Ore Geology Reviews 144 (2022) 104843

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Ore Geology Reviews

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Textures, trace element geochemistry and in-situ sulfur isotopes of pyrite

from the Xiaojiashan gold deposit, Jiangnan Orogen: Implications for
ore genesis
Huajie Tan a, b, Yongjun Shao a, b, Qingquan Liu a, b, *, Yu Zhang a, b, Yuzhou Feng a, b,
Yuce Zhang a, b, Sajjad Ahmad Shah a, b
a
Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitoring (Central South University), Ministry of Education, Changsha
410083, China
b
School of Geosciences and Info-Physics, Central South University, Changsha 410083, China

A R T I C L E I N F O A B S T R A C T

Keywords: The northeastern Hunan region in the Jiangnan Orogen (South China) is endowed with many important gold
Pyrite deposits, whose genesis remains controversial. The Xiaojiashan is a representative gold deposit (7.77 t Au @
Trace element geochemistry 2.88 g/t) in NE Hunan, and is characterized by multi-stage pyrite formation. Its mineralization can be divided
In-situ sulfur isotope
into 3 stages: (I) quartz-ankerite-pyrite-gold; (II) quartz-ankerite-polymetallic sulfide-gold; (III) quartz-ankerite
Xiaojiashan gold deposit
stage. Three pyrite generations were identified: fine-grained porous Py1 and coarse-grained Py2 in stage I,
Jiangnan Orogen
and core-rim-textured Py3 in stage II. Py1 and Py2 are enriched in Co, Ni, Se and Te, but depleted in As and Au.
Comparatively, Py3a and Py3b have higher As, Au, and Zn, but lower Co, Ni, Se and Te contents, indicating the
compositional variations of ore-forming fluids from stage I to stage II. The Au- and As-poor Py1 and Py2 have
similarly low δ34S values (Py1: − 33.30 to − 16.23 ‰; and Py2: − 25.41 to − 15.45 ‰), indicating that the sulfur
of Py1 and Py2 may have been derived from metamorphism of sedimentary strata, such as Neoproterozoic
Lengjiaxi Group. Meanwhile, both the core (Py3a) and rim (Py3b) of the Au-As-rich Py3 have high δ34S values
(Py3a: − 3.44 to − 1.72 ‰; and Py3b: − 1.00 to − 0.99 ‰), resembling typical magmatic sulfur. The trace element
compositions and sulfur isotopes of pyrite in stages I and II suggest a distinct shift of ore-forming fluids source
from metamorphic (stage I) to magmatic (stage II). Therefore, we propose that the Xiaojiashan gold minerali­
zation was likely associated with early metamorphism and late magmatic-hydrothermal overprinting, and its
multistage and complex ore-forming process had recorded the complexity of gold mineralization in NE Hunan.

1. Introduction a geochemical tracer to decipher the physicochemical conditions, hy­

drothermal fluids evolution and ore genesis in various types of gold
Pyrite is a common and omnipresent sulfide mineral in hydrothermal deposits, including IOCG (Groves et al., 2010; Steadman et al., 2021),
deposits of various types (Keith et al., 2018; Augustin and Gaboury, epithermal (Deditius et al., 2009; Kouhestani et al., 2017; Liu et al.,
2019). Previous research has highlighted that pyrite can contain sig­ 2018), intrusion-related (Li et al., 2019; Feng et al., 2020a, b; Sun et al,
nificant concentrations of trace elements (e.g., Mn, Co, Ni, Cu, Zn, As, 2020), Carlin-type (Large et al., 2011; Deditius et al., 2014; Hu et al.,
Se, Ag, Cd, Sb, Te, Au, Pb, Bi, Hg and Tl) as solid solution, nano- or 2018; Wei et al., 2020), orogenic (Cassidy, et al., 1998; Large et al.,
micro-inclusions (MacLean et al., 2008; Deditius et al., 2011; Ciobanu 2007, 2009; Deditius et al., 2014; Liu et al., 2021), and skarn deposits
et al., 2012; Reich et al., 2013). Concentration variations of these trace (Zhang et al., 2017; Zhang et al., 2022).
elements in pyrite are influenced by various factors, such as the element The Jiangnan Orogen in South China Block (Fig. 1a) was formed by
concentrations, temperature (T), pressure (P), acidity (pH) and oxygen the Neoproterozoic Yangtze–Cathaysia Block continent–continent
fugacity (fO2) of the hydrothermal fluids (Deditius et al., 2009, 2016; collision along the Shaoxing–Jiangshan–Piangxiang–Shuangpai fault
Voute et al., 2019; Wu et al., 2021). Therefore, pyrite is usually taken as zone (Yan et al., 2015). The orogen is a key gold producer in South

* Corresponding author at: School of Geosciences and Info-Physics, Central South University, No. 932 Lushannan Street, Changsha 410083, China.
E-mail address: [email protected] (Q. Liu).

https://doi.org/10.1016/j.oregeorev.2022.104843
Received 21 November 2021; Received in revised form 12 March 2022; Accepted 12 March 2022
Available online 15 March 2022
0169-1368/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
H. Tan et al. Ore Geology Reviews 144 (2022) 104843

Fig. 1. (a) Location map of the Jiangnan Orogen. (b) Simplified geologic map showing the gold deposits distribution in NE Hunan of the central Jiangnan Orogen
(modified after Xu et al., 2017a).

