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Hydrothermal processes at the Axi epithermal Au deposit, western Tianshan:

Insights from geochemical effects of alteration, mineralization and
trace elements in pyrite

Article in Ore Geology Reviews · September 2018

DOI: 10.1016/j.oregeorev.2018.09.009

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 Ore Geology Reviews 102 (2018) 368–385

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Hydrothermal processes at the Axi epithermal Au deposit, western Tianshan:

Insights from geochemical eff ects of alteration, mineralization and trace
elements in pyrite
⁎ ⁎
Zhankun Liua,b, Xiancheng Maoa,b, , Hao Denga,b, , Bin Lia,b, Shugen Zhanga,b, Jianqing Laia,b,
Richard C. Baylessc, Min Pana,b, Longjiao Lia,b, Qinghua Shanga,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
c
Department of Natural Sciences, Shawnee State University, Portsmouth, OH 45662, USA

ART I C LE I N F O ABSTRACT

Keywords: As the largest low-sulfidation (LS) epithermal deposit in the Tulasu basin, western Tianshan, NW China, the Axi
Alteration-mineralization gold deposit has a poorly understood geologic history. It is not clear whether hydrothermal mineralization
eff ects occurred during a single event or multiple events. In this paper, new data consist of whole rock geochemistry and
Pyrite trace elements mass-change calculations for hydrothermal alteration. LA-ICP-MS trace element analysis of pyrite was conducted in
Mass-change order to develop a comprehensive metallogenic model. The pyrite-sericite-quartz alteration at the Axi deposit is
Hydrothermal characterized by replacement of plagioclase and mafic phenocrysts by sericite, quartz, pyrite (py1), smectite, and
process illite, indicating slightly acidic and reducing conditions during the early ore stage. Medium subhedral pyrite crystals
Axi epithermal Au deposit (py1) with porous texture are typically sited adjacent to iron-rich minerals (e.g., hornblende) and are characterized
NW China
by Co-Ni-Mn enrichment with high ratios of Co/Ni (avg. 1.114) and Cu/As (avg. 0.655), implying preferential
sulfidation reactions in magmatic hydrothermal systems. The quartz ± calcite ± pyrite ± adularia
assemblages in silicified rocks and the strong mobility of LREE both reflect a slightly acidic chloride- rich solution
phase during the later ore stage. Coarse anhedral pyrites with cataclastic texture (py2) and medium euhedral pyrites
(py3) have a mixed hydrothermal origin and were deposited with quartz during Au-pyrite- quartz and Au-
polysulfide-quartz stages, respectively. Py2 and py3 both have significantly lower Cu/As ratios (avg. 0.103 and
avg. 0.088, respectively) than py1, indicating the input of meteoric fluid during the later ore stage. The three
generations of pyrite, especially py3, have significant lattice-bound gold contents (py1:
0.01–38.86 ppm, median 1.51 ppm; py2: 0.03–234.37 ppm, median 1.21 ppm; py3: 3.31–231.56 ppm, median
42.72 ppm). Gold precipitation is associated with the destabilization of Au-bearing chlorine (Au(Cl)2−) and
bisulfide complexes (Au(HS)2−) via sulfidation and fluid boiling. All of these characteristics indicate the Axi
epithermal deposit is the result of two stages of mineralization.

1. Introduction
The Tulasu basin is an important mineral district in the western
Tianshan, NW China (Fig. 1). The basin hosts numerous low-sulfidation
(LS) (e.g., Axi, Tawuerbieke, and Tabei), and high-sulfidation (HS)
epithermal deposits (e.g., Jingxi-Yelmend), as well as porphyry-skarn
deposits (e.g., Abiyindi and Kexiaxi) (Fig. 2a). All these deposits are
hosted by andesites and granitic and dioritic porphyries, which have
similar trace element and Sr–Nd–Pb–Hf isotopic composition, with a
broadly contemporaneous age of ca. 370–347 Ma (Sha et al., 2005;
Tang et al., 2013; Xue et al., 2013; Zhao et al., 2014a,b; Peng et al.,
2016; Gu et al., 2016). The S–Pb–C–O isotopic composition of ore mi-
nerals indicates that mineralization is intimately related to Carboni-
ferous tectonic-magmatic and hydrothermal events (Zhao et al., 2014a;
Gu et al., 2016). These characteristics provide compelling evidence for a
causal link among these epithermal and porphyry deposits, which likely
resulted from the Tulasu polymetallic mineralization system (Zhao et
al., 2014a; Peng et al., 2016; Gu et al., 2016).
The Axi gold deposit is the largest (over 50 t) LS epithermal deposit
in the Chinese Western Tianshan. Gold mineralization is typically

⁎
Corresponding authors at: Central South University, Changsha 410083, China.
E-mail addresses: mxc@csu.edu.cn (X. Mao), haodeng@csu.edu.cn (H. Deng).

