of trace elements (As, Bi, Co,
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Mn, Ni and Tl) also support the existence of Py2a (Fig. 8). Moreover, the sulfur isotope composition of
Py2a is similar to that of Py2b and Py2c, only with wider range. If Py2a is sedimentary pyrite same as
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Py1, the average sulfur isotope of Py2a should be ~0‰ (similar to Py1) and much lower than we
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observed here. Besides, the distribution of sulfur isotope of Py2a tends to be normal (Fig. 3), not like
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Py1, which shows more depleted δ34S values- and a skew distribution to the negative side. Although
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the limited analysis of Py2a could obscure the difference between Py2a and Py1, given the evidences
Sulfur is the complexing agent for gold (Goldfarb and Groves, 2015; Saunders et al., 2014;
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Tomkins, 2013), sulfur isotope compositions of sulfide minerals can, therefore, provide information on
the source, transport, and precipitation of gold and genesis of sediment-hosted gold deposits. Besides,
previous research has shown that aside from sulfur, pre-ore stage pyrite could possibly offer Au for
ore-forming fluid (Large et al., 2009; Large et al., 2007). So, the potential contribution of sulfur, and
even gold, from Py1 during ore formation is very important and need to be illustrated at Qiuling.
Since gold is most abundant in Py2b and Py2c (Figs. 8, 10f), the ore-forming fluid should best be
represented by Py2b and Py2c. Since the main metallic mineral phases during gold mineralization are
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pyrite, arsenopyrite, tetrahedrite, sphalerite and stibnite that mainly formed in reduced fluid (Fig. 2) (no
magnetite or hematite present) (Zhang and Shen, 1996), the oxygen fugacity should be relatively low,
and the difference between pyrite and ore-forming fluid should be minimal (< 3.4‰, Fig. 12b)
(Ohmoto and Goldhaber, 1997). A pH vs logfO2 diagram (Ohmoto and Goldhaber, 1997) is adapted to
further constrain possible fractionation of sulfur isotope between pyrite and ore-forming fluid (Fig.
12c). The diagram modeled sulfur isotope fractionation at 250oC, which we think is appropriate for
Qiuling at which the temperature of the ore-forming fluid was determined to be around 182 ~ 300oC
of
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based on fluid inclusion study (Zhang and Shen, 1996). Petrologic investigation in this study (Fig. 2e)
and previous study (Appendix S1) (Zhang et al., 2000) shows that carbonate minerals (e.g., calcite and
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ankerite) is a stable phase in ore stage, indicating that the pH of the ore-forming fluid should be around
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7 or higher. Given that no magnetite, sulfate or pyrrhotite is present, the oxygen fugacity of the
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ore-forming should be best represented by the gray area in figure 12c. In this case, the difference
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between ore-forming fluid and pyrite should be < 4‰, consistent with modeling result in figure 12b. So,
the δ34S value of ore-forming fluid should be similar to the average δ34S value of Py2b and Py2c
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(+14.2‰). A δ34S value of +14.2‰ is not consistent with magmatic sulfur, which clusters around 0‰
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(Ohmoto and Goldhaber, 1997; Seal, 2006). The absence of igneous rocks in and around deposit area
(Shen, 1996; Zhang et al., 2000; Zhang and Shen, 1996) does not support a magmatic contribution of
sulfur. This is also not consistent with sulfur from seawater sulfate whose sulfur isotope composition is
The most reasonable source with such δ34S value in this area is probably metamorphic sulfur
which eventually sourced from metamorphism of sedimentary strata formed before gold mineralization
(Chen et al., 2015; Goldfarb et al., 2005; Goldfarb et al., 1991; Wu et al., 2018). The sulfur released
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from metamorphized sedimentary rocks are mainly sourced from breakdown of pyrite during its
transition to pyrrhotite (Large et al., 2009; Tomkins, 2010; Tomkins and Evans, 2015). Buffered by
pyrrhotite and at relatively high temperature (Tomkins, 2010), the sulfur isotope composition of the
S-bearing species released during breakdown of pyrite should be similar with parent pyrite (Fig.3 in
Chang et al., 2008), which enables us to compare the deduced ore-forming fluid at Qiuling with pyrite
in older sedimentary rocks. Sulfur isotope data of diagenetic pyrite in the underlying Paleozoic
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sedimentary sequences of the Qinling orogen has been sporadically reported (Liu et al., 2000; Luo et al.,
2004; Nan et al., 2012; Qi et al., 2003). The δ34S values in Devonian phyllite and metagraywacke has
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been reported to be in the range of -29.0 ~ +17.5‰ with an average value of -0.9‰ (Qi et al. 2003; Luo
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et al. 2004; Nan et al. 2012), similar with the average value of pyrite in the ore-hosted wall rocks
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determined in this study (+0.8‰, Fig. 3). This is too low to be the sulfur source for the ore-forming
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fluid at Qiuling. The δ34S values reported in Cambrian black shale in western part of the Qinling
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orogen seems to be more positive and clusters in the range of -10.0 ~ 46.9‰, with an average of +13.1‰
(Liu et al. 2000). This value approximates the deduced value of the ore-forming fluid, but the Cambrian
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black shales in Qinling orogen only experienced sub-greenschist to greenschist metamorphism, which
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may be too low to result in breakdown of pyrite. A more plausible source would be the Neoproterozoic
basement in Qinling orogen, which is widespread in studied region and metamorphosed to greenschist
to amphibolite facies (Zhang et al., 1995; Zhu et al., 2014), which generally meets the condition for
Neoproterozoic strata of South China has long been reported to be 34S-rich (Cui et al., 2018), consistent
with global record which has an average δ34S value around +10‰ (Canfield and Farquhar, 2009).
The variation in sulfur isotope of ore stage pyrite is large (26.8‰, Fig. 3), which could possibly
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result from change in temperature, oxygen fugacity and sulfur composition of the ore-forming fluid or
Rayleigh fractionation process. The variation in sulfur isotope of ore stage pyrite is hard to be
explained only by temperature change even we assume a fully oxidized system (Fig. 12b) given the
temperature range (182 ~ 300oC) (Zhang and Shen, 1996). The change of oxygen fugacity is not likely
to account for the sulfur isotope change either, supported by the presence of sulfide phase that mainly
formed in relatively reduced fluid (e.g., pyrite, arsenopyrite, tetrahedrite, sphalerite and stibnite).