China, hosting a total gold resource more than 950 t (Deng et al., 2017). 2. Regional geology
Despite extensive studies on the regional gold mineralization, the
multiphase orogenic activities and the close spatial–temporal relation­ Northeastern Hunan district is one of the vital gold metallogenic
ship between the gold mineralization and granite, as well as the regions in Hunan Province, central Jiangnan Orogen (Fig. 1b). In this
complexity of the ore-forming fluids and materials source have led to the region, major gold deposits have been discovered (e.g., Huangjindong,
proposal of several metallogenic models, including SEDEX-type (Gu Wangu, Dadong, Tuanshanbei and Zhengchong; Fig. 1b; Fu et. al., 2002;
et al., 2005; Gu et al., 2007; Gu et al., 2012), intrusion-related (Jia et al., Han et al., 2010; Xu et al., 2017c; Liu et al., 2019). Exposed stratigraphy
2019; Li et al., 2019; Feng et al., 2020a, b; Li et al., 2021), orogenic-type in the region consists of the early-middle Neoproterozoic Lengjiaxi and
(Zhao et al., 2013; Xu et al., 2016; Zhang et al., 2020; Liu et al., 2019), Banxi Group metamorphic basement, and Paleozoic to Cenozoic sedi­
epithermal (Ye et al.; 1994), and intracontinental reactivation-type mentary rocks (Fu et. al., 2002; Han et al., 2010). The Lengjiaxi Group is
model (Deng et al., 2017; Xu et al., 2017a). a complex low-grade metamorphosed turbidites consisting of meta­
The Xiaojiashan gold deposit (reserve: 7.77 t @ 2.88 g/t; Hunan GSI, morphic siltstones and metagreywackes (zircon U–Pb age: 860 – 820
2015) is located in the central Jiangnan Orogen (Fig. 1b). Several studies Ma; Gao et al., 2011; Sun et al., 2012; Meng et al., 2013; Bai et al., 2021).
have been investigated on the geological features (Xie et al., 2007; Liu It is uncomfortably overlain by the Banxi Group metamorphosed clastic
et al., 2016; Cha et al., 2018; Liang and Wu, 2018; Long et al., 2018; Lin rocks of sandstones, slate, phyllites, intermediate-felsic tuffs, and con­
2020), fluid inclusions microthermometry (Tao et al., 2015) and ore- glomerates (Dong, et al., 2008; Gao et al., 2011). The Lengjiaxi and
forming materials source (Jiang et al., 2016). Due to the multistage Banxi Groups are the dominant wallrocks for most gold deposits in NE
and complex ore-forming process, and the deficiency of conventional Hunan. Unconformity by overlying the basement is the Sinian–Silurian
bulk isotope analyses, more precise mineralization data are needed to and Devonian–Triassic sandy shales, conglomerates and carbonates, as
reveal its genesis. Here, we conducted detailed geological investigations, well as the Cretaceous–Tertiary sandstones, conglomerates and grey­
and reported data for a paragenetically well-constrained suite of gold- wackes (Deng et al., 2017).
bearing pyrite samples from Xiaojiashan, using scanning electron mi­ Different episodes of intrusive activity were documented in NE
croscope (SEM) imaging of pyrite internal texture, combined with Hunan from the Neoproterozoicto to Mesozoic (Fig. 1b; Xu et al.,
EPMA, in-situ LA–ICP–MS trace element and LA–MC–ICP–MS sulfur 2017a). The Neoproterozoic and early Paleozoic intrusions are repre­
isotope analyses. Our results provide new clues into the ore-forming sented by the Daweishan granodiorite (biotite K–Ar age: 802 Ma; Jia
process and genesis of the Xiaojiashan gold deposit and help to under­ et al., 2002), and the Hongxiaqiao biotite granodiorite and Banshanpu
stand gold mineralization in the Jiangnan Orogen. biotite monzogranite (zircon U–Pb age: 423 – 421 Ma; Li et al., 2015),
respectively. Triassic intrusions are represented by the Wangxian

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Fig. 2. (a) Simplified geologic map of the Xiaojiashan gold deposit (modified after Jiang et al., 2015). (b) Generalized geological cross-section along the Xiaojiashan
prospecting line No. 3. Green stars denote the sampling locations (modified after Hunan GSI, 2015).

granodiorite-porphyry (zircon U–Pb age: 224.7 ± 4.4 Ma; Yang et al., The NW- and NE-trending faults are the primary structure at Xiao­
2018). Jurassic intrusions are the most widespread and characteristi­ jiashan, and NW-trending faults commonly crosscut the NE-trending
cally S-type, e.g., the Lianyunshan two-mica monzogranite (zircon U–Pb ones (Fig. 2a). The NE-trending faults are mainly present as inter-/
age: 149 ± 1 Ma; Xu et al., 2017b) and the Mufuxian biotite mon­ intra-layer detachment faults, which show a ductile to brittle deforma­
zogranite (zircon U–Pb age: 151.5 ± 1.3 Ma; Wang et al., 2014). tion history (Fig. 3a). In addition, The ENE-trending Hongjiachong
Regional structures in northeastern Hunan district include mainly overturned syncline is the main fold at Xiaojiashan, and controls the
three ductile-shear zones (Cili–Linxiang, Xiaochijie–Lianyunshan and orebodies distribution (Fig. 2a). The NE-trending structures have been
Anhua–Liuyang ductile-shear zone) and Basin-and-Range-like topog­ interpreted to be the auriferous fluid conduits and ore precipitation sites
raphy (Fig. 1b; Han et al., 2010; Xu et al., 2017c; Zhou et al., 2019). of auriferous fluids in this region (Xu et al., 2017c).
Various E-W-, NE- and NW-trending faults formed in the early episode The Xiaojiashan gold deposit consists of 109 orebodies, most of
are cut or reactivated by the dominantly NE- to NNE-trending faults. The which (esp., V1–1 and V19–1 orebodies) occur as NE-trending veins/
gold deposits are spatially concentrated along the regional NNE- veinlets in the Hongjiachong overturned syncline (southern flank).
trending faults, which imposed first-order structural control. However, Orebodies V1–1 are 200 – 270 m long and 0.80 – 3.83 m wide with a
the gold mineralization is mainly hosted within the second- or third- gold grade of 0.66–6.04 g/t (Hunan GSI, 2015). Metallic minerals are
order faults, such as the NNE- and NW-trending ones. dominated by pyrite, arsenopyrite (Fig. 3b–g), native gold, and minor
sphalerite, galena, chalcopyrite, tetrahedrite and pyrrhotite. Gangue
3. Deposit geology minerals consist mainly of quartz, ankerite, sericite and chlorite. Ore-
related alterations include mainly sulfidation (pyrite and arsenopy­
The Xiaojiashan gold deposit is situated southeast of the regional rite), silicification, carbonatization, sericitization and chloritization
Changsha–Pingjiang Fault in NE Hunan (Fig. 1b). It has three orebody (Fig. 3h and i).
clusters, which are mainly hosted in the low-grade metamorphic Leng­ Based on the vein cross-cutting relationships and mineral assem­
jiaxi Group (Huanghudong Formation) turbidites and deep-marine pel­ blages, the mineralization at Xiaojiashan can be divided into three stages
itic sequences (Fig. 2a). The Huanghudong Formation comprises three (Fig. 3b–g), namely: (I) quartz-ankerite-pyrite-gold, (II) quartz-ankerite-
members: (lower member) quartz sandstones and silty slates; (middle polymetallic sulfide-gold; (III) quartz-ankerite. The paragenetic
member) phyllites and silty slates/sandy slates; (upper member) meta­ sequence is illustrated in Fig. 4.
sandstones and silty slates (Jiang et al., 2016). Most of the gold-bearing Stage I represents the first Au mineralization stage and is charac­
quartz veins occur within the lower and middle members (Fig. 2a and b). terized by NE-trending white and smoky-gray quartz-ankerite veins/
No plutons are exposed on the surface, and only a few mafic rocks veinlets (0.2 to 5 cm in width; Fig. 3b). The bedding and sinuous quartz-
were intercepted at depth by drilling (Liu and Xu, 2016; Liang and Wu, ankerite-pyrite veins are commonly parallel (Fig. 3b), and metallic
2018), although magnetic anomaly infers possible existence of con­ minerals are dominated by fine-grained pyrite (Py1) in early stage I,
cealed plutons beneath the Zhengchong–Xiaojiashan–Yanlinsi goldfield coarse-grained pyrite (Py2) in middle stage I and minor native gold,
(Huang et al., 2012; Xu and Wen, 2016). chalcopyrite, sphalerite, galena, tetrahedrite and pyrrhotite in late stage