https://doi.org/10.1016/j.oregeorev.2018.09.009
Received 17 November 2017; Received in revised form 21 August 2018; Accepted 10 September 2018
Available online 12 September 2018
0169-1368/ © 2018 Elsevier B.V. All rights reserved.
Z. Liu et
al.
Fig. 1. (a) Schematic map showing the position of the Central Asian Orogenic Belt. (b) Geological and tectonic map of the Chinese Western Tianshan Belt (modified
from Zhang et al., 2012).
identified as disseminated-style and vein-style (Li and Xue, 1994; Feng,
2005; Dong et al., 2018). The crosscutting relationships (An and Zhu,
2017; Liu et al., 2017; Zhang et al., 2017) clearly indicate that the low-
grade disseminated ore was followed by the overprinting of high-grade
vein-style ore. In previous studies, however, there is little information
about whether a single mineralization event or multiple events were
involved in the formation of the Axi deposit. Thus, a detailed study of
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Ore Geology Reviews 102 (2018) 368–
385
Fig. 2. (a) Geological map of the Tulasu basin
showing the locations of porphyry and epithermal
deposits (modified from Zhai et al., 2009; ages are
taken from An et al., 2013; Tang et al., 2013; Xue et
al., 2013; Zhao et al., 2014a,b; Peng et al., 2016; Dong
et al., 2018). (b) Geological map of the Axi district
(ages are taken from Zhai et al., 2006; An
et al., 2013; Dong et al., 2018).
the hydrothermal process at the Axi deposit is necessary to better un-
derstand ore genesis.
The Axi deposit exhibits clear alteration-mineralization zonation,
which transitions outwards from silicification, quartz-carbonate al-
teration, to pyrite-sericite-quartz alteration, and propylitic alteration
(Zhai et al., 2009; Zhao et al., 2014a; An and Zhu, 2017; Liu et al.,
2017). The hydrothermal alteration and mineralization provide a
Z. Liu et
al.
convincing geological record of hydrothermal events at the Axi district. In
addition, pyrite, as the most abundant host mineral for gold, is
ubiquitous in all the alteration-mineralization zones in the Axi deposit,
which is also regarded as a sensitive record of the ore-forming process
(Large et al., 2007, 2009; Zhang et al., 2014; Franchini et al., 2015).
However, to date, few studies in this area have focused on hydro-
thermal alteration and pyrite as means for understanding the evolution of
mineralizing events.
This study focuses on alteration-mineralization assemblages and
zonation as well as geochemical behavior during water-rock interac-
tions at the Axi deposit in order to determine its hydrothermal evolu-
tionary history. Laser-ablation inductively coupled plasma-mass spec-
trometry (LA-ICP-MS) trace element analysis of hydrothermal pyrite is
conducted to further constrain the hydrothermal environment during
diff erent ore-forming stages. Our results, in combination with previous
studies, yielded a refined model of the hydrothermal processes at the
Axi gold deposit, which has important implications for understanding
the ore genesis of epithermal deposits.
2. Geological setting
2.1. Regional geology
The Tulasu basin is located between the south Keguqin Mountain
and north Yili Basin thrust fault zones in the Borohoro area (Fig. 2a).
The two fault zones strike NNE and dip 50°–70°, extending for more
than 10 km. Their structural directions are parallel to the boundary of
sutures between the Yili and Kazakhstan domains (Zhang et al., 2002).
The secondary structures in the Tulasu basin are commonly NW- and N-
trending steep strike-slip faults that control the occurrence of Paleozoic
strata (Fig. 2). Ring and radial fractures developed around the volcanic
edifice within the Jingxi, Abiyindi, and Axi districts (Zhang et al., 2002;
Chen et al., 2012).
The basement of the Tulasu basin, which formed during the
Mesoproterozoic to Paleozoic, consists of two suites of rocks. The lower
part consists of metamorphosed shallow marine carbonates, siltstones
and sedimentary clastic rocks of the Mesoproterozoic Jixian and the
Neoproterozoic Qingbaikou Group. The upper part consists of the
Middle Ordovician Nailenggeledaban Formation, which comprises ba-
salt and limestone intercalated with arkose, and the Lower Silurian
Nileke Formation, mainly consisting of intermediate to felsic volcani-
clastic rocks, as well as carbonate and clastic rocks. Unconformably
overlying these basement rocks are the subaerial intermediate to in-
termediate-felsic volcanic and volcaniclastic rocks of the Paleozoic
Dahalajunshan Formation (C1d), which comprise tuff , basalt, andesite,
dacite, rhyolite, as well as volcaniclastic rocks (e.g., volcanic breccia,
volcanic agglomerate, and ignimbrite), with a wide range of ages be-
tween ca. 417 and 347 Ma (An et al., 2013; Tang et al., 2013; Zhao
et al., 2014a,b; Peng et al., 2016). The C1d is further subdivided into
1
five lithologic members, from bottom to top: gray conglomerate (C1d ),
acid tuff (C1d2), lower andesite (C1d3), volcanoclastic (C1d4), and upper
andesite members (C1d5). It is generally associated with the late Pa-
leozoic subduction of the South Tianshan Ocean (Zhu et al., 2009) or
North Tianshan Ocean (An et al., 2013; Tang et al., 2010, 2013; Zhao
et al., 2014b). These volcanic rocks host numerous large (> 10 t) epi-
thermal deposits, including the Axi and Jingxi-Yelmand deposits
(Fig. 2).
Several granitic intrusions, which are comprised of syenite por-
phyry, granitic porphyry, and diorite, intruded into the basement or
volcanic strata (Fig. 2a). They show similar geochemical and isotopic
characteristics to the C1d volcanic rocks, and are broadly con-
temporaneous with the nearby ca. 357–348 Ma volcanic rocks (Tang
et al., 2013; Xue et al., 2013; Zhao et al., 2014a). The granitic intrusions
that outcrop in the southeastern, northeastern, and western parts of the
Tulasu basin lack economic mineralization, while the Abiyindi, Kexiaxi,
and Tabei intrusions host some porphyry-skarn Au-Cu-Mo deposits and
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385
an epithermal Pb-Zn deposit. Some younger dioritic aplites are ob-
served in the Tawuerbieke area (315.2 ± 3.5 Ma; Peng et al., 2016).
2.2. Ore deposit geology
The strata overlying the Axi district consist of the uppermost
member of the Dahalajunshan (C1d5) and Aqialehe (C1a) Formations
(Fig. 2b). The former comprises tuff , hornblende andesite, andesite, and
dacite, with zircon SHRIMP ages of ca. 367–356 Ma (Zhai et al., 2006;
An et al., 2013). These volcanic rocks are commonly mauve, light gray-
brown, or gray-green, with textures variable from massive or flow
structures to porphyritic. The phenocrysts, dominated by plagioclase, are
euhedral–subhedral and platy in shape (0.5–5 mm in size). Por-
phyroclasts mainly consist of euhedral and subhedral plagioclase to-
gether with hornblende and quartz. The Lower Carboniferous Aqialehe
Formation (< 288 Ma; Dong et al., 2018), which is only exposed in the
northern segment (Fig. 2b), consists mainly of conglomerate, calcareous
sandstone, and mudstone.
Calderas with ring and radial faults are well developed around the
paleovolcanic zone (Zhang et al., 2002; Sha et al., 2005). The ore-
controlling fault, F2, strikes to NW 340°, NE 25°, and NW 325° and dips
60°–70°, 50°–80°, and 55°–85° in the northern section (north of line No.
44), middle section (between line No. 44 and No. 27), and southern
section (south of line No. 27), respectively (Fig. 2b, 3).
Orebodies generally occur in the hanging wall of F2 and the footwall
of the pyrite-sericite-quartz zone (Figs. 3 and 4), extending to ∼1 km
along the strike (Fig. 2b), with varying thickness (11–15 m), dip
(46°–78°), and grade (2–16 g/t and mean 5.6 g/t). The ores can be
subdivided into two types: silicified vein type ore (Fig. 5a–e) and dis-
seminated ore (Fig. 5a, f). The silicified vein type is the main economic
ore, accounting for more than 80% of gold reserves. It typically has a
relatively higher gold grade (> 5 g/t) than disseminated ore (ca. 2 g/t).
Silicified vein type ore is closely associated with quartz ±
chalcedony ± sulfide vein and overprinting silicification (Fig. 5b–d),
and mainly consists of quartz (or quartz-chalcedony, quartz-sulfide)
veins, silicified wall rocks, and breccias (Fig. 5a–d). Most of the ores are
smoky or dark gray (Fig. 5a, c), due to the fine-grained sulfide and
metasomatic debris. The Au-bearing minerals in this type of ore are
identified as native gold, electrum, and sulfide (Fig. 5g and h) that are
commonly located in the quartz-sulfide aggregate (Fig. 5b, e), and
strongly altered breccia (Fig. 5d). Gold grade correlates with sulfide
content. Gold disseminations in altered rocks are associated with ex-
tensive pyrite-sericite-quartz alteration, showing breccia structure and
pyrite disseminated texture (Fig. 5a, f). Neither visible gold nor elec-
trum are observed in the disseminated ore.
The Axi deposit displays a successive alteration-mineralization
zoning pattern centrally from the core outward that mainly consists of
several zones of silicification, quartz-carbonate, pyrite-sericite-quartz,
and propylitic alteration (Fig. 4). The alteration-mineralization zones are
parallel to F2 (Figs. 3 and 4), with the widths variable from several meters
to a few hundred meters. Propylitic alteration, as the earliest alteration
(Chen et al., 2003), forms the outer zone with a wide halo (> 500 m)
from the present-day surface to depth. Propylitic alteration is
characterized by pale-green or green rock and chlorite-epidote-calcite
assemblages (Fig. 6a and b). The alteration partially to completely
transformed mafic minerals (e.g., pyroxene and amphibole) and plagi-
oclase into chlorite, epidote, sericite, carbonate, quartz, and pyrite
(Fig. 6c and d).
Pyrite-sericite-quartz alteration forms in the outer zone and par-
tially overprints the propylitic alteration. This alteration is character-
ized by gray-white and tan coloration (Fig. 5a, f) and partial to com-
plete replacement of plagioclase and mafic phenocrysts by sericite,
quartz, pyrite, and epidote (Fig. 6e–g). Sericite partially or totally re-
places plagioclase (Fig. 6e) or appears as veinlets filling in fractures of
the former alteration minerals (Fig. 6g). Most quartz grains are fine-
grained, with irregular shapes (Fig. 6e and f).
Z. Liu et
al.
Fig. 3. 3D models of orebodies, F2 and pyrite-sericite-quartz zone.
Fig. 4. The distribution of orebody and alteration at 1370 m level (a) and
section No. 24 (b).
The silicification and quartz-carbonate alteration zone, which hosts
the main orebodies, is well developed in the pattern center and has a
variable thickness (15–40 m). These zones have gradational or sharp
contact with the surrounding rocks and are characterized by quartz,
chalcedony and/or quartz-carbonate vein, veinlet, stockwork, and
breccia (Figs. 5a, 6h and i). Hydrothermal breccias with the irregular
and angular shapes are typically cemented by quartz ± chalcedony
stockworks and veinlets, and can be jointed (Fig. 5b and c). The clasts of
these breccias also occur in quartz veins, which have been totally sili-
cified (Fig. 6j). The silicification is successive with near quartz veins
(Figs. 5c, 6h) and varies from gray to smoky-gray in color (Fig. 6h and
i). Alteration minerals are mostly comprised of quartz, chalcedony, and
sericite, with a small and variable component of pyrite, arsenopyrite,
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Ore Geology Reviews 102 (2018) 368–
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and marcasite.
Multiple episodes of quartz deposition occurred in the Axi deposit.
The early quartz typically associates with pyrite-sericite-quartz altered
rock (Fig. 6g). It is commonly crosscut by late veins or coeval calcite
veins in propylitic alteration (An and Zhu, 2017). The second episode of
silicification is characterized by black chalcedony veins and veinlets
(Figs. 5b, 6j), white or light gray quartz-chalcedony veins (Fig. 7a), and
minor pyrite veins (Fig. 7c). The chalcedony veins and breccias are cut
or cemented by coeval quartz-chalcedony veins (Fig. 6j and k). Most
quartz grains are fine- to medium-grained in veins, but this is not the
identifying characteristics. The late silicification typically occurs as
gray and smoky-gray quartz-chalcedony stockworks, veins (Fig. 5a, c) or
tan quartz-polysulfide veins (Fig. 5e). Vug infill (Fig. 6l), comb, and
crustiform textures and drusy cavities are common in this type of sili-
cification.
Quartz-carbonate veins commonly crosscut (Fig. 6m), cement
(Figs. 5c and d, 6n, 7d) and replace (Fig. 6o) all other stages, indicating
later formation. The veins are mainly composed of carbonate (e.g.,
calcite, dolomite, and siderite), quartz, and barite, with minor amounts of
fine-grained pyrite. Comb texture (Fig. 6p) and platy calcite (Zhai et al.,
2009) are commonly observed in the quartz-carbonate veins.
Pyrite is the predominant sulfide mineral in the Axi epithermal
system. Based on hand specimen and microscopic-observations of
samples, four main types of pyrites have been recognized. Pyrite 1 (py1) is
commonly distributed as disseminations in phyllic-altered rock or
breccia (Figs. 5f, 7a and b). It spatially associates with altered horn-
blende (Fig. 6e and f). Py1 rarely occurs as pyrite clusters. The textures of
py1 are variable: mainly medium- to coarse-grained, euhedral to
subhedral crystals, typically with porous texture, filled by quartz
(Fig. 7e and f). Some grains of py1 have complex core-mantle-rim
textures, revealed by SEM-BSE imaging (Zhang et al., 2017), or develop
oscillatory zonation (Fig. 7g). Py1 grains are overgrown or replaced by
pyrite 2 (Fig. 7g and h), pyrite 3, and another sulfide (e.g., arsenopyrite;
Fig. 7f), and are considered to be the oldest pyrite type.
Pyrite 2 (py2) occurs as disseminations, veins or veinlets (Figs. 6k,
7a and b), and massive accumulations (Fig. 7c) in quartz veins and
silicified rocks. Py2 is commonly observed in the contact areas between
quartz veins and altered breccias (Figs. 6k, 7b, 7i). Py2 is characterized
by coarse- to medium-grained, subhedral to anhedral grains, with cat-
aclastic textures (Fig. 7j). They are typically intergrown, filled, or
Z. Liu et Ore Geology Reviews 102 (2018) 368–
al. 385