Besides, if there do exist change in oxygen fugacity, a systematic change in δ 34S would be expected.
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Imagine a system rise in oxygen fugacity of the ore-forming fluid, 34S would preferentially enter sulfate
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(solid or dissolved), leaving sulfide rich in 32S, and a systematic decrease of δ34S would be expected in
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sulfide minerals but not with a wide range of variation (a reverse trend would be expected if there is a
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decrease in oxygen fugacity). This process is thought to have happened in Daqiao deposit in west
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Qinling because of the systematic decrease in δ34S of sulfide minerals (Wu et al., 2019), but no such
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systematic decrease or increase trend is observed at Qiuling (Fig. 5), indicating that oxygen fugacity
variation in ore-forming fluid is negligible. Rayleigh fractionation would allow early pyrite
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preferentially take 32S from the fluid, resulting in a systematic increase in sulfur isotope of the residual
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fluid and later pyrite, which is not observed in our samples (Fig. 5).
The discussion above leaves a change in sulfur isotope of the ore-forming fluid the only possible
cause for variation in sulfur isotope of the ore stage pyrite, which is different from a single sulfur
source model. Actually there is a long history of controversy referring to whether or not Py1 has
offered sulfur (and more importantly gold) during formation of Py2 (Chen et al., 2015; Zhang and Shen,
1996). Previous sulfur isotope results in Chen et al. (2015) observed δ34S values clustering around
-20‰, in dramatic contrast with ore stage pyrite (>10‰), by which the authors claimed that Py1
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couldn’t contribute sulfur during formation of Py2. However, our results show that 1) the range of δ34S
value of Py1 is very wide, completely covered the range of Py2 (and Py2a) (Fig. 3), indicating that Py1
has the potential to offer sulfur for Py2a; 2) δ34S values show a more intimate relationship between Py1
and Py2a than that of Py1 and Py2b (Fig. 6); 3) Py2a and Py1 are similar in trace element concentration
(Figs. 7e-f, 8) and BSE images (Fig. 7d), but in clear contrast with that of Py2b and Py2c. All these
lines indicate that Py1 may have contributed sulfur and some related metals into early ore stage pyrite
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(i.e., Py2a). But the contribution of Py1 during formation of Py2a should be less important compared
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with the ore-forming fluid given the large difference between Py1 and Py2a (Fig. 3).
characterize As concentration in pyrite when As concentration is much higher than the detection limit
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of the EMPA. According to the As mapping (Figs. 7a-f) and quantitative determination result (Tab. 1),
it is clear that the As concentration in Py1 is very low (< 1700ppm), and couldn’t be a candidate source
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for As in Py2. So, the most plausible source for As at Qiuling should be the ore-forming fluid. The
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increasing As concentration from Py1 to Py2c (Fig. 8) derived from LA-ICP-MS also support this
hypothesis.
It has been reported that sedimentary pyrite could act as Au source during Au mineralization (Large
et al., 2007), so it is important whether or not Py1 has offered Au at Qiuling. Actually, it has been
debated in previous studies referring to the source of Au at Qiuling, with some researchers claim that
Py1 offered the Au (Shen, 1996; Zhang and Shen, 1996) and others claim that Au (and sulfur) came
from ore-forming fluid (Chen et al., 2015). The key to resolve this problem is to know the Au
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concentration of Py1, which has not been achieved in previous research because of the small size of the
Py1. We obtained 33 spots of Py1 using LA-ICP-MS, and the results vary from below detection limit to
34.7 ppm (Tab. 2). However, the very high As concentrations in Py1 indicate contamination of As and
possibly Au from Py2 (Tab. 2, Fig. 7a). As discussed in Section 4.3, the spots of Py1 with As
concentration higher than 1700 ppm are not suitable to evaluate Au of Py1 and have been ruled out
accordingly. Using this as a screening criterion, the Au concentration in Py1 is lower than 9.4 ppm
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(average 1.6 ppm), which is much lower than that in Py2 (Fig. 8). Based on the discussion above, the
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Au concentration in Py1 is very low and the Au at Qiuling should be largely sourced from ore-forming
fluid. Similar with As, the increasing trend of Au concentration from Py2a to Py2c supports this
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hypothesis.
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According to the deduced sulfur source for ore-forming fluid, the As and Au in Py2 at Qiuling
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deposit is most likely introduced along with sulfur from the metamorphic fluid. Unlike sulfur isotopes,
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Au concentration of pyrite in sedimentary rocks of Qinling orogen has not been reported, but there are
reports about Au concentration derived from sedimentary rocks with age ranging from Neoproterozoic
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to Neogene (Appendix S3) (Guo et al., 2006 and references therein). The Au concentration of
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sedimentary rocks in Qinling orogen shows a decrease trend from Neoproterozoic to Neogene, and this
trend is also observed in west Qinling (Li, 2013 and references therein). With the published results in
the studied region, we think that the Neoproterozoic sedimentary rocks, which contains the highest Au
concentration, may have the potential to contribute Au (and possibly As) for Qiuling deposit during
regional metamorphism. This hypothesis is consistent with the fact that the Neoproterozoic strata in
this area has been metamorphosed to greenschist to lower amphibolite facies during the Triassic
orogeny (Zhang et al., 1995; Zhu et al., 2014), which generally meets the condition for breakdown of
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To evaluate the possible contribution of metal from Py1 during formation of the Qiuling deposit, it
is important to know the trace element concentration in Py1. Similar with As and Au, Py1 spots with
As concentration higher than 1700 ppm are dismissed because of possible contamination from Py2.
Co/Ni ratios have long been used to determine the origin of pyrite (hydrothermal vs.