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Fig. 3. Field photographs of parallel gold-bearing quartz-ankerite veins (a), hand-specimens of the ore veins and their crosscutting relationships (b-g) and polarized
light photomicrographs of the ore-related alteration (h-i) from Xiaojiashan: (a) Mineralization occurred in the NE-trending inter-/intra-layered detachment faults. (b)
Stage I sinuous smoky-gray quartz-ankerite veins are parallel to bedding. (c) Stage II smoky-gray quartz-ankerite vein and alteration halo with disseminated pyrite
and arsenopyrite. (d) Alteration halo with disseminated pyrite and arsenopyrite along stage II quartz-ankerite vein. (e) Stage II quartz-ankerite vein overprinted stage
I quartz-ankerite vein. (f) Stage III quartz-ankerite vein cut stage I quartz-ankerite vein. (g) Stage III quartz-ankerite vein cut stage II quartz-ankerite vein. (h) Silicic
and carbonate alterations associated with gold mineralization. (i) Silicic, sericite and chlorite alterations associated with gold mineralization. Py – pyrite, Apy –
arsenopyrite, Ccp – chalcopyrite, Qz – quartz, Ank – ankerite, Ser – sericite, Chl – chlorite.

I. These veins are surrounded by alteration halos displaying sulfidation, internal texture of pyrite. Among these 33 pyrite samples, nine were
silicification, carbonatization, sericitization and chloritization, which selected for EPMA analysis, eight for trace element spot analysis, and six
are usually several times wider than the veins. for in-situ sulfur isotope analysis. Detailed samples descriptions and
Stage II represents the second Au mineralization stage and is marked analytical methods are given in Appendix I and II, respectively.
by NE-trending bed-parallel smoky-gray quartz-ankerite veins (0.2 to
10 cm in width). Metallic minerals are dominated by medium-grained 5. Results
pyrite (including Py3a core and Py3b rim) and arsenopyrite with
minor native gold, sphalerite, galena, chalcopyrite and tetrahedrite Three generations of pyrite are identified at Xiaojiashan, i.e., Py1
(Fig. 3c-d). The alteration minerals are represented by quartz, ankerite, and Py2 in stage I, and Py3 in stage II. The 190, 143 and 51 spot analyses
sericite and chlorite. Disseminated arsenopyrite is the main sulfide for EPMA (Py1 = 60, Py2 = 93, Py3a = 19, Py3b = 18), for LA–ICP–MS
mineral in the alteration halos (Fig. 3d). These veins commonly over­ (Py1 = 60, Py2 = 47, Py3a = 22, Py3b = 14) and for LA–MC–ICP–MS
printed the stage I quartz-ankerite veins (Fig. 3e). (Py1 = 20, Py2 = 16, Py3a = 13, Py3b = 2) were performed on the four
Stage III is characterized by the thick milky quartz-ankerite veins types of pyrite. The data are summarized in Appendix III to V and the
with widths from 1 to 15 cm, which are ore-barren and commonly cut variation are exhibited in Figs. 5-9.
stage I and II veins (Fig. 3f and g). The alteration halos generally have
weak silicification and carbonatization.
5.1. Petrogenesis of the Xiaojiashan pyrite
4. Samples and analytical methods
Py1 (stage Ia) is fine-grained (10 – 50 μm) euhedral-subhedral
Thirty-three pyrite-bearing samples were collected from the drill (Fig. 5a), and commonly occurs as irregularly-shaped porous aggre­
cores (ZK0304, ZK0703, ZK3502, ZK3507 and ZK4701) at different gates (size: 50 to hundreds of μm) (Fig. 5b) with silicate inclusions. Py1
levels. The samples were prepared into thin sections for optical and SEM is texturally homogenous under BSE imaging (Fig. 5a). In addition, some
petrographic observation, particularly to identify the generation and Py1 aggregates have abundant polymetallic sulfides (mostly chalcopy­
rite, sphalerite, galena, tetrahedrite, pyrrhotite) and some native gold in