Fig. 5. Images of diff erent types of ore from the Axi

gold deposit. (a) Silicified vein type ore and dis-
seminated ore; (b) Andesite breccias, which are ce-
mented by quartz-chalcedony-sulfide veins, can be
jointed, implying the hydraulic fracturing; (c) and
(d) Gray quartz or silicified breccias cemented by
white quartz-carbonate veins; (e) Chalcedony-
quartz-sulfide vein; (f) Pyrites are disseminated in
pyrite-sericite-quartz altered andesite; (g) Native
gold occurring as an inclusion in pyrite crystal; (h)
Electrum intergrown with pyrite. Abbreviations: Au-
native gold; Apy-arsenopyrite; Cab-carbonate; Cln-
chalcedony; El-electrum; Py-pyrite; Qtz-quartz.

Fig. 6. Images showing characteristics of

hydrothermal alteration-mineralization at
the Axi epithermal deposit. (a) and (b)
Propylitic alteration gives the rock a green
color. The altered hornblendes are infilled
locally by calcite and quartz in Fig. 6a. (c)
Augites were locally replaced by chlorite.
(d) Plagioclases were locally or totally re-
placed by epidote and calcite. (e) Mineral
assemblage associated with pyrite-sericite-
quartz alteration comprises sericite, quartz
and disseminated pyrite. The plagioclase
was totally replaced by sericite and quartz
and reserved intergrown apatites. (f) The
hornblendes have been slightly replaced by
illite-smectite and pyrite. (g) Sericite forms
veinlet filling in fractures of chlorite/epi-
dote. (h) and (i) Silicified and pyrite-ser-
icite-quartz altered rock showing a grada-
tional relationship and quartz veinlet
crosscutting altered rock; (j) Chalcedony
and quartz vein cutting and replacing rock
breccia. (k) Early formed chalcedony cut by
quartz-chalcedony-pyrite vein. (l) Quartz
with vug infill texture. (m) Carbonate
veinlet cutting the early formed silicified
rocks. (n) Calcite containing the quartz-
chalcedony breccia (o) Calcite-quartz vein.
(p) Calcite vein with comb texture. Ab-
breviations: Ap-apatite; Aug-augite; Cal-cal-
cite; Chl-chlorite; Cln-chalcedony; Ep-epi-
dote; Hbl-hornblende; Ill-Illite; Qtz-quartz;
Pl-plagioclase; Py-pyrite; Ser-sericite, Sm-
smectite. (For interpretation of the refer-
ences to color in this figure legend, the
reader is referred to the web version of this
article.)