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syngenetic/diagenetic; Bajwah et al., 1987; Bralia et al., 1979; Gregory et al., 2015; Large et al., 2014;
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Loftus-Hills and Solomon, 1967), and a Co/Ni < 2 is generally thought to be of sedimentary origin
(Large et al., 2014). The Co/Ni ratios of both Py1 and Py2 are ≤ 1, indicating that Py2 has a major
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contribution of sedimentary metal. This does not rule out the potential contribution from the
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ore-forming fluid, because metamorphic fluid derived from metamorphism of old sedimentary strata
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could possibly maintain its original nature (Co/Ni < 2). However, Py1 has higher concentrations in Co
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and Ni than Py2 (Fig. 8), and it is obvious that there is a decreasing trend from Py2a to Py2c in Co and
Ni. This makes it less possible that Co and Ni were sourced from the ore-forming fluid, and Py1 or the
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deep sedimentary strata is the most optimizing source for Co and Ni. Similar with Co and Ni, a
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decreasing trend from Py2a to Py2c is also observed in Bi, Mn and Tl, which support that they might
be also sourced from Py1. However, Cu and Sb concentration increase from Py1 to Py2c, indicating
Based on the discussion above, the ore-forming fluid should be rich in As, Au, Cu and Sb, while
depleted in other metals such as Bi, Co, Mn, Ni and Tl. Recent experiment study shows that, the pyrite
in pelite, which was possibly set to represent average composition of sediment rocks, could be
transformed to pyrrhotite at temperature down to 350~400 oC (Zhong et al., 2015). In the experiment,
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530oC is the watershed, before which (< 530oC) Au is released first, with other base metals (e.g., Cu,
Pb and Zn) tend to be maintained in the pelite, and after which (> 530oC) both Au and other base
metals (e.g., Cu, Pb and Zn) can be released. So, the As-, Au-, Cu- and Sb-rich nature of the
ore-forming fluid at Qiuling may indicate that the metamorphism temperature of the Neoproterozoic
basement had exceed 530oC, which is consistent with the observation that the Neoproterozoic basement
was generally metamorphosed to greenschist to lower amphibolite facies (Zhang et al., 1995; Zhu et al.,
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2014). Arsenic is not fully investigated in Zhong et al. (2015), but given their similar geochemical
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behavior (Deditius et al., 2014) and common presence of both elements in gold deposits (Xing et al.,
2019), it is possible that both As and Au would enter ore-forming fluid during breakdown of pyrite to
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pyrrhotite (Kusebauch et al., 2019). The conclusion above is in agreement with data collected from
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porphyry copper and geothermal system (Reich et al., 2013; Román et al., 2019; Tardani et al., 2017),
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in which elements including As, Au, Cu and, to a minor case, Sb are geochemically coupled at
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relatively high temperature. Besides, phase separation, which is thought to be able to alter fluid
composition and trace element partitioning into pyrite (Román et al., 2019), is unlikely at Qiuling
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because of the scarce of voids and mineral inclusion in Au-rich Py2b and Py2c.
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5.3. Ore-forming fluid evolution and implications for orogenic gold deposit modelling
Py1 was formed during diagenesis process, during which trace elements such as Bi, Co, Mn, Ni and
Tl were incorporated into the pyrite lattice. Py2 formed mainly from the ore-forming fluid with some
contribution of sulfur and trace element from Py1 during interaction of the ore-forming fluid with Py1.
The most convincing evidence supporting the interaction between Py1 and ore-forming fluid comes
from the texture. Two different types of pyrite were observed in the sedimentary host rocks, i.e.,
framboidal and euhedral pyrite (Figs. 2a-b). If there is no interaction between Py1 and the ore-forming
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fluid, the morphology of both types of pyrite should not change, which is hard to explain the ragged
rims of Py1 in many grains (Figs. 4b, 5g, 11a). Two additional evidences also support this hypothesis:
1) The intimate relationship of Py2a and Py1 in their sulfur isotope (Fig. 6a) indicates that Py1 may
have contributed some sulfur to Py2a; 2) The decreasing trend in the concentration of Co, Mn and Ni
(and maybe Bi and Tl) from Py1 to Py2c (Fig. 8) indicates that Py1 may have contributed some of
these trace elements to Py2. The contribution of sulfur and trace element could not happen if there is no
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interaction between Py1 and the ore-forming fluid. Py2a formed at the first introduction of the
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ore-forming fluid and may have leached some of the trace elements and sulfur from Py1 into the
ore-forming fluid (Fig. 13), which resulted in ubiquitous voids in Py1 (Fig. 2d). Euhedral Py2b may
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have formed in a situation similar to that of Py2a but with more contribution from the ore-forming fluid.
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The ore-forming fluids may have reacted with preexisting Py2a, leaching part of the trace elements
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(Fig. 10) from Py2a and resulting some voids in Py2a (Figs. 4d, 13). Py2c may have formed in a
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water-dominate environment, with no detectable contribution of base and precious trace elements and
sulfur from sedimentary pyrite. Since no replacement texture is observed between Py2b and Py2c,
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The deposition mechanism of Au is a complicated process that may relate to phase separation,
water-rock reaction, cooling, etc. (Goldfarb et al., 2005; Saunders et al., 2014). Based on the texture
observed in this study, water-rock reaction (Fig. 11) is possible. At the same time, the increasing
concentration of Au and As from Py2a to Py2c (Fig. 8) may suggest decreasing temperature because of
their retrograde solubility in pyrite (Deditius et al., 2014). Except for the mechanisms mentioned above,
carbonaceous matter in the host sedimentary rocks, which is suggested to have played a role during Au
deposition at Daqiao epizonal orogenic gold deposit in West Qinling orogen (Wu et al., 2020), also
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need investigation. The evidence present here is preliminary, and further studies are needed to fully
There are some debate on the genesis of Qiuling deposit, with previous research favoring it a
Carlin-like deposit in view the disseminated, low-temperature alteration assemblages and the Au-As-Sb
elemental association (Zhang et al., 2000). But there are a few characteristics at Qiuling that suggest
similarities with unequivocal orogenic gold deposits: 1) The Qiuling deposit is primarily controlled by
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NE-trend fault and its conjunction with NWW-trend faults (Fig. 1b). 2) Suggested formation age of this
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deposit is 232.7 ± 6.9 Ma (Zhao et al., 2001), synchronous with formation of the Qinling orogen (Dong
and Santosh, 2016; Dong et al., 2011) and other orogenic gold deposit in this region (Mao et al., 2002;
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Zeng et al., 2013). 3) The presence of visible gold (Liu et al., 2019; Yang et al., 2012). 4) Lack of
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decarbonatization. 5) The metamorphic ore-forming fluid identified in this study. We think that Qiuling
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deposit may share some characteristics with Carlin-like deposit, but given the evidences above we
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prefer it to be an epizonal manifestation of an orogenic gold system in the East Qinling orogen, which
has also been found in West Qinling orogen (e.g., Daqiao, Pangjiahe and Yangshan deposits) (Li et al.,
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The dispute rages regarding the genesis of the orogenic gold deposits at both Qiuling and many
other deposits of this type (Chang et al., 2008; Chen et al., 2015; Goldfarb and Groves, 2015; Large et
al., 2009; Large et al., 2007; Shen, 1996; Tomkins, 2013; Zhang et al., 2000; Zhang and Shen, 1996;
Zhang et al., 2002). Of all the models for orogenic gold formation, sources of fluid and metal have
been highly debated. Based mostly on limited bulk S and Pb isotope research, ore-forming fluid and
metal sourced from formation water and pyrite hosted in sedimentary wall rocks have long been
proposed at Qiuling (Shen, 1996; Zhang et al., 2000; Zhang and Shen, 1996; Zhang et al., 2002).