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Fig. 4. Mineral paragenetic sequence for the Xiaojiashan gold deposit.

their voids (Fig. 5b). 17 – 6798 ppm (avg. 1663 ppm) As.
Py2 (stage Ib) is coarse-grained (40 μm – 1.5 mm) subhedral- Py3 has significantly higher Au and As concentrations than Py1 and
euhedral (Fig. 5c–e), and is free of silicate inclusions. Py2 is also Py2 (Fig. 7), consistent with the EPMA results. Concentrations of many
texturally homogenous under BSE imaging (Fig. 5e), and locally display other elements (e.g., Mn, Co, Ni, Cu, Se, Ag, Cd, Sb, Te, Pb and Bi) of Py3
the characteristics of cataclastic textures (Fig. 5f). Minor sulfides (e.g., are lower than Py1, but Zn concentration is higher. The Au concentra­
chalcopyrite, sphalerite, galena, tetrahedrite, pyrrhotite) and native tion of Py3a (0.43 – 487 ppm, avg. 104 ppm) is slightly higher than Py3b
gold occurred within or locally along the fractures of Py2 (Fig. 5e and f). (0.25 – 115 ppm, avg. 17 ppm). The As concentrations of Py3a (2964 –
Py2 commonly replaced and overgrown onPy1 (Fig. 5c–e). 41310 ppm, avg. 20081 ppm) and Py3b (3602 – 25519 ppm, avg. 9929
Py3 (stage II) is commonly medium-grained (100 – 600 μm) ppm) are similar.
subhedral-euhedral (Fig. 5g). Under BSE imaging, Py3 is characterized All types of pyrite show a significant positive Au vs. As (Fig. 8a), Co
by core-rim texture (Fig. 5g), with the core (Py3a) being brighter than vs. Ni (Fig. 8b), and Pb vs. Ag, Bi, Sb (Fig. 8f–h) correlations, while no
the rim (Py3b) (Fig. 5g). Py3a is locally oscillatory or irregularly zoned obvious correlation is observed between Au and Cu, Ag, Te (Fig. 8c–e).
(Fig. 5g), whereas Py3b is homogeneous (Fig. 5g). Native gold occurs as
fine grain (Fig. 5h) or along the grain margin (Fig. 5i) of Py3. In some
places, Py3a is overgrown on the darker Py1 and Py2 core (Fig. 5g) with 5.4. LA–MC–ICP–MS in-situ sulfur isotopes of pyrite
corrosive texture along the boundaries between Py2 and Py3a (Fig. 5g).
Py1 has the δ34S values of –33.30 to –16.23 ‰ (mean value –22.36‰;
Fig. 9a and b); Py2 has are the δ34S values of –25.41 to –15.45 ‰ (Fig. 9a
5.2. EPMA pyrite major element compositions and b) and similar mean value of –22.60‰ to that of Py1. Py3 has higher
δ34S values than those of Py1 and Py2: Py3a has a narrow δ34S range
Major element compositions of Py1 and Py2 have no systematic (–3.44 to –1.72‰; Fig. 9a and b) and mean δ34S = –2.32‰. Py3b has
difference, with 45.04 – 47.83 wt% Fe, 51.30 – 54.11 wt% S, and 0.16 – similar and slightly higher δ34S values than Py3a, which range from
0.98 wt% As. Py3a and Py3b have higher As than Py1 and Py2, with –1.00 to –0.99‰ (mean –1.00‰; Fig. 9a and b).
Py3a and 3b having 45.05 – 47.57 wt% Fe, 50.28 – 53.47 wt% S and 0.29
– 4.02 wt% As. The Fe, S and As concentrations of Py1 to Py3 are shown
6. Discussion
in the ternary Fe–S–As (Fig. 6a) and S vs. As (Fig. 6b) plots.
6.1. Trace element occurrence in pyrite
5.3. LA–ICP–MS trace element compositions of pyrite
Pyrite is a sink for many trace elements, such as Co, Ni, As, Au, Ag,
Py1 contain a variety of trace elements, especially chalcophile ones Se, Te and other metals, and these trace elements are incorporated into
(Co, Ni, Cu, Se, Ag, Sb, Te, Pb and Bi). Concentrations of Zn, As and Au pyrite in different ways, e.g., (1) micro- to nano-sized mineral in­
are generally low (Fig. 7). Py1 has the highest Cu, Ag, Sb, Pb and Bi clusions, (2) solid solution within the crystal lattice via isovalent or
concentrations among the different pyrite types. Py1 has 0.04 – 1.50 coupled heterovalent substitutions for Fe2+ or S− (Chouinard et al.,
ppm (avg. 0.45 ppm) Au and 414 – 8745 (avg. 2079 ppm) As. 2005; Deditius et al., 2008, 2009, 2011; Large et al., 2014; Deditius and
Py2 has slightly lower concentrations of Co, Cu, Zn, As, Se, Te and Au Reich, 2016; George et al., 2019).
than Py1, while its Ni concentration is slightly higher. The concentra­ Cobalt, Ni and Cu are likely to be an isovalent substitution of Fe2+ by
tions of some chalcophile elements (e.g., Ag, Cd, Sb, Pb and Bi) are much Co2+, Ni2+ and Cu2+, owing to the structural affinity of FeS2-CoS2-NiS2-
lower than Py1 (Fig. 7). Py2 has 0.03 – 1.07 ppm (avg. 0.28 ppm) Au and CuS2 system (Deditius et al., 2008; Román et al., 2019). The smooth and

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Fig. 5. Scanning electron microscopy (SEM) imaging (a, b, d, e and g) and reflected-light (c, f, h and i) photomicrographs of the Xiaojiashan Py1 to Py3 mineral
assemblages and textural features. (a) Py1 occurred as fine-grained and irregularly shaped aggregates in quartz-ankerite vein. (b) Irregularly-shaped Py1 aggregates
with abundant silicate, galena and native gold inclusions. (c-d) Py1 aggregates replaced and enveloped by subhedral Py2. (e) Coarse-grained euhedral Py2 is
inclusion-free and enveloped Py1. (f) Chalcopyrite, sphalerite and native gold in Py2 fractures. (g) Py3 shows core-rim texture (Py3a and Py3b). Py3a shows local
oscillatory zoning, and partially replaced/overprinted Py2. (h) Arsenopyrite and native gold occur as fine-grained in Py3a. (i) Native gold occurs along the margin of
Py3a. Py – pyrite, Ccp – chalcopyrite, Sp – sphalerite, Gn – galena, Apy – arsenopyrite, Au – native gold, Qz – quartz, Ank – ankerite, Ser – sericite, Red circles – sulfur
isotopic values, Yellow circles – As and Au concentrations.