372
Z. Liu et
al.
sealed by late marcasite (Fig. 7k), arsenopyrite, native gold (Fig. 7k;
Wei, 2012) and electrum (An and Zhu, 2017). Obvious zonation or
textures, related to the crystallization path, rarely occur in py2.
Pyrite 3 (py3) is mainly distributed as random disseminations or
aggregates (Fig. 7d) in quartz-sulfide veins, breccia, and silicified rocks.
Py3 is distinguished from py1 by its relatively small size, clean surface,
and pyrite-marcasite-arsenopyrite assemblage. Py3 grains are dom-
inantly medium- to fine-grained, euhedral to subhedral crystals ranging
from 20 to 80 μm in size (Fig. 7l–n), occasionally up to 150 μm. Py3
overgrows py2, showing zonation (Fig. 7l and m) or developing clear
crystallization features (Wei et al., 2011; Zhang et al., 2017). Py3 grains
are locally crosscut or overgrown by marcasite and arsenopyrite
(Fig. 7n). Py3 commonly coexists with other sulfide minerals (arseno-
pyrite, chalcopyrite, sphalerite, and galena), comprising polymetallic
sulfide veins/veinlets.
Pyrite 4 (py4) generally occurs as veinlets or isolated grains in
carbonate-quartz veins. It is characterized by fine-grained (less than
40 μm) and cubic crystals (Li and Xue, 1994; Wei et al., 2011). Py4
characteristics that vary most from other pyrite generations are the
small size, low content of sulfides, and unique gangue minerals (i.e.,
calcite-quartz veins).
Based on mineral assemblages, textural characteristics, crosscutting
and overprinting relationships, four paragenetic sequences have been
identified (Fig. 8): (1) pyrite-sericite-quartz (Stage I), characterized by
the assemblage of quartz + py1 + sericite; (2) gold-pyrite-quartz (Stage
II), identified in black chalcedony veinlets, white and gray quartz veins,
stockworks, and breccias, and pyrite ± marcasite ± arsenopyrite ±
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Ore Geology Reviews 102 (2018) 368–
385
Fig. 7. Images showing textures of diff erent
types of pyrite at the Axi epithermal deposit.
(a), (b) and (c) Hand specimen photographs
showing disseminated pyrite 1 (py1) in al-
tered andesite breccia and pyrite 2 (py2)
occurring as veins. (d) Assemblages of pyrite
3 (py3), marcasite and arsenopyrite in
quartz breccia. (e) and (f) Disseminated
medium- to coarse-grained euhedral to
subhedral py1. (g) Py1 with oscillatory
zoning. (h) Py2 overgrown on py1. (i)
Clusters of anhedral to subhedral py2 in
quartz vein. (j) Coarse-grained py2 with
cataclastic texture in quartz vein. (k) Free
gold intergrown with py2 (from Wei, 2012).
(l) and (m) Euhedral py3 overgrown with
fractured py2 showing zonation. (n) Py3
locally or totally replaced by arsenopyrite.
Abbreviations: Au-native gold; Apy-arseno-
pyrite; Cab-carbonate; Cln-chalcedony; Mar-
marcasite; Py-pyrite; Qtz-quartz.
electrum assemblage; (3) gold-polysulfide-quartz (Stage III), domi-
nated by gray and smoky-gray quartz veins, stockworks and veinlets, as
well as mahogany quartz + polysulfide (e.g., pyrite, marcasite, ar-
senopyrite, sphalerite, galena, and chalcopyrite) ± chalcedony veins;
(4) quartz-carbonate (Stage IV), marked by white and light gray car-
bonate + quartz ± barite veins or veinlets.
3. Samples and analytical methods
3.1. Whole rock geochemistry
A total of 21 samples from the Axi district, which consisted of un-
altered or minimally altered andesites (n = 4), altered rocks (n = 9)
and vein type ores (n = 8), were analyzed for geochemical composition.
The four andesite samples were taken from near the quartz-sericite-
pyrite halo. The altered rocks are related to pyrite-sericite-quartz al-
teration (Stage I, n = 4), silicification (Stage II, n = 3) and quartz-
carbonate alteration (Stage IV, n = 2) (Fig. 8). Vein type ores included
two gray quartz veins from Stage II, three smoky-gray quartz veins from
Stage III, and three white quartz-carbonate veins from Stage IV (Fig. 8).
The detailed locations of these samples are listed in Supplementary
Table 1.
Analysis of whole rock major and trace elements was performed at
ALS Chemex (Guangzhou) Co Ltd. Samples, which were first culled out
of breccias, xenoliths, and veins, were crushed to less than 200 mesh by
using a steel mortar. Major elements were determined by using X-ray
fluorescence spectrometry, with the analytical precision better than 1%.
Z. Liu et
al.
Fig. 8. Paragenetic sequence of mineral, alteration, and mineralization at the Axi deposit.
Trace elements were detected by using the lithium borate dissolution
method and ICP-MS, with the analytical precision better than 5%.
3.2. Trace element analyses by LA-ICP-MS
A total of 73 spot analyses (22 on py1; 27 on py2; 24 on py3) were
completed on pyrites. Py4 was not analyzed in this study, due to its
small grain size. Spot analyses were conducted on both rim and core of
three types of pyrite (6 on py1; 7 on py2; 3 on py3). Note that py2 does
not show the rim-core texture, and we define that rim and core of py2
as the edge and central parts of subhedral crystals. The detailed lo-
calities of pyrite-bearing rocks are listed in Supplementary Table 2.
Analytical instrumentation employed in this study at the Institute of
Geochemistry, Chinese Academy of Sciences, Guiyang consists of a New
Wave UP-213 nm Laser Ablation System coupled with an Agilent 7700x
Quadrupole ICP-MS. Each analysis was performed by ablating 40-µm
diameter spots at 8 Hz with a laser beam energy of 6–7 J/cm2. The
analysis time for each sample was 80 s, consisting of ∼ 15 s of back-
ground measurement with laser off , and a ∼45 s analysis with laser on.
Helium was applied as a carrier gas for the ablated materials. Every set of
eight analyses was followed by one analysis of GSE-1G as quality
control of the time-dependent signal drift and mass discrimination.
Data were processed using ICPMSDataCal (Liu et al., 2008). The fol-
lowing elements were monitored: 49Ti, 51V, 55Mn, 59Co, 60Ni, 65Cu,
66
Zn, 75As, 77Se, 95Mo, 107Ag, 111Cd, 121Sb, 125Te, 197Au, 205Tl,
208
Pb,
209
Bi.
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4. Results
4.1. Whole rock geochemistry
Analytical results for the whole rock geochemistry of the Axi gold
deposit are presented in Supplementary Table 1.
4.1.1. Geochemical composition and REE pattern
Quartz veins in Stages II and III share similar major elements, which
are mainly SiO2 (84.43–97.70 wt%), with minor CaO (0.06–3.58 wt%),
MgO (0.03–1.98 wt%), Total iron (TFe2O3) (0.47–3.25 wt%), and K2O
(0.07–0.22 wt%). The SiO2 content of the samples in Stage IV ranges
widely from 21.09 to 61.22 wt%, with high CaO (10.49–24.20 wt%),
MgO (4.63–11.90 wt%) and TFe2O3 (4.83–8.37 wt%). There are good
negative correlations between SiO2 and MgO, CaO, MnO, TFe2O3, and
LOI with hydrothermal processes (Fig. 9). In addition, Al2O3 and K2O
show a significant positive correlation (Fig. 9), implying that Al and K
are jointly located in sericite.
Two quartz veins in Stage II are characterized by the lowest abun-
dance of Ag, As, Co, Ni, Li, Pb, Mo, and Sb. Quartz veins in Stage III
contain higher concentrations of Ag (avg. 7.49 ppm) and Li (avg.
70.63 ppm).
Total rare earth elements concentrations (∑REE) of andesite samples
vary from 73.83 to 101.30 ppm, with (La/Yb)N values from 6.37 to
7.72, showing enrichment of LREE, depletion of HREE (Fig. 10a) and no
Eu anomaly (δEu = 0.95–1.02). Regardless of slightly negative Eu
Z. Liu et
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Fig. 9. Binary plots of selected major elements for quartz vein ores. Pearson correlation coefficients are displayed with each binary plot.
anomalies (avg. δEu = 0.87), the samples which underwent the pyrite-
sericite-quartz alteration and silicification share similar REE patterns
with protoliths. The pyrite-sericite-quartz alteration is more enriched in
REE (∑REE = 74.79–92.07 ppm) in comparison with the silicification
(∑REE = 46.06–87.38 ppm). The rocks with quartz-carbonate altera-
tion have an overall parallel REE pattern, but with low ∑REE
(26.28–30.79 ppm) and a relatively weak LREE enrichment (Fig. 10a).
Quartz vein samples show a low ∑REE (avg. 8.52 ppm) and present a
systematic increase from Stage II to IV (1.55–3.84 ppm →
2.05–9.94 ppm → 10.37–24.88 ppm; Supplementary Table 1). The REE
distribution patterns of these samples show slight LREE enrichment,
low degrees of REE fractionation (avg. (La/Yb)N = 6.56), and positive
Eu anomalies (avg. δEu = 1.36; Fig. 10b; Supplementary Table 1).
4.1.2. Mass change
In this study, pyrite-sericite-quartz alteration, silicification, and
quartz-carbonate alteration were selected to calculate mass change by
the isocon method (Grant, 1986, 2005). The method is derived from the
mass balance equation of Gresens, which can be written as CiA = (MO/
MA)(CiO + ΔCi), where MO and MA are the masses of protolith and
corresponding altered rock, respectively, and CiA and CiO are the con-
centrations of element i in rocks. This equation can be formulated as
ΔCi/CiO = (MA/MO)(CiA/CiO) − 1, where ΔCi is the change in con-
centration of element i, and ΔCi/CiO represents the relative intensity of
hydrothermal alteration. The immobile element during hydrothermal
processes is an integrant in the isocon, given ΔCimmobile = 0. The
equation for immobile elements is CimmobileA = (MO/MA)CimmobileO. The
immobile elements in pyrite-sericite-quartz alteration at the Axi deposit
include TiO2, Ge, Zr, Hf, and In. In addition, P2O5, Hf, Zr, and Nb re-
main immobile during silicification, and Al2O3, In, Hf, Nb are immobile
in quartz-carbonate alteration. We choose TiO2, P2O5, and Al2O3 as
immobile elements in the isocon equation (Fig. 11). The calculated
mass change values are listed in Table 1, and gains and losses are shown
in Fig. 12.
Pyrite-sericite-quartz altered samples are enriched in SiO2, MnO,
K2O, and P2O5, and are depleted in CaO and Na2O (Fig. 12a). In sili-
cification, there is a significant enrichment in SiO2 and TFe2O3 with the
obvious reduction of MnO, MgO, CaO, and Na2O. The quartz-carbonate
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altered rock is strongly enriched in MgO, CaO, MnO and TFe2O3 and
significantly depleted in P2O5 and TiO2 (ΔCi/CiO > 25%; Table 1).
Most trace elements, particularly Ag, As, Mo, Sb, Tl, and W, are
enriched in pyrite-sericite-quartz alteration, while only Ba, Cs, and Sr
are depleted. Silicified samples show significant mass gains in Pb, Ag,
Sb, Ni, Li, Cr, Co, and As and losses of Ba, V, and U (Fig. 12b). Quartz-
carbonate alteration and silicification have a similar pattern of trace
element migration, whereas As and Zn are strongly depleted.
Pyrite-sericite-quartz alteration generally enriches REE, particularly La
and Ce (ΔCi/CiO > 10%; Table 1). The geochemical behavior of REE in
silicification is analogous to pyrite-sericite-quartz alteration but diff ers
in the enrichment of Eu and the mass change (Fig. 12c). During the
process of quartz-carbonate alteration, REE shows diff erent fea- tures,
such as the depletion of LREE and the enrichment of HREE. Europium,
Gd, Tb, and Dy have a weaker mobility than other REE in three types
of hydrothermal alteration.
4.2. Pyrite geochemistry
Trace element concentrations in the three types of pyrite are listed in
Supplementary Table 2. Selected trace element compositions are shown
with boxplots in Fig. 13. In general, concentrations of most trace elements
(e.g., Au, As, Co, Bi, and Mo) in the three types of pyrite grains vary
considerably (Fig. 13). Gold content in py1 and py2 are similar, with
medians of 1.513 ppm (n = 20) and 1.212 ppm (n = 24), respec- tively.
There are several outliers of 38.86 ppm and 21.57 ppm in py1, and 234.4
ppm and 22.28 ppm in py2. Gold content in py3 is distinctly higher than
py1 and py2, varying from 3.101 to 231.6 ppm, with a median of
42.72 ppm (n = 24). Gold has a clear positive correlation with Se in
the three generations of pyrite (R = 0.620; Fig. 14a), but no covariation
with other analyzed elements.
Silver contents in the three types of pyrite show a similar variation
with Au, such that py1 and py2 contain lower medians of 16.00 ppm
and 12.38 ppm, and py3 grains host a significantly higher content
(57.43 ppm). Silver and gold generally show a minor positive correla-
tion in py3, but there is no correlation in neither py1 nor py2 (Fig. 14b).
The ratios of Au/Ag in most of the pyrite crystals are lower than 10
(Fig. 14b), with an upward trend (0.23, 0.91 and 1.60). There is a
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Fig. 10. Chondrite-normalized patterns of REE for andesites, altered rocks (a),
and veins (b). Chondrite normalization values are from Sun and McDonough
(1989).