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However, as shown in this study, the δ34S range of pyrite hosted in sedimentary rocks can be over 135‰
(Fig. 3), which could be easily overlooked by bulk analysis and sampling bias and result in
misinterpretation of the data. In-situ sulfur isotope research by Chen et al. (2015) is the first attempt at
Qinling orogen to reveal the possible contribution of sulfur and Au from pre-ore pyrite hosted in
sedimentary wall rocks. But due to limited sulfur isotope data and failure to find large pyrite grain to
apply trace element analysis on pre-ore stage pyrite (Chen et al., 2015), concerns remain to the
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problems mentioned above. With a relatively large in-situ sulfur isotope data set on both pre-ore and
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multiple zonation of ore stage pyrite, coupled with trace element analysis of both stages, it is now
relatively sound to draw the conclusion here that the S-, As- and Au-bearing ore-forming fluid of the
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main Au mineralization is sourced from metamorphism of older strata at depth, with minor contribution
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of S, As and base metals from pre-ore stage pyrite in host rocks at the start of ore stage. Given the
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ubiquitous presence of complex zonation in pyrite hosted in orogenic gold deposits (Hazarika et al.,
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2017; Large et al., 2009; Large et al., 2007; Lawrence et al., 2013; Li et al., 2014; Tang et al., 2019;
Thomas et al., 2011), we suggest that in-situ sulfur isotope and trace element analysis based on detailed
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texture characterization is a powerful tool to reveal ore-fluid source and genesis of deposits of this type.
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6. CONCLUSION
Pre-ore stage pyrite (Py1) and three sub-stages of ore stage pyrite (Py2a, Py2b and Py2c) were
recognized at Qiuling deposit. Detailed in-situ sulfur isotope study has revealed that Py1 analyzed in
this study was formed by diagenesis process. The sulfur during formation of Py2 has contribution from
both Py1 and the ore-forming fluid, which has δ34S around +14.2‰. The ore-forming fluid eventually
came from sulfur released from pyrite possibly in Neoproterozoic basement during transition of pyrite
to pyrrhotite in regional metamorphism. Sulfur isotope suggest Py1 has contributed some sulfur during
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formation of Py2a. Py2b formed with elevated contribution from the ore-forming fluid, while
Au-bearing Py2c solely formed from the ore-forming fluid with no detectable contribution from
previous pyrite. Trace elements in Py2 such as Bi, Co, Mn, Ni and Tl are largely sourced from Py1.
Gold and As are sourced from the ore-forming fluid, which was eventually released from pyrite along
ACKNOWLEDGEMENTS
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This research was jointly supported by the Chinese National Science Fund for Distinguished Young
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Scholars (41725009) and the National Natural Science Foundation of China (41921003, U1603244,
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41903010). Comments from the editor, two anonymous reviewers and Prof. Martin Reich (Universidad
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de Chile, Santiago) significantly enhanced the manuscript, which is appreciated very much by the
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authors. Drs. Haoran Dou and Yang Xiao are thanked for helping with the EPMA and LA-ICP-MS
analysis, respectively.
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FIGURE CAPTIONS
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Fig. 1. (a) Simplified map showing tectonic division of the Qinling orogen. Also shown are the major
faults, gold deposits, and the location of Qiuling (adaped from Wu et al., 2018). The insert indicates the
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location of the West Qinling orogen in China. (b) Geology of the Qiuling gold deposit (dapted from
ur
Fig. 2. Different generations of pyrite and ore-stage mineral assemblages at Qiuling deposit. (a) Pre-ore
stage pyrite framboids (BSE image). Note the overprint of Py1 by ore stage Py2b (also shown in Fig.
3a). (b) Pre-ore stage euhedral pyrite (BSE image). (c) Typical mineral assemblage in ore stage. Note
that ore stage pyrite (Py2) is subdivided into Py2a, Py2b and Py2c (BSE image). Py2a is characterized
by dark BSE core and ubiquitous voids, Py2b by bright BSE bands and Py2c by BSE bands between
Py2a and Py2b. (d) Another ore stage pyrite grain (BSE image). Note euhedral Py2b and Py2c. (e)
Fig. 3. δ34S histogram of Py1 and Py2 at Qiuling deposit. Also shown are the average δ 34S values
(dashed lines).
Fig. 4. BSE images and δ34S values of Py2a, Py2b and Py2 at Qiuling deposit. The spots indicate
location of SIMS analysis spot and the number near them are δ34S values. The spots in white are Py1,
of
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spots in pink are Py2a, spots in yellow are Py2b and spots in blue are Py2c. Note the coexistence of
Fig. 6. δ34S relationship between pre-ore stage and ore stage pyrite. (a) Pre-ore stage vs Py2a. (b)
na
Fig. 7. BSE images and coupled EPMA As and S mapping of different generations of pyrite at Qiuling
ur
deposit. (a)-(c) Pre-ore stage pyrite overprinted by Py2b. (d)-(f) Coexistence of Py1 and Py2 in a single
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grain. (g)-(i) Typical ore stage pyrite grain showing different BSE bands and element concentration
zonation.
Fig. 8. Box plot of trace element concentration of Py1, Py2a, Py2b and Py2c.
Fig. 9. Co vs Ni plot of in-situ LA-ICP-MS analysis of Py1, Py2a, Py2b and Py2c. All analyses have a
Fig. 10. BSE image and coupled elemental mapping of major and trace elements in typical grain of Py2.