Fig. 6. Ternary As–Fe–S (a) and S vs. As (b) plots for the Xiaojiashan pyrite.

flat time-resolved depth-profiles of Co, Ni and Cu for most of our pyrite via substitution of the tetrahedrally-coordinated S− by As− or
samples indicate that Co, Ni and Cu likely occur as solid solution in octahedrally-coordinated Fe2+ by As2+/3+ (Fig. 6a; Deditius et al.,
pyrite (Fig. 10a and b). Arsenic can be integrated into the pyrite lattice 2009). As shown in Fig. 6a, the substitution of As2+/3+ for Fe2+ could be

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Fig. 7. Concentration boxplot showing selected trace element concentrations of Py1 to Py3 from Xiaojiashan.

excluded. Moreover, the substitution of As2+/3+ by Fe2+ commonly oc­ (pH) of the ore-forming fluids (Ohmoto, 1972). Sulfur isotopes of sul­
curs under relatively oxidizing conditions (Deditius et al., 2008; Deditius fides can approximate those of the ore-forming fluids under medium-low
et al.,2009), inconsistent with the ore-forming environment at Xiaojia­ temperature and reducing conditions (Ohmoto, 1972; Zheng et al.,
shan by the mineral association, which is likely reducing as evidenced by 2020). At Xiaojiashan, the ore-forming fluids are 202 to 282 ◦ C for stage
the absence of hematite or sulfates (Xie et al., 2007; Liu et al., 2016; Lin, I, 238 to 305 ◦ C for stage II, and 164 to 224 ◦ C for stage III (fluid in­
2020). Selenium commonly enters the pyrite lattice via isovalent sub­ clusions microthermometric data), respectively, and contain CH4, CO2,
stitution of S− (Maslennikov et al., 2009; Keith et al., 2018; Zhang et al., N2 and H2O (#416 Brigade Hunan BGMR, 2019), and no hematite or
2022). The smooth and flat time-resolved depth-profiles of As and Se for sulfates (e.g., gypsum and barite) were recognized, suggesting that the
our pyrite samples suggest that As and Se occur as solid solution in pyrite ore-forming fluids are medium-low temperature and reducing. Hence,
(Fig. 10a and b). For Py3, As and S show strong negative correlation δ34S values of the Xiaojiashan pyrite can approximate those of the ore-
(rPy3 = –0.78; Fig. 6b), indicating major substitution of S− by As− . forming fluids.
Meanwhile, As and S in Py1 and Py2 show weak negative correlation Py1 (− 33.30 to − 16.23 ‰, avg. –22.36 ‰) and Py2 (− 25.41 to
(rPy1 = –0.30; rPy2 = –0.32), suggesting that the S− substitution could be − 15.45 ‰, avg. –22.60 ‰) have wide-range and low δ34S values
related to other elements (such as Se). Previous studies suggested that (Fig. 11a and b), indicating that their sulfur source is similar and un­
substitution of S− by As− could lower the symmetry of iron atoms in related to magmatic sulfur (δ34S = 0 ± 3 ‰; Ohmoto, 1972) or seawater
pyrite, causing pyrite structural defects, which is conducive to gold sulfate (δ34S = ca. +23 ‰; Wu et al., 2014). The most reasonable source
incorporation into the distorted octahedral sites (Simon et al., 1999a, b; for Py1 and Py2 with such low δ34S values at Xiaojiashan is probably
Reich et al., 2005; Reich et al., 2013). Hence, the relatively high Au metamorphic sulfur which sourced from metamorphism of sedimentary
content in Py3 is likely related to the high As content. strata. The δ34S values from the Neoproterozoic Lengjiaxi Group in NE
The smooth and flat time-resolved depth-profiles of Au indicate the Hunan have been reported at − 13.10 to − 6.26 ‰ (Fig. 9a; Luo, 1988;
existence of invisible gold, which can occur as: (1) solid solution Au+ Liu et al., 1994; Liu et al., 1999; Xu et al., 2017a). The δ34S values of Py1
replacing Fe in the crystal lattice; (2) native Au0 nanoparticles (Reich and Py2 are similar to the end-member value (δ34S = − 13.10 ‰) of the
et al., 2005; Deditius et al., 2008). Strong positive Au vs. As correlation Lengjiaxi Group, suggesting that the Lengjiaxi Group may have been a
(r = 0.85; Fig. 8a) is present in our samples, and the coupled potential sulfur source for Py1 and Py2. Previous S–Pb–H–O isotopes
geochemical behaviors could be observed in numerous gold deposits, studies on other gold deposits (e.g., Huangjindong and Wangu) in NE
such as Carlin-type (Reich et al., 2005; Deditius et al., 2014; Yan et al., Hunan have also yielded similar conclusion, that the main sulfur source
2018), epithermal (Kouhestani et al., 2017; Sykora et al., 2018) and was likely the Lengjiaxi Group metasedimentary rocks (Fig. 9a; Deng
orogenic gold deposits (Cook et al., 2013; Zhang et al., 2014; Wu et al., et al., 2017; Xu et al., 2017a; Huang et al., 2020).
2019). As shown in Fig. 8a, all the data from Xiaojiashan points fall Py3a (–3.44 to –1.72 ‰, avg. –2.32 ‰) and Py3b (− 1.00 to − 0.99
below the Au solubility curve, indicating that the invisible gold occurs as ‰, avg. –1.00 ‰) have similar δ34S values (Fig. 9a and b), respectively,
solid solution in all Py1 to Py3. similarly to the δ34S values of pyrite (–5.25 to –2.05‰) and arsenopyrite
Lead usually cannot occur within the pyrite lattice due to the larger (–1.15 ‰) from Xiaojiashan (Jiang et al., 2016), pyrite (mostly –6.04 to
ionic radius than Fe2+, and thus it occurs mainly as micro/nano-sized –0.45 ‰) and arsenopyrite (–1.67 to 1.16 ‰) from Yanlinsi (Dong et al.,
Pb-bearing mineral inclusions in pyrite. Galena micro-sized inclusions 2008; Jiang et al., 2016), pyrite (–8.90 to –1.70 ‰) and arsenopyrite
were identified by the signal spikes of Pb in the time-resolved depth- (–2.10 to –0.10 ‰) from Zhengchong (Liu et al., 2019) and pyrite (–0.11
profiles (Fig. 10c and d). In some spots, the signal spikes of Pb-Bi-Ag-Sb to 0.65 ‰) from Jinkengchong (Xu et al., 2016). This indicates that Py3a
are consistent with the positive correlation between these elements and Py3b are derived from a similar magmatic-related sulfur reservoir
(Fig. 8f–h; Fig. 10c and d), indicating that the Pb-Bi-(Ag-Sb)-bearing (δ34S = 0 ± 3‰; Ohmoto, 1972), but markedly different from that of
mineral inclusions are also present. Meanwhile, Cu-bearing micro- stage I mineralization (Py1 and Py2). The possible magmatic source may
sized mineral inclusions (possibly chalcopyrite) can be identified from have been the concealed plutons interpreted from the magnetic anomaly
the Cu signal spikes (Fig. 10c and d). beneath the Zhengchong–Xiaojiashan–Yanlinsi goldfield (Huang et al.,
2012; Liu and Xu, 2016; Xu and Wen, 2016; Liang and Wu, 2018).
6.2. Source of sulfur The trace element compositions of Py1, Py2 and Py3 support that the
sulfur source and composition may have shifted from metamorphic
The sulfur isotope composition of sulfide is determined by the total (stage I) to magmatic (stage II). Py1 and Py2 are enriched in Co, Ni, Se
sulfur composition, temperature (T), oxygen fugacity (fO2), and acidity and Te, but depleted in As and Au contents. Comparatively, Py3a and