positive correlation between Ag with Sb (Fig. 14c).

Arsenic is the most abundant trace element in all pyrite crystals in
the Axi deposit (Supplementary Table 2). The As contents in py1, py2,
and py3 range from 14.48 to 23,467 ppm, 2.66 to 30,946 ppm, and
5029 to 55,735 ppm, respectively, and py3 contains a narrower range of
As compared with py1 and py2 (Fig. 13). Although there is no sig-
nificant correlation between As and Au (Fig. 14d), gold and Au/As
ratios show a good correlation (R = 0.612) with the strongest positive
correlation (R = 0.791) in py3 (Fig. 14f). Plots of Au/Ag vs. Au/As
allow discrimination of the three types of pyrite (Fig. 14g). Fig. 11. Isocon diagrams of pyrite-sericite-quartz alteration (a), silicification (b)
and quartz-carbonate alteration (c) at the Axi deposit. Elements above the isocon
Cobalt, Ni, Cu, Pb, Ti, and Sb are enriched in pyrite grains
line are enriched in the altered rock, and elements below the isocon line are
(Supplementary Table 2). Py1, the early pyrite, contains higher con-
depleted. The protolith for pyrite-sericite-quartz alteration is andesite and the
centrations of Co, Mn, V, and Bi than py2 and py3, and concentrations protolith for silicification and quartz-carbonate alteration is pyrite-sericite- quartz
of Ni, Pb, Zn, and Cu that are similar to py3 (Fig. 13). Cobalt correlates altered andesite.
closely with Ni and Bi in the analyzed pyrite grains (R = 0.981 and
0.967; Fig. 14h). The Co/Ni ratios of py1, py2, and py3 range from
Au/As. There is no correlation between Cu and As, but a notably high
0.057 to 5.460 (avg. 1.114), 0.043 to 1.716 (avg. 0.584), and 0.001 to
ratio of Cu/As is observed in py1 (Fig. 14i). Comparing py1 and py3,
0.638 (avg. 0.142), respectively. This trend contrasts with Au/Ag and
only py2 crystals are only enriched in Tl, and Ti (Fig. 13).

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Table 1
The mass change of selected elements during hydrothermal alteration.

Element Pyrite-sericite-quartz Silicification Quartz-carbonate

ΔCi ΔCi/ΔCi O
ΔCi ΔCi/ΔCO
i ΔCi ΔCi/ΔCiO

SiO2 1781.57 29.84 4550 69.43 5704 87.04

TiO2 0.00 0.00 −6.25 −8.31 −21.79 −28.96
Al2O3 96.51 6.33 277.11 20.21 0.00 0.00
MgO −26.36 −12.84 −50.71 −33.53 1067.17 705.57
MnO 2.42 35.79 −3.81 −49.12 49.05 632.91
TFe2O3 −41.57 −7.57 136.06 31.70 412.73 96.15
CaO −130.94 −34.12 −77.23 −36.13 1992.55 932.19
Na2O −57.08 −86.16 −1.84 −23.69 −4.41 −56.89
K2O 217.57 57.75 −45.13 −8.98 −111.58 −22.21
P2 O5 2.65 14.94 0.00 0.00 −6.11 −35.44
Ag 215.42 3746 378.31 202.30 247.35 132.27
As 236,110 4734 95,905 47.05 −118761 −58.26
Ba −3011.63 −17.21 −6828 −55.74 −6681.36 −54.54
Co 415.99 28.35 1182 74.24 568.13 35.68
Cr 3045.26 35.51 10,677 108.68 7215.05 73.44
Cs −720.61 −31.30 8.99 0.67 721.78 53.97
Cu 1563.31 42.80 −546.00 −12.38 −1492.03 −33.83
Li 584.88 26.23 2864.00 120.34 6273.67 263.60
Mo 588.08 1104.38 −29.68 −5.47 454.54 83.82
Ni 19.14 63.96 31.07 49.44 130.81 63.53
Pb 351.66 55.82 1959.57 236.09 963.10 116.04
Rb 8647.09 50.20 −2007.93 −9.18 32.04 0.15
Sb 6322.36 277.42 10,406 143.09 31,206 429.11
Sr −6971.96 −42.83 −925.64 −11.76 6029.33 76.61
Th 91.34 19.27 155.81 32.60 −18.03 −3.77
Tl 393.80 194.95 −88.76 −17.62 −34.87 −6.92
U 117.24 83.74 −45.00 −20.69 5.25 2.41
V 6735.30 69.62 −5595.00 −40.32 1271.71 9.17
W 1027.59 178.71 −206.64 −15.25 −475.15 −35.07
Zn 1576.41 25.43 −118.57 −1.80 −4124.80 −62.73
La 297.09 19.23 542.07 34.80 −310.12 −19.91
Ce 396.59 11.45 1062.28 32.54 −781.39 −23.93
Pr 33.18 8.10 105.54 28.18 −115.00 −30.71
Eu −6.12 −5.54 6.38 7.23 1.96 2.22
Nd 101.59 6.07 358.07 23.87 −486.51 −32.43
Sm 11.14 3.22 57.05 18.91 −56.73 −18.80
Gd 8.37 2.52 32.36 11.24 −24.05 −8.35
Tb 0.17 0.35 4.33 10.31 1.44 3.42
Dy −1.64 −0.56 16.41 6.61 21.27 8.57
Ho 1.50 2.64 3.49 7.08 7.55 15.33
Er 4.67 3.01 14.83 10.98 22.04 16.32
Tm 1.15 5.13 3.16 15.82 4.50 22.51
Yb 10.53 7.43 20.59 15.99 48.33 37.54
Lu 0.13 0.60 4.17 22.55 6.00 32.44
Y 135.14 8.82 78.43 5.56 449.93 31.91

Note: The units for ΔCi of major elements and trace elements are % and ppm, respectively. The ΔCi/ΔC Oi unit is %.