(a) BSE image. (b)-(c) Elemental mapping of As and S by EPMA. (d)-(m) Trace element mapping by
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LA-ICP-MS. Py2a is rich in Ag, Bi, Pb, Sb and Tl, Py2b is rich in Ag, Bi, Pb, Sb, Tl and As, while
Fig. 11. BSE image and coupled elemental mapping of trace elements in another grain of Py2. The
Fig. 12. Modeled δ34S values of (a) sedimentary pyrite and (b-c) the ore-forming fluid at Qiuling
deposit. The fractionation between seawater sulfate (+23‰) and pyrite (as low as -31.1‰) in panel a is
set at 54.1‰. The fractionation coefficient between SO42- and pyrite at different temperatures in panel
of
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b is taken from Sakai (1968). The diagram in panel c is modified from Ohmoto (1972). The diagram
denotes the fractionation of sulfur isotope at 250 oC, and more details please see text. Py: pyrite.
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Fig. 13. Schematic diagram showing formation of zonation in Py2 at Qiuling deposit.
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Table. 1 EMPA major element (wt%) and SIMS sulfur isotopic compositions (‰) of pyrite from
the Qiuling gold deposit
Sample ID Stage δ34 Fe S Ni As Co Zn Pb Cu Co/
na
S Total Ni
18QL04-18QL00 Py1 -31 45. 52. bdl bdl 0.2 bdl 0.0 bdl 98.6 --
ur
9@1 .1 94 32 1 9 9
18QL04-18QL00 Py1 -19 46. 53. 0.2 bdl 0.0 bdl bdl bdl 100. 0.40
9@2 .2 39 62 1 8 30
Jo
18QL03-18QL00 Py1 -30 45. 52. 0.0 bdl 0.1 bdl bdl bdl 98.8 1.80
9@1 .4 90 64 5 0 0
18QL03-18QL00 Py1 -25 46. 53. 0.0 bdl 0.0 bdl bdl bdl 100. 1.34
9@3 .2 11 68 6 9 06
18QL03-18QL03 Py1 31. 46. 52. bdl bdl 0.1 bdl bdl 0.0 99.1 --
9@10 5 34 55 3 6 6
18QL03-18QL00 Py1 -30 46. 52. 0.0 bdl 0.1 bdl bdl bdl 99.1 1.89
9@1 .4 04 90 6 1 1
18QL03-18QL00 Py1 -25 46. 53. bdl bdl 0.0 bdl 0.1 bdl 100. --
9@3 .2 10 84 8 0 15
18QL02-18QL04 Py1 -22 45. 53. 0.0 bdl 0.1 bdl bdl bdl 99.0 2.10
1@2 .1 30 44 5 1 1
18QL02-18QL04 Py1 -21 45. 53. bdl bdl 0.0 bdl bdl bdl 99.5 --
1@3 .6 65 72 9 4
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18QL02-18QL04 Py1 -34 45. 53. bdl bdl 0.0 bdl 0.0 bdl 98.9 --
1@4 .2 75 01 7 5 5
18QL02-18QL04 Py1 -21 46. 53. bdl bdl 0.0 bdl bdl bdl 99.6 --
7@1 .7 11 42 7 6
18QL02-18QL02 Py1 58. 45. 53. 0.1 bdl 0.0 bdl bdl 0.0 99.5 0.75
0@1 0 96 32 1 8 6 3
18QL02-18QL02 Py1 63. 45. 53. 0.2 bdl 0.1 bdl bdl bdl 99.2 0.50
0@2 8 56 31 3 1 7
18QL02-18QL04 Py1 -0. 45. 53. bdl bdl 0.0 bdl bdl bdl 99.5 --
7@6 5 75 61 9 6
18QL01-18QL03 Py1 3.8 46. 53. bdl bdl 0.1 bdl bdl bdl 99.4 --
8@2 16 05 1 0
18QL05-18QL00 Py1 2.1 45. 53. bdl bdl 0.0 bdl bdl 0.0 99.2 --
of
1@1 53 54 7 7 4
18QL05-18QL02 Py1 19. 46. 53. bdl bdl 0.0 bdl bdl bdl 100. --
ro
9@1 4 46 97 7 53
18QL05-18QL02 Py1 15. 46. 53. bdl
-p bdl 0.0 bdl 0.0 bdl 100. --
9@2 1 36 74 9 6 34
18QL05-18QL02 Py1 -5. 45. 53. bdl bdl 0.0 bdl bdl bdl 99.0 --
re
4@1 0 82 07 9 8
18QL05-18QL02 Py1 6.5 45. 52. 0.1 bdl 0.1 bdl bdl bdl 99.0 0.89
4@2 90 81 4 2 9
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18QL05-18QL01 Py1 0.2 46. 54. bdl bdl 0.0 bdl bdl bdl 100. --
1@1 15 00 8 23
18QL05-18QL01 Py1 0.8 46. 53. bdl bdl 0.0 bdl bdl bdl 99.8 --
na
1@2 17 49 6 2
18QL05-18QL01 Py1 0.2 47. 53. bdl bdl 0.0 bdl bdl 0.0 100. --
ur
1@3 05 80 7 5 99
18QL06-18QL00 Py1 4.8 46. 52. 0.0 bdl 0.0 bdl bdl bdl 99.3 1.18
5@1 14 98 6 7 3
Jo
18QL06-18QL00 Py1 6.1 46. 53. bdl bdl 0.0 bdl bdl bdl 99.4 --
5@2 16 22 8 7
18QL08-18QL02 Py1 -10 46. 52. bdl bdl 0.0 bdl bdl bdl 99.1 --
8@2 .4 03 92 8 1
18QL09-18QL03 Py1 -18 46. 53. 0.1 bdl 0.1 bdl bdl bdl 99.9 1.50
7@1 .3 20 48 1 6 7