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Fig. 8. Bivariate plots of trace elements in Py1 to Py3 from Xiaojiashan. (a) Au vs. As. (b) Co vs. Ni. (c) Ag vs. Au. (d) Te vs. Au. (e) Cu vs. Au. (f) Ag vs Pb. (g) Bi vs.
Pb. (h) Sb vs. Pb.

Py3b have higher As, Au, and Zn, but lower Co, Ni, Se and Te contents. In 6.3. Origin of pyrite
the As/Au vs. Co/Ni binary plot, Py1 and Py2 have wider Co/Ni range
and higher As/Au ratio than Py3a and Py3b (Fig. 11). The sharp grain Pyrite Co-Ni and Co/Ni contents are sensitive to physicochemical
boundary between Py2 and Py3a (Fig. 5g) and distinct mineral assem­ conditions and can provide information to identify its origin (Bajwah
blages (Py3-arsenopyrite) also support that the fluid sulfur source and et al., 1987, Brill, 1989, Hou et al., 2016). Generally, pyrite with Co/Ni
composition have changed. Similar conclusion is drawn from the <2 is attributed to sedimentary origin (Large et al., 2014; Gregory et al.,
Huangjindong Au deposit (NE Hunan), based on S-Pb isotopes, Ar-Ar 2015), whilst hydrothermal pyrite usually has Co/Ni >1 (1.17–5.00)
dating and fluid inclusions evidence (Xia et al.,2017; Deng et al., 2020). (Bajwah et al., 1987; Large et al., 2009; Deol et al., 2012; Reich et al.,
2016; Chinnasamy et al., 2021). Most Co/Ni data points of Py1 and Py2

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H. Tan et al. Ore Geology Reviews 144 (2022) 104843

Fig. 9. (a) δ34S boxplot of pyrite and arsenopyrite from the Lengjiaxi Group and the gold deposits in NE Hunan. Sulfur isotope data of the Lengjiaxi Group (Luo,
1988; Luo, 1990; Liu et al., 1999; Xu et al., 2017a) and the gold deposits of Wangu (Deng et al., 2017; Xu et al., 2017a), Huangjindong (Xu et al., 2017a), Jing­
kenchong (Xu et al., 2017a), Zhengchong (Liu et al., 2019), Yanlinsi (Dong et al. 2008; Jiang et al., 2016), and Xiaojiashan (Jiang et al., 2016) are shown for
comparison. (b) δ34S histograms of Py1 to Py3 from Xiaojiashan.