Our results show that the rims of analyzed pyrites are enriched in tents of Au and Se show a significant correlation in pyrites, but without
Au and As, with a high Au/As ratio. Detailed analysis reveals that py1 the parallel spectra in LA-ICP-MS profiles (Fig. 16). Notwithstanding
rims have a higher concentration of Au, Ag, As, Sb and Bi, with a higher
Au/Ag ratio (avg. 0.12) than cores (n = 6; Fig. 15a). Py2 has an Au-As-
rich rim (Fig. 15b). In this type of pyrite, silver shows a strong en-
richment in cores, causing a low Au/Ag ratio. The rims of py3 grains are
enriched in Au, Ag, As, Co, and Mn. Trace element concentrations
within the core and rim of py3 grains share a similar pattern (Fig. 15c).

5. Discussion

5.1. Genetic relationship between pyrite and hydrothermal alteration

Pyrite is the most typical and abundant mineral at every stage in the
Axi deposit and it has a close association with the hydrothermal al-
teration. Since pyrite in the deposit often contains ample gold whereas
only minor native gold grains occur as inclusions in pyrite (Fig. 5f), the
existence of abundant invisible gold is implied. In this study, the con-

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the occurrence of some spiky Au profiles (Fig. 16e and f), gold dis-
tribution in pyrite crystals exhibits a general flat signal that is similar to
As, especially in the pyrites with high Au contents (Fig. 16a, c, e). This is
consistent with recent EPMA studies (Zhang et al., 2017). In addition, the
Au-bearing pyrites from the Axi deposit reveal the relatively low Au/As
ratios that plot below the gold saturation line (Fig. 14d; Reich et al.,
2005). These key observations suggest that gold is mainly present in solid
solutions in the lattices of three types of pyrite (e.g., Large et al.,
2007; Zhang et al., 2014; Franchini et al., 2015; Gregory et al., 2015).
This also indicates that pyrite co-precipitated with Au. Thus, discussion of
relationships between pyrite and hydrothermal alteration help us to not
only investigate pyrite genesis but also to further understand the
mineralization conditions and mechanisms of gold precipitation.
In pyrite-sericite-quartz alteration, feldspars are commonly desta-
bilized by low pH hydrothermal fluids that are rich in Si, K+, H2S, and
HS- (Dai et al., 2008; Parsapoor et al., 2009). Some H+, K+, and Si may
be transported from the peripheral propylitic zone (Liu et al., 2017).
The altered rock is characterized by the noticeable addition of SiO2 and
K2O, and removal of Na2O, CaO, Ba, Cs, and Sr (Fig. 12), which results
from feldspar dissolution as well as sericite and quartz generation