18QL09-18QL04 Py1 -26 45. 53. 0.1 bdl 0.1 bdl 0.1 0.2 99.1 1.42
0@1 .7 21 23 1 6 1 2 6
18QL01-18QL03 Py1 -22 45. 53. 0.1 bdl 0.0 bdl bdl bdl 99.5 0.50
4@1 .8 91 38 6 8 6
18QL01-18QL03 Py1 -25 45. 53. bdl bdl 0.1 bdl bdl bdl 98.9 --
4@2 .4 76 09 1 8
18QL01-18QL02 Py1 -24 45. 53. 0.1 bdl 0.0 0.0 bdl bdl 99.1 0.78
7@1 .7 70 03 1 8 6 3
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18QL06-18QL01 Py1 -29 46. 53. bdl bdl 0.0 bdl 0.0 bdl 99.9 --
8@2 .9 00 72 9 5 0
18QL06-18QL00 Py1 -18 46. 53. bdl 0.1 0.0 bdl bdl bdl 99.8 --
4@6 .3 29 21 7 9 3
18QL06-18QL01 Py1 -31 45. 53. bdl bdl 0.0 bdl bdl bdl 99.1 --
8@1 .1 95 05 8 3
18QL02-18QL04 Py1 -17 46. 53. bdl bdl 0.0 bdl 0.1 bdl 100. --
1@5 .6 20 87 8 3 35
18QL09-18QL03 Py1 -30 45. 52. 0.0 bdl 0.1 bdl bdl bdl 98.9 1.24
7@2 .4 91 74 8 0 7
18QL03-18QL03 Py1+P -18 45. 48. 0.0 4.2 0.1 bdl 0.0 bdl 98.5 1.30
9@1 y2b .1 04 96 8 5 0 6 0
18QL03-18QL03 Py1+P -19 45. 50. bdl 3.4 0.1 bdl bdl 0.0 99.7 --
of
9@1 y2b .3 51 57 6 1 6 6
18QL07-18QL01 Py1+P 11. 44. 48. 0.0 5.4 0.1 bdl bdl 0.0 99.1 2.31
ro
7@3 y2b 4 44 99 5 5 3 7 9
18QL07-18QL01 Py1+P 12. 44. 50. 0.0
-p 3.0 0.1 bdl bdl 0.0 98.8 2.21
7@4 y2b 0 91 56 6 4 4 5 2
18QL03-18QL00 Py2a -2. 46. 53. 0.0 0.1 0.0 bdl bdl bdl 100. 0.89
re
9@2 7 40 77 8 6 7 54
18QL03-18QL03 Py2a 11. 45. 52. bdl 1.0 0.0 bdl bdl 0.0 99.8 --
9@3 8 81 74 4 9 9 2
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18QL03-18QL03 Py2a 10. 46. 53. bdl 0.8 0.0 0.0 0.1 0.0 100. --
9@6 9 13 05 9 6 7 5 6 41
18QL06-18QL00 Py2a 13. 46. 53. bdl bdl 0.0 bdl bdl 0.0 100. --
na
7@1 7 44 37 7 8 10
18QL07-18QL01 Py2a 15. 45. 52. 0.0 0.2 0.0 bdl 0.1 0.0 99.0 1.56
ur
7@5 4 73 72 5 0 8 1 6 0
18QL07-18QL01 Py2a 4.6 45. 54. bdl 0.1 0.0 bdl bdl 0.0 100. --
0@1 93 66 8 8 6 95
Jo
18QL08-18QL01 Py2a 33. 45. 53. bdl bdl 0.0 bdl bdl bdl 98.9 --
9@1 7 77 05 7 3
18QL08-18QL01 Py2a 31. 45. 52. bdl bdl 0.0 bdl bdl bdl 98.7 --
9@4 4 78 89 7 9
18QL01-18QL03 Py2a 13. 43. 47. bdl 7.6 0.0 bdl bdl 0.0 99.7 --
8@4 3 93 96 7 7 6 3
18QL03-18QL03 Py2b 12. 44. 49. bdl 7.1 0.0 bdl bdl 0.1 101. --
9@4 0 88 06 3 7 5 30
18QL03-18QL03 Py2b 12. 44. 48. bdl 7.6 0.0 bdl bdl 0.0 100. --
9@7 3 62 46 0 8 6 83
18QL06-18QL00 Py2b 13. 44. 50. bdl 4.2 0.0 bdl bdl 0.0 99.4 --
7@2 7 95 13 5 8 6 9
18QL07-18QL01 Py2b -- 44. 48. bdl 6.7 0.0 bdl bdl 0.1 99.9 --
7@1 47 58 0 7 1 5
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18QL07-18QL01 Py2b 13. 44. 49. bdl 6.1 0.0 bdl bdl 0.1 100. --
7@6 6 47 15 6 8 3 00
18QL07-18QL01 Py2b -- 44. 48. bdl 7.0 0.0 bdl bdl 0.1 99.8 --
7@8 18 43 1 6 2 5
18QL07-18QL01 Py2b -- 44. 48. bdl 7.2 0.0 bdl bdl bdl 100. --
0@2 45 38 0 8 18
18QL07-18QL01 Py2b 9.7 43. 47. bdl 8.3 0.0 bdl bdl 0.1 99.7 --
0@3 72 49 1 5 4 4
18QL08-18QL01 Py2b 19. 45. 50. bdl 4.5 0.0 bdl bdl 0.0 100. --
9@5 4 24 34 5 5 8 27
18QL01-18QL03 Py2b 9.2 44. 50. bdl 4.0 0.0 bdl bdl 0.0 99.5 --
8@5 96 40 2 6 7 1
18QL07-18QL01 Py2b -- 44. 48. bdl 7.1 0.0 bdl 0.0 0.1 100. --
of
7@2 39 50 1 9 6 4 31
18QL03-18QL03 Py2c 13. 46. 50. bdl 4.3 0.0 bdl bdl 0.0 101. --
ro
9@5 0 01 85 5 9 8 40
18QL03-18QL03 Py2c 12. 45. 49. bdl
-p 5.6 0.0 bdl bdl 0.0 100. --
9@8 6 04 73 7 7 5 58
18QL01-18QL03 Py2c 12. 45. 50. bdl 4.7 0.0 bdl bdl 0.0 100. --
re
8@6 1 07 43 2 6 8 39
18QL07-18QL01 Py2c 13. 44. 50. bdl 4.9 0.0 bdl bdl 0.0 100. --
7@7 1 99 05 5 9 5 15
lP
18QL08-18QL01 Py2c 16. 44. 51. 0.0 2.9 0.0 bdl bdl 0.2 99.7 0.87
9@2 5 98 46 8 2 7 0 1
18QL08-18QL01 Py2c 21. 45. 51. bdl 3.1 0.0 bdl bdl 0.0 100. --
na
9@3 7 19 56 4 7 8 06
18QL08-18QL01 Py2c 17. 45. 51. bdl 2.4 0.0 bdl bdl 0.0 99.1 --
ur
9@6 0 11 42 3 8 8 5
bdl: below detection limit.
--: no data.