are <2 (Fig. 8b), indicating a mainly sedimentary origin, which agrees Furthermore, the As/Ni (8.90–187.63, avg. 93.99; 13.03–493.80, avg.
with the sulfur isotope data afore mentioned. In addition, our Py1 and 86.17, respectively), Te/Au (0.01–1.63, avg. 0.20; 0.02–0.51, avg.
Py2 samples have mostly As/Ni (0.54–28.83, avg. 0.54; 0.01–27.84, avg. 0.20), and Bi/Au (0.01–3.23, avg. 0.32; 0.01–5.40, avg. 0.68) ratios for
6.83), Te/Au (1.67–138.31, avg. 17.53; 0.88–226.23, avg. 69.15) and Py3a and Py3b are inconsistent with a sedimentary origin. Py3a and
Bi/Au (2.03–715.28, avg. 66.91; 0.29–190.91, avg. 30.97), respectively, Py3b have a magmatic sulfur-like δ34S values (Py3a: − 3.44 to − 1.72‰;
which also support the conclusion as sedimentary pyrite has 0.01< As/ Py3b: − 1.00 to − 0.99‰). Hence, Py3a and Py3b is likely genetic links
Ni <10, 1< Te/Au <1000, and 1< Bi/Au (Gregory et al., 2015). The with magmatic-hydrothermal fluids.
coexistence of Py1 and Py2 with hydrothermal quartz, ankerite, sericite
and chlorite demonstrate the hydrothermal origin of Py1 and Py2, and
suggest major metamorphic fluid input derived from the metamorphism 6.4. Trace element variations and implications on ore-forming fluid
of sedimentary strata. This conclusion is supported by fluid inclusions evolution
microthermometry (#416 Brigade Hunan BGMR, 2019). The stage I
fluids are characterized of high CO2 content, medium temperature, and Previous investigations have demonstrated that Se incorporation in
low salinity, similar to typical metamorphic-derived hydrothermal pyrite correlates negatively with hydrothermal fluid temperature, irre­
fluids (Goldfarb et al., 2001; Goldfarb et al., 2005; Tomkins, 2013; spective of pH and fO2 (Huston et al. 1995; Maslennikov et al., 2009;
Groves et al., 2020). Keith et al. 2018). The median Se content increases from Py1 (38.88
The Co/Ni ratios of Py3a and Py3b are in the range of 0.06–0.61 ppm) to Py2 (43.71 ppm) in stage I (Fig. 7), and from Py3a (19.12 ppm)
(avg. 0.25), and 0.06–0.23 (avg. 0.14), respectively, indicating Py3a and to Py3b (20.73 ppm) in stage II (Fig. 7), suggesting fluids temperature
Py3b may have a sedimentary origin. However, this cannot rule out could decrease from Py1 to Py2 in stage I, and from Py3a to Py3b in stage
potential hydrothermal contribution, because due to the coexistence of II. In addition, pyrite Co content is also affected by the fluids tempera­
Py3 with hydrothermal quartz, ankerite, sericite and chlorite. Adam ture (Migdisov et al., 2011; Roman et al., 2019), and a temperature drop
et al. (2020) and Zhang et al. (2022) reported that mineralogical char­ from 300 to 200 ◦ C could be accompanied by up to two orders of
acteristics and ore genetic type should also be considered when evalu­ magnitude decrease in Co solubility, resulting in Co content drop in the
ating the pyrite origin, because some hydrothermal pyrite has Co/Ni <1, late-stage pyrite (Migdisov et al., 2011; Roman et al., 2019; Feng et al.,
caused probably by intensive fluid-rock interactions. The alteration 2020a). The median Co contents change from Py1 (235.13 ppm) to Py2
halos of stage II quartz-ankerite-polymetallic sulfide-gold veins suggest (17.11 ppm) in stage I (Fig. 7), and from Py3a (45.83 ppm) to Py3b
intensive fluid-rock interactions, which may have contributed to the low (23.28 ppm) in stage II (Fig. 7), suggesting that Py1 and Py3a were
Co/Ni ratios of Py3a and Py3b (Real et al. 2020; Zhang et al., 2022). precipitated under higher temperature than Py2 and Py3b, and the re­
sults are consistent with those of the Se content.

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H. Tan et al. Ore Geology Reviews 144 (2022) 104843

Fig. 10. Representative time-resolved depth-profiles from the Xiaojiashan gold deposit on different types of pyrite. (a-b) Stable and flat signal of As, Au, Co, Ni and Se
suggest that these elements are incorporated into pyrite structure. (c) Cu-bearing and Pb-Bi-bearing mineral inclusions in pyrite. (d) Cu-bearing and Pb-Bi-Ag-Sb-
bearing mineral inclusions in pyrite.

the higher As content in Py1 than in Py2 may be associated with rapid
precipitation of pyrite. The abundant co-precipitation of Py3a and
arsenopyrite may have caused a major As drop in the fluids, and thus
fluids temperature may have less influence on the As content in Py3a
and Py3b.
The solubility of Te is higher when the fluid is neutral to alkaline
with high oxygen fugacity, and thus the Te contents in the precipitated
pyrite are higher (Grundler et al., 2013). The median Te contents
decreas from Py1 (14.09 ppm) to Py2 (3.09 ppm) in stage I (Fig. 7), and
from Py3a (1.06 ppm) to Py3b (0.81 ppm) in stage II (Fig. 7), suggesting
that the pH and fO2 of the ore-forming fluids could decrease from Py1 to
Py2 in stage I, and from Py3a to Py3b in stage II.

6.5. Implications for ore genesis

Fig. 11. Plot of As/Au vs. Co/Ni for the Xiaojiashan pyrite.
Previous studies suggested that the gold metallogeny in NE Hunan is
orogenic-style (Fu et al., 2002; Xu et al., 2015; Xu et al., 2016; Deng
Arsenic enrichment in pyrite could be related to temperature drop et al., 2017; Zhang et al., 2018; Zhang et al., 2020; Liu et al., 2019) and/
and/or rapid crystallization (Huston et al., 1995; Li et al., 2018; Sykora or intrusion-related (Jiang et al., 2016; Xia et al., 2017; Xu et al., 2017a;
et al., 2018). The temperature change inferred from the Se and Co Deng et al., 2020). At Xiaojiashan, some workers have proposed that the
concentrations is inconsistent with the median As content drop from Py1 Xiaojiashan gold mineralization is intrusion-related by conventional
(1737 ppm) to Py2 (1167 ppm) in stage I, and from Py3a (19673 ppm) bulk isotope (Jiang et al., 2016) and fluid inclusion analysis (Tao et al.,
and Py3b (8823 ppm) in stage II (Fig. 7). The high trace element con­ 2015; Lin, 2020). For example, sulfur isotope study by Jiang et al.
tents and the fine-grained porous texture of Py1 are indicative of rapid (2016) suggested that the sulfur was sourced from the magma with
precipitation (Simon et al., 1999b). In contrast, Py2 is characterized by probably minor Lengjiaxi Group wallrock input; fluid inclusions
being subhedral-euhedral coarse-grained and texturally homogeneous microthermometry and H-O isotopes reported by Tao et al. (2015) and
with no inclusions (Fig. 5e), which is indicative of a stable and sus­ Lin (2020) demonstrated that the ore-forming fluids with medium
tainable fluid precipitation environment (Román et al., 2019). Hence, temperature (180 to 308 ◦ C) and low salinity (3.12 to 9.48 wt% NaCl