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Fig. 12. Histograms showing gains and losses of selected elements during hydrothermal alteration.
(Fig. 6e and f). Although TFe2O3 is weakly depleted in this alteration,
we observe that py1 is typically located adjacent to iron-rich minerals
(e.g., hornblende; Fig. 6e and f), implying the original preferential
sulfidation of hornblende. Some py1 is associated with sericite, chlorite,
and quartz (Fig. 6e, g), via this reaction: 3Al(Mg, Fe)5AlSi3O10(OH)8
(chlorite) + 2 K+ + 18H2S + 7O2 + 10H+ → 2KAl3Si3O10(OH)2 (ser-
icite) + 9FeS2 (pyrite) + SiO2 (quartz) + 33H2 + 6 Mg2+. Additionally,
the trace elements (Co, Ni, Cu, Pb, Mn, and Zn) are enriched in py1
(Fig. 13), consistent with the whole-rock elemental gains during pyrite-
sericite-quartz alteration (Fig. 12b). These characteristics suggest that
py1 directly precipitated during hydrothermal fluid/rock interaction.
During silicification, feldspar, sericite, carbonate, chlorite, and
epidote are totally or partly replaced by quartz and pyrite in a high
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fluid/rock ratio environment. Silicification strongly increases Ag, As,
Co, Cr, Ni, Pb, and Sb (Fig. 12). Generally, these element gains during
silicification are likely partly related to the formation of pyrite, which
can incorporate some contents of the chalcophile and siderophile ele-
ments from hydrothermal fluid during crystallization (e.g., Large et al.,
2009; Reich et al., 2013; Franchini et al., 2015). Py2 and py3 show a
close association with quartz (Fig. 6k, 7), indicating the generation
through silicification. The Ag/Pb ratios of py2 and py3 range from
0.017 to 4.217 (avg. 0.945) and 0.355 to 1.130 (avg. 0.954), close to
the values of mass change (0.857; Table 1). Additionally, the Co/Ni
ratio associated with the mass change in silicification is 0.568 (Table 1),
similar to py2 (avg. 0.584), indicating a hydrothermal origin for py2.
Hydrothermal pyrite is typically characterized by Co/Ni > 1, whereas
Fig. 13. Comparative box plots of trace element
concentration in three types of pyrites. Copper, Co, Ni,
Pb, Mn, V and Bi are enriched in py1; Tl and Ti are
enriched in py2; Au, Ag, As, Se, Zn, and Sb are
enriched in py3. Median metal content in py1–3,
respectively, is as follows: Cu (129.3, 93.25, 126.0),
Co (60.45, 18.13, 10.37), Ni (102. 6, 36.51, 105.4),
Pb (171.3, 20.74, 151.4), Mn (10.48, 2.87, 2.50), V
(0.70, 0.41, 0.40), Bi (2.09, 0.72, 0.25), Tl (3.23,
13.27, 7.58), Ti (28.47, 38.11, 31.1), Au (1.51, 1.21,
42.72), Ag (16.00, 12.38, 57.43), As (5670, 8695,
15,380), Se (1.68, 1.888, 3.75), Zn (3.74, 2.06,
4.82), and Sb (0.53, 0.32, 2.74).
Z. Liu et
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Fig. 14. Binary plots of selected trace elements (in ppm) for three types of pyrites. The blue dashed curve in Fig. 14d represents the solubility limit of Au as a function of
As, as determined by Reich et al. (2005). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
the Co/Ni ratios of py2 and py3 are mostly below 1, especially in py3
(< 0.4). The likely conclusion then is that py2 and py3 are syn-sedi-
mentary pyrites (Bralia et al., 1979; Bajwah et al., 1987; Koglin et al.,
2010) or diagenetic pyrites associated with deposition of organic matter
(Large et al., 2007, 2009; Berner et al., 2013; Gregory et al., 2015).
However, if the early pyrite was remobilized by fluid (Koglin et al.,
2010; Pasava et al., 2013), or the hydrothermal fluid mixed meta-
morphic and/or epizonal fluid (Clark et al., 2004; Zhang et al., 2014),
hydrothermal pyrite could form at low Co/Ni ratios (< 1). Previous
studies of silicifying hydrothermal fluids in the Axi deposit show mixing
between magmatic and external water (Jia et al., 1999; Feng, 2005;
Zhang et al., 2007; Zhai et al., 2009; An and Zhu, 2017). Considering
the clear links between pyrite and quartz veins and their common
coarse and euhedral textures, we suggest that both py2 and py3 were
deposited together with quartz and are related to a mixed hydrothermal
origin.
5.2. Ore-forming fluid characteristics
5.2.1. Fluid composition and source inferred by pyrite
Gold and many other trace elements, such as Ag, As, Co, Ni, Cu, Pb,
Se, and Te, can partition from hydrothermal fluids into pyrite in solid
solution and/or as micro- to nano-sized mineral inclusions during
growth and/or recrystallization (Reich et al., 2005, 2013; Large et al.,
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2009; Deditius et al., 2009; Gregory et al., 2015; Tardani et al., 2017).
The trace element concentrations and distributions in pyrite depend on
both the geochemical properties of elements and the nature of hydro-
thermal fluid (e.g., composition, temperature, and phase). Thus, the
diverse Au-bearing pyrites in the Axi deposit have tremendous potential for
providing useful information on the evolving composition and
physical-chemistry of ore-forming fluids (e.g., Zhang et al., 2014;
Franchini et al., 2015).
Three types of pyrite contain variable concentrations of siderophile and
chalcophile elements (e.g., As, Cu, Co, Ni, Pb, and Sb) from py1 to py3
as well as from the core to rim of one pyrite crystal (Fig. 15),
suggesting that the hydrothermal fluids vary in composition. The early
pyrites occurring in pyrite-sericite-quartz altered rock generally have
high concentrations of Co, Ni, Cu, Pb, Zn, and Mn (Fig. 13), with high
Co/Ni ratios. In addition, those elements are notably enriched in the
cores of py1 (Fig. 15a). High Co and Ni concentrations in pyrite with a
higher Co/Ni ratio are typically interpreted to be produced in high-
temperature magmatic-hydrothermal systems (Reich et al., 2016). The
reported temperatures of mineralization at the Axi deposit suggest that
Stage I was likely above 285 °C; subsequently Stages II and III were at
temperatures of ∼ 285–120 °C, and Stage IV was below 120 °C (Li and
Xue, 1994; Jia et al., 1999; Feng, 2005; Zhai et al., 2009; An and Zhu,
2017). These temperature conditions are appropriate for the substitu-
tion of Co and Ni during pyrite-sericite-quartz alteration (Huston et al.
Z. Liu et
al.
Fig. 15. Spidergram showing the average concentrations of trace elements at
core and rim of three pyrite types. The far outliers of Co and Ni in the rim of py2
(G045-3, Co 24,454 ppm, Ni 22,945 ppm) were rejected when calculating the
average concentrations.
1995). Previous studies have shown that Mn can be enriched in hy-
drothermal fluids by extensive interactions with carbonate rocks. The
fluid inclusions from the Axi deposit typically contain some organic gas
(e.g., C2H4, C2H6, C4H6, and C6H6) (Jia et al., 1999; Feng, 2005; Sha
et al., 2005; Zhang et al., 2007). δ13C values of calcite vary between
1.7‰ and +4.9‰ (Zhang et al., 2007; Zhai et al., 2009), approxi-
mately coincident with the δ13C of marine carbonate (−2‰ to +6‰;
Veizer et al., 1999), reflecting derivation of the carbon from basement
limestone. The δ34S values of py1 are +4.03‰ to +4.30‰ (Li and
Xue, 1994), indicating a magmatic source. In summary, py1 was likely
formed in magmatic-hydrothermal systems, and hydrothermal fluids
contained some magmatic waters derived from deep intrusion.
Py2 and py3 generally occur in quartz veins and silicified rocks
associated with SiO2-bearing fluids. The SiO2 content of quartz veins
shows a descending trend from Stages II to IV, whereas MgO, CaO,
MnO, and TFe2O3 are the opposite (Fig. 9), implying that the major
element composition of ore-forming fluids transitioned from SiO2-rich
to MgO-, CaO-, MnO-, and TFe2O3-rich.
Our data clearly show that py2 and py3 both have lower Cu/As
ratios (0.103 and 0.088) than py1 (0.655), but are nearly the same as
the ratios in quartz veins (avg. 0.014) and in bulk pyrite geochemistry
(avg. 0.022; An and Zhu, 2017). The diff erence likely represents che-
mical changes in hydrothermal ore fluids (Deditius et al., 2009, 2014;
Reich et al., 2013; Tardani et al., 2017). Copper is slightly depleted, and
arsenic strongly enriched during silicification (Fig. 12b), which seems
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arsenopyrite (Fig. 7n), and these pyrites generally occur in the As-rich
growth zones, with relatively low ratios of Cu/As. Therefore, the high-
As fluid was more likely to occur in association with the low Cu/As
ratios of py2 and py3, and their As-rich zones, rather than being due to
the Cu losses during water/rock reaction. Experimental data, fluid in-
clusion and geochemical analysis of pyrite have determined that Cu has a
higher affinity for the high-density saline brine, while As pre-
ferentially partitions into low density and low salinity aqueous vapor
(Pokrovski et al., 2002, 2005; Seo et al., 2009; Tardani et al., 2017).
The H–O isotope data suggest that there was an input of meteoric fluid
during Stages II and III in the Axi epithermal deposit (Sha et al., 2005;
Zhai et al., 2009; An and Zhu, 2017). It is plausible that the diluted
meteoric water decreased the density, salinity, and temperature of ore
fluid, thereby promoting the partitioning of As into the ore system (e.g.,
Tardani et al., 2017). Thus, the As-rich pyrite may be related to a low
density and low salinity fluid environment that resulted from a large
input of meteoric fluid.
5.2.2. Physicochemical conditions of hydrothermal fluids
The sericite-pyrite-quartz altered rock at the Axi deposit contains
some quartz, kaolinite, illite, and smectite, which indicates that the
infiltrating fluid was slightly acidic (Simmons et al., 2005; Dai et al.,
2008). Due to the loss of H+ during alteration, the pH might have in-
creased, resulting in the formation of calcite (Fig. 6f). The presence of
pyrite in sericite-pyrite-quartz alteration is originally associated with
reduced sulfur, indicating that local conditions were reducing during
Stage I.
The quartz-pyrite ± sericite ± adularia ± marcasite silicification
assemblages (Stages II and III) represent formation from slightly acidic
pH solutions (Simmons et al., 2005; Cooke et al., 2011). During Stage
IV, the occurrence of calcite and dolomite reflects decreasing acidity of
fluids during quartz-carbonate alteration (Dai et al., 2008).
Europium has two oxidation states, Eu3+ and Eu2+, and the oxi-
dation state of Eu changes from Eu3+ to Eu2+ in a reducing-high
temperature (> 250 °C) environment (Sverjensky, 1984). The geo-
chemical behavior of Eu can be used to indicate the relative oxygen
fugacity of hydrothermal fluids. Our data show that quartz and carbo-
nate veins have positive Eu anomalies (avg. δEu = 1.36; Fig. 10b;
Supplementary Table 1), reflecting the relative gain of Eu2+ . In addi-
tion, fluid inclusion studies show that the ore-forming fluid typically
contains H2O, CO2, and CH4, with small amounts of CO, H2S and or-
ganic matter (Jia et al., 1999; Feng, 2005; Zhang et al., 2007). More-
over, pyrrhotite was formed in quartz veins during Stages II and III (Li
and Xue, 1994; Jia et al., 1999; An and Zhu, 2017). These observations
indicate that Stages II to IV all had relatively reducing conditions.
5.2.3. Eff ects of complexes in hydrothermal fluids on REE mobility
Complexes are important for the transportation and precipitation of
metal elements in magmatic-hydrothermal ore deposits (Heinrich et al.,
2004; Williams-Jones and Heinrich, 2005; Seo et al., 2009). REE are
supposed to be carried in aqueous solutions as complexes (Taylor and
Fryer, 1980; Michard, 1989; Lottermoser, 1990; Haas et al., 1995;
ff ects
Williams-Jones et al., 2012) and the occurrence as complexes a
their geochemical behavior (e.g., Bau, 1991; Allen and Seyfried, 2005;
Parsapoor et al., 2009; Craddock et al., 2010).
REE in pyrite-sericite-quartz alteration (Stage I) exhibit no sig-
nificant variation (Table 1; Fig. 12c), resulting in the parallel pattern of
altered rock and protoliths (Fig. 10a). As mentioned earlier, this al-
teration was related to high temperature and reducing environment in
the early hydrothermal stage. It was detrimental to REE enrichment
since REE3+ rarely combines with sulfide-complexes (HS− or S2−) and
Z. Liu et Ore Geology Reviews 102 (2018) 368–
al. 385
to suggest that water/rock reactions result in the decrease in the Cu/As even then the complex is unstable at high temperature. The dissolution
ratios of py2 and py3. The Cu abundances in several generations of of plagioclases may release REE into fluids, nevertheless low fluid/rock
−

ratios restrict the subsequent migration. The chloride anion (Cl ) is

pyrite are, however, relatively constant (Fig. 13). In addition, our ob-
servation and analysis show that some pyrites were replaced by regarded as a good complexing agent for LREE and Eu (Taylor and
Fryer, 1980; Sverjensky, 1984; Michard, 1989; Lottermoser, 1990;

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al. 385

Fig. 16. Representative time-resolved depth profiles of pyrite LA-ICP-MS analyses. (a) and (b) are from Py1; (c) and (d) are from Py2; (e) and (f) are from Py3.

Allen and Seyfried, 2005; Craddock et al., 2010). Complexation with Cl-
may result in the loss of Eu (Fig. 12c) and weak negative Eu anomalies
(Fig. 10a).
Although most major elements were strongly depleted by silicifi-
cation, the REE distribution patterns of the silicified rock were weakly
aff ected (Fig. 10a). There is a clear positive correlation (R2 > 0.89)
between REE and P2O5, TiO2, Al2O3, and K2O in the Stages II to IV
(Fig. 17), suggesting that the REE-bearing minerals may include apatite,
titanite, epidote, and sericite (Gieré and Sorensen, 2004; Vuorinen and
Hålenius, 2005; Horie et al., 2008; Williams-Jones et al., 2012). Ore-
forming fluids were supplemented by much meteoric water during
Stages II and III. It increased the fluid/rock ratio and introduced ligands
that could transport REE (e.g., Cl−, F−, SO42−, and CO3 2− ), resulting
in REE mobilization and enrichment. Jia et al. (1999) reported that the
Cl- concentration in fluid inclusions trapped in quartz veins can reach
up to 8.0 ppm (avg. 2.3 ppm). LREE exhibits relatively strong mobility in
silicification (Fig. 12c), which may be attributed to the dissolution of REE-
bearing minerals to form REE chloride species in acid chloride-rich
hydrothermal fluids (Bau, 1991; Parsapoor et al., 2009; Craddock et al.,
2010). Although fluoride is perhaps responsible for LREE behavior
(Oreskes and Einaudi, 1990; Ayers and Watson, 1993), chloride species
dominate and are able to transport REE under acidic conditions (Bau,
1991; Benaouda et al., 2017). Additionally, F-rich aqueous liquids also
enrich HSFE, with high Hf/Sm, Nb/La, and Th/La ratios (> 1). How-
Fig. 17. Plot of ∑REE versus P2O5, TiO2, Al2O3, and K2O for veins and altered
ever, in our samples, the ratios of mass change and geochemistry of rocks related to silicification and quartz-carbonate alteration.
altered rock and quartz veins are below 1 (Supplementary Table 1).
This suggests that Cl− was the most important factor for LREE en- 2−
(Haas et al., 1995).
be attributed to CO3
richment. Quartz fluid inclusion data reveal that the Axi epithermal
During Stage IV, LREE, P2O5, TiO2, Na2O, and K2O display strong
deposit hosts some H2O-CO2 fluid inclusions (Jia et al., 1999; Feng,
compositional drifts (Fig. 12), whereas Al2O3 remains constant. The
2005; Zhang et al., 2007; Wei, 2012), so the enrichment of HREE may
losses of LREE (Fig. 12c) reflect the consumption of LREE-rich accessory
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al. 385

Fig. 18. Schematic model showing hydrothermal processes of the Axi epithermal deposit. (a) Pyrite-sericite-quartz alteration developed along the inchoate F2, as fluid
conduits, during the early ore stage. (b) F2 occurred right strike-slip movements during the later ore stage, resulting in the dilatation zones, which are conducive to fluid
flow and confinement. The mineralized quartz vein and breccia system are located in the center of the pyrite-sericite-quartz zone. (c) The orebodies were broken by
the fault activity and overprinted by quartz-carbonate alteration during the post-ore stage.
minerals (e.g., sericite, apatite, and titanite), due to the leaching and/or thereby resulting in the destabilization of Au-bearing agents causing
dissolution of susceptible ions by suitable complexing agents in fluids. gold to deposit (Phillips and Powell, 2010). It is noted that the ore and
However, HREE clearly undergo a diff erent process, since carbonate py1 generated during the early stage typically contain relatively low
2−

and barite crystallization deplete the complexing agents SO4
2−
CO 3 (Haas et al., 1995), and result in the decomposition of HREE
complexes.
5.3. Gold deposition mechanism
Gold deposition from hydrothermal fluids in epithermal deposits is
induced by the decoupling of Au-bearing complexes via water/rock
interaction, and fluid boiling or mixing with diff erent fluids (Sillitoe
and Hedenquist, 2003; Simmons et al., 2005; Li et al., 2015; Zhong et
al., 2017a, 2017b). As discussed above, py1 was formed in a mag-
matic-hydrothermal system, and the concentrations of sulfur and
chlorine are relatively high in the early pyrite-forming fluids. The high
temperature and the reducing environment in Stage I is also inferred
from mineral assemblages. These fluid conditions are conducive to gold
transportation as Au-bearing chlorine- and/or sulfur- complexes, such
and gold grade. There are two possible reasons: (1) the limitation of water/
rock interaction, because the low-permeability of wall rocks (Fig. 5f)
constrains the fluid infiltration (e.g., Ronacher et al., 2004), and (2) the
constrained breakdown of Au-bearing complexes because of the weak
changes in physicochemical conditions, such as fO2 and fS2 (e.g., Li
et al., 2015) or the limited iron supplied by country rocks (i.e., dacitic
andesite) (Feng, 2005; Sha et al., 2005; and references therein).
As discussed above, the geochemical compositions of pyrite indicate
that the ore-forming fluids in Stages II and III are composed mostly of
low-salinity meteoric water under slightly acidic and reduced condi-
tions. In this environment, gold is most likely transported as the bi-
sulfide complex (Au(HS)2− ) rather than as chloride complexes
(Benning and Seward, 1996; Williams-Jones et al., 2009). The forma-
tion of this complex is expressed as: Au + H2S + HS− = Au
−
(HS) 2 + 0.5H 2. The ore-forming fluids contain some carbonate ions,
which may play an important role in gold transportation and enrich-

− +
as AuCl2− and Au(HS)2− (Gammons and Williams-Jones, 1995; ment. Due to the presence of CO2 within the fluid, the pH of fluid would
3 3
Sverjensky et al., 1997; Williams-Jones et al., 2009). The precipitation be buff ered through CO2 + H2O ↔ H2CO3, H2CO3 ↔ H(CO)3 + H

− 2−
of gold during pyrite-sericite-quartz alteration accompanies the base- and H(CO) ↔ CO + H+. This buff ering eff ect enhances the sta-

384
Z. Liu et
al.
metal minerals (predominantly sulfides) and sericitic assemblages
(Fig. 6f). An important gold mineralization process in the disseminated
ore of the Axi deposit involved hydrothermal fluid/rock interaction,
especially sulfidation, during which Fe consumed the reduced sulfur,
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Ore Geology Reviews 102 (2018) 368–
385
bility of Au(HS)2− and elevates gold solubility in fluids (Phillips and
Evans, 2004; Brugger et al., 2008; Chi et al., 2009).
The mineralized