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Table. 2 LA-ICP-MS trace element (ppm) in pyrite from the Qiuling gold deposit
Stage Mn Co Ni Cu As Ag Sb Au Tl Pb Bi
(ppm) (ppm) (ppm (ppm) (ppm) (ppm) (ppm (ppm) (ppm (ppm (ppm
) ) ) ) )
Py1@ 6.9 850.0 273.0 684.0 4630 4.8 670.0 1.5 1.1 1619. 34.8
1* 0.0 0
Py1@ 3.0 696.0 237.0 552.0 4060 3.7 546.0 0.6 1.0 1403. 26.1
2* 0.0 0
Py1@ 6.2 588.0 762.0 4300. 1268. 4.0 247.6 bdl 2.0 796.0 24.3
3 0 0
Py1@ 5.1 489.0 854.0 350.0 764.0 4.7 116.6 bdl 1.6 1193. 32.9
4 0
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Py1@ 114.1 396.0 385.0 330.0 3062 0.6 183.0 0.4 0.8 851.0 8.3
5* 0.0
Py1@ 251.1 164.5 302.0 74.3 501.0 0.5 117.2 bdl 0.6 240.7 5.1
6
Py1@ 203.0 118.6 258.0 63.4 426.0 0.5 58.4 bdl 0.5 240.0 5.5
7
Py1@ 174.3 107.5 236.0 58.7 403.0 0.5 74.2 bdl 0.5 216.0 5.4
8
Py1@ 3.8 1559. 870.0 411.0 3500 30.7 378.0 23.1 3.3 503.0 23.1
9* 0 0.0
Py1@ 3.5 1245. 493.0 394.0 3690 25.4 396.0 26.8 3.0 510.0 17.7
10* 0 0.0
Py1@ 26.2 1229. 512.0 428.0 4210 25.7 639.0 34.7 2.2 789.0 22.3
of
11* 0 0.0
Py1@ 1.7 0.5 14.7 41.8 8.8 0.6 0.6 bdl 0.2 3.5 bdl
ro
12
Py1@ 4.8 0.3 9.2 28.7 6.7 0.4
-p 0.1 bdl 0.2 6.0 bdl
13
Py1@ 1.9 5.1 41.8 46.3 10.4 0.8 0.9 bdl 0.3 9.6 bdl
re
14
Py1@ 106.6 28.4 189.5 146.7 119.6 1.2 31.3 0.4 4.1 404.7 bdl
15
lP
Py1@ 0.8 1.4 19.1 38.7 8.9 0.5 1.6 bdl 1.8 42.8 bdl
16
Py1@ 4.8 208.6 1128. 170.8 432.9 4.7 57.1 0.8 0.4 140.3 0.5
na
17 1
Py1@ 13.9 246.3 1079. 184.1 523.5 5.0 69.7 0.8 0.6 219.3 0.6
ur
18 9
Py1@ 81.2 36.1 167.6 133.6 43.7 0.4 4.2 0.9 3.0 425.9 0.2
19
Jo
Py1@ 7.9 7.5 41.9 55.7 81.0 0.2 1.2 bdl 0.3 61.6 bdl
20
Py1@ 64.7 1.3 39.4 96.9 22.8 2.2 2.6 9.4 0.5 26.6 0.4
21
Py1@ 18.2 107.2 492.9 545.9 80.3 2.2 15.8 4.3 0.3 214.0 2.1
22
Py1@ 3.7 1.2 19.0 54.8 9.0 0.9 0.5 bdl 0.2 5.1 bdl
23
Py1@ 70.1 21.3 156.2 155.0 181.7 0.9 46.1 0.7 2.3 509.3 bdl
24
Py1@ 37.6 64.8 208.1 106.2 137.3 1.0 38.3 0.4 2.2 361.6 bdl
25
Py1@ 71.9 55.0 226.2 143.3 117.8 1.3 32.1 0.4 2.9 467.9 bdl
26
Journal Pre-proof
Py1@ 43.7 18.7 91.4 124.2 27.6 1.7 7.9 bdl 4.6 182.3 bdl
27
Py1@ 49.2 49.2 208.8 108.3 63.8 0.7 13.7 bdl 2.3 547.8 bdl
28
Py1@ 1.3 4.3 114.0 41.9 133.7 0.4 24.2 0.2 2.3 119.4 bdl
29
Py1@ 0.9 1.9 40.0 31.8 13.7 0.4 3.0 bdl 1.9 60.4 bdl
30
Py1@ 82.2 3.3 104.4 130.4 42.2 0.6 1.9 0.5 0.6 76.6 bdl
31
Py1@ 15.0 11.6 94.5 42.8 28.4 1.1 12.8 bdl 0.4 81.1 bdl
32
Py1@ 2.4 1.4 15.9 35.1 7.5 0.6 0.3 0.2 0.2 8.2 bdl
of
33
256. 202. 246.