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H. Tan et al. Ore Geology Reviews 144 (2022) 104843

Fig. 12. Schematic genetic model for the different types of pyrite from Xiaojiashan.

eq.) were possibly derived from a magmatic-hydrothermal source with magmatic hydrothermal activity.
meteoric water mixing. However, owing to the multi-stage and
complicated ore-forming process, the data obtained by bulk analysis and 7. Conclusions
sampling bias would be a mix isotopic signature and easily result in
misinterpretation of data. Hence, the genesis of deposit at Xiaojiashan (1) The Xiaojiashan alteration and gold mineralization comprise
has been equivocal due to lack of the high-quality geochemical data three stages: (I) quartz-ankerite-pyrite-gold, (II) quartz-ankerite-
constrain the origin of the ore-forming materials and fluids, as well as polymetallic sulfide-gold, (III) quartz-ankerite. Three generations
mineralization process. of pyrite were identified in stage I (Py1 and Py2) and stage II
In this study, based on pyrite textural and compositional features, we (Py3, core: Py3a, rim: Py3b).
have proposed the following model for the multistage pyrite formation (2) Variations of trace elements contents (e.g., Se, Co, As and Te) in
at Xiaojiashan: (early stage I) fine-grained Py1 precipitated rapidly from Py1, Py2, Py3a and Py3b may be attributed to the decrease in
the metamorphic-hydrothermal fluids (Fig. 12a); (middle stage I) temperature, pH and fO2 of the ore-forming fluids, as well as fast
coarse-grained inclusion-free Py2 precipitated from the metamorphic- crystallization and coexisting mineral assemblages (pyrite-
hydrothermal fluids, and partially/completely replaced or overgrown arsenopyrite).
on Py1 under relatively low temperature and a stable environment (3) Trace elements geochemistry and in-situ sulfur isotopes indicate
(Fig. 12b); (late stage I) some native gold and chalcopyrite, sphalerite, that Py1 and Py2 were likely associated with metamorphic fluids
galena, tetrahedrite and pyrrhotite occurred in the voids of Py1 aggre­ derived from sedimentary strata, whereas Py3a and Py3b were
gates and the fracture of Py2, or along the grain boundaries of Py1 and formed from magmatic-sourced fluids. Therefore, the Xiaojiashan
Py2; (stage II) the Au-As-rich magmatic-hydrothermal fluids again mineralization may have been associated with early meta­
incurred along the NE-trending detachment faults and locally over­ morphism overprinted by later magmatic-hydrothermal activity.
printed stage I veins (Fig. 3e), precipitating the Au-As-rich Py3a and
arsenopyrite (Fig. 5h–i; Fig. 12d). Fine native gold may have precipi­
tated from the Au-As-rich hydrothermal fluids within these Py3 and Declaration of Competing Interest
arsenopyrite grains or along their margin (Fig. 5h–i; Fig. 12d). In some
cases, Py1 and Py2 could be replaced by Py3a. With the evolution of The authors declare that they have no known competing financial
hydrothermal fluids, the Au and As concentrations in the residual fluids interests or personal relationships that could have appeared to influence
decreased, and the Au-/As-poor Py3b precipitated around Py3a the work reported in this paper.
(Fig. 12e). This is similar to the model proposed by Xu et al. (2015) for
the gold mineralization in NE Hunan, which is featured by metamorphic Acknowledgements
fluid input in the early mineralization, and major magmatic-
hydrothermal fluid in the late mineralization. Such ore-forming pro­ This work has been jointly supported by the Natural Science Foun­
cess has also been proposed for many orogenic gold deposits/orefields dation of Hunan Province (2021JJ30809), Open Project of Hunan Key
worldwide, such as Lac Herbin (Canada) (Rezeau et al., 2017), Madrid Laboratory of Land Resources Evaluation and Utilization (SYS-ZX-
(Canada) (Kerr et al., 2018), and Mana (Burkina Faso) (Augustin and 202004), Geological Scientific Research Project of Land and Resources
Gaboury, 2019). Hence, we propose that the Xiaojiashan gold deposit is of Hunan Province (2016-04), Geological Scientific Research Project of
genetically associated with early metamorphism and late overprinting Hunan BGMR (201701), Fundamental Research Funds for the Central
Universities of Central South University (2019zzts882), Science and

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Technology Innovation Program of Hunan Province (2021RC4055), and Fu, G.G., Xu, D.R., Chen, G.H., Li, P.C., 2002. New recognitions on geological
characteristics of gold ore deposits in northeastern Hunan province, China and new
the Open Research Fund Program of Key Laboratory of Metallogenic
prospecting advances. Geotectonica et Metallogenia 4, 416–422 in Chinese with
Prediction of Nonferrous Metals and Geological Environment Moni­ English abstract.
toring (Central South University, Ministry of Education) (2021YSJS12). Gao, L.Z., Chen, J., Ding, X.Z., Liu, Y.R., Zhang, C.H., Zhang, H., Liu, Y.X., Pang, W.H.,
The authors thank Jianping Liu and Dexian Zhang (Central South Uni­ Zhang, Y.H., 2011. Zircon SHRIMP U-Pb dating of the tuff bed of Lengjiaxi and Banxi
groups, northeastern Hunan: constraints on the Wuling Movement. Geological
versity) for helping with the EPMA and LA-ICP-MS analyses, Bulletin of China. Geological Bulletin of China 30 (7), 1001–1008 in Chinese with
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George, L.L., Biagioni, C., Lepore, G.O., Lacalamita, M., Agrosì, G., Capitani, G.C.,
Bonaccorsi, E., d’Acapito, F., 2019. The speciation of thallium in (Tl, Sb, As)-rich
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