ro
Ave
49.0 86.8 1 270.7 3 1.4 36.3 1.6 1.4 7 7.7
Py2a 4.5 13.7 183.0 780.0 3970 3.9
-p 795.0 1.2 0.8 1784. 21.4
@1 0.0 0
Py2a 1.0 4.2 81.2 802.0 7220 1.4 324.0 2.8 0.6 482.0 8.6
re
@2 0.0
Py2a 2.0 5.2 50.0 891.0 7040 2.5 340.0 2.3 0.7 561.0 11.1
@3 0.0
lP
Py2a 82.6 12.5 273.0 759.0 4590 3.2 734.0 1.3 1.5 1270. 23.3
@4 0.0 0
Py2a 29.1 176.0 170.0 429.0 2940 3.0 418.0 0.8 2.3 880.0 16.0
na
@5 0.0
Py2a 7.8 4.7 40.2 706.0 4700 3.4 511.0 0.9 1.8 877.0 9.7
ur
@6 0.0
Py2a 1.0 2.6 75.6 644.0 7200 1.6 251.0 8.5 0.6 521.0 7.1
@7 0.0
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Py2a 1.4 1.4 39.1 577.0 3730 2.0 287.0 31.6 0.8 527.0 4.8
@8 0.0
Py2a 0.8 1.6 36.4 850.0 5760 1.4 279.0 5.5 0.4 425.0 4.5
@9 0.0
Py2a 0.9 5.9 63.0 735.0 5450 1.7 346.0 0.6 1.0 562.0 9.0
@10 0.0
Py2a 1.9 18.3 190.0 663.0 3940 2.6 416.0 3.5 0.5 2150. 10.4
@11 0.0 0
Py2a 8.9 6.6 147.0 903.0 3670 5.0 831.0 4.6 2.5 1228. 11.9
@12 0.0 0
Py2a 2.4 285.0 335.0 216.0 6800. 0.9 160.4 10.8 2.1 433.0 5.9
@13 0
Py2a 3.2 15.5 71.2 717.0 5380 14.6 767.0 9.9 1.5 1276. 3.1
@14 0.0 0
Journal Pre-proof
Py2a 1.7 22.4 45.3 795.0 4720 24.5 1280. 81.0 2.4 1870. 21.3
@15 0.0 0 0
Py2a bdl 11.0 37.0 722.0 2850 27.0 1730. 38.5 2.5 2869. 11.4
@16 0.0 0 0
Py2a 2.4 9.4 39.9 864.0 5720 23.1 863.0 11.7 2.1 995.0 7.8
@17 0.0
Py2a 6.6 16.2 68.2 726.0 4020 22.2 865.0 54.7 2.1 1029. 7.2
@18 0.0 0
Py2a 2.4 9.3 78.5 1420. 2990 25.2 859.0 8.5 2.1 1425. 4.9
@19 0 0.0 0
Py2a 2.0 6.6 81.3 645.0 9580. 21.8 938.0 0.5 1.5 1605. 2.1
@20 0 0
8.6 31.4 105.2 742.2 4376 9.5 649.7 14.0 1.5 1138. 10.1
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Ave
4.0 5
Py2b 1.2 1.1 27.2 788.0 7370 1.2 175.0 15.3 0.3 370.0 4.8
ro
@1 0.0
Py2b bdl 5.4 165.0 881.0 7580 0.6
-p 122.7 5.9 0.6 186.7 8.6
@2 0.0
Py2b bdl 2.6 48.0 867.0 7730 1.2 286.0 3.7 0.7 435.0 10.6
re
@3 0.0
Py2b 0.9 16.8 128.0 736.0 6020 1.1 145.2 15.9 0.8 250.0 9.5
@4 0.0
lP
Py2b bdl 5.7 74.1 781.0 7670 0.3 100.1 40.2 0.4 148.2 5.2
@5 0.0
Py2b bdl 0.9 24.4 872.0 7340 0.2 87.1 39.6 0.2 190.0 4.1
na
@6 0.0
Py2b 1.6 3.3 58.2 817.0 6900 0.6 163.0 52.0 0.5 316.0 4.8
ur
@7 0.0
Py2b 2.3 15.0 85.5 864.0 7050 2.2 373.0 50.6 1.1 584.0 9.9
@8 0.0
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Py2b bdl bdl 40.7 1136. 8460 1.5 202.0 13.5 0.6 312.0 4.5
@9 0 0.0
Py2b 9.3 3.8 71.0 1094. 8920 0.3 40.9 77.3 0.1 87.9 2.3
@10 0 0.0
Py2b bdl 5.7 22.3 1182. 8720 19.3 394.0 31.8 1.0 377.0 4.9
@11 0 0.0
Py2b 4.8 9.7 88.0 1038. 7480 16.3 522.0 101.2 2.1 552.0 9.7
@12 0 0.0
Py2b 1.8 12.4 28.0 1490. 6850 49.6 920.0 22.2 1.9 572.0 8.8
@13 0 0.0
Py2b 0.9 3.3 30.7 776.0 7090 1.0 161.0 19.8 0.5 362.0 6.4
@14 0.0
Py2b bdl 2.8 17.8 946.0 7540 1.0 150.0 18.1 0.3 145.2 2.6
@15 0.0
Journal Pre-proof
Py2b 1.2 1.0 17.4 670.0 6990 0.6 105.0 7.9 0.3 180.0 3.3
@16 0.0
Py2b bdl 5.5 46.1 738.0 6030 1.0 165.0 5.3 0.4 320.0 8.4
@17 0.0
Py2b 1.0 0.9 23.7 683.0 7210 0.5 76.0 24.8 0.2 119.0 3.4
@18 0.0
2.5 5.6 55.3 908.8 7386 5.5 232.7 30.3 0.7 305.9 6.2
Ave
1.1
Py2c 2.2 2.7 40.1 867.0 7920 0.4 99.0 41.5 0.2 204.0 3.8
@1 0.0
Py2c 1.1 2.0 10.6 665.0 6630 0.5 55.8 49.5 0.1 93.0 2.7
@2 0.0
Py2c 1.6 bdl 34.2 747.0 7910 0.8 98.7 51.2 0.3 172.0 4.3
of
@3 0.0
Py2c 3.7 11.9 58.0 684.0 6060 0.6 58.0 70.5 0.3 123.5 3.0
ro
@4 0.0
Py2c 1.2 37.0 91.0 711.0 6760 1.9
-p 256.0 17.2 0.6 413.0 9.7
@5 0.0
Py2c 2.6 7.8 78.0 516.0 5340 0.5 73.9 52.3 0.5 98.8 3.1
re
@6 0.0
Py2c 5.3 4.1 49.0 919.0 7520 4.8 358.0 71.6 1.1 528.0 10.5
@7 0.0
lP
Py2c 4.9 7.1 23.4 523.0 5630 2.0 73.6 68.5 0.3 130.3 1.3
@8 0.0
Py2c 1.2 14.7 24.6 1020. 1019 20.9 433.0 38.0 1.2 255.0 4.9
na
@9 0 00.0
Ave 2.6 10.9 45.4 739.1 7106 3.6 167.3 51.1 0.5 224.2 4.8
ur
6.7
bdl: below detection limit. Py1@1*: rejected data. The average values for Py1 do not include the
rejected points.
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Journal Pre-proof
☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests:
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Journal Pre-proof
Graphical abstract
Highlights
1. This study highlights the importance of detailed texture characterization coupled with
relatively large data set of in-situ sulfur isotope and trace elements for orogenic gold
deposit research.
2. The ore-forming fluid at Qiuling deposit may have sourced from metamorphism of the
regional Neoproterozoic basement, with no detectable contribution from magmatic
hydrothermal fluids.
3. Sedimentary pyrite in the wall rocks contributed negligible Au and As for mineralization
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at the Qiuling orogenic gold deposit.
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Figure 1
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Figure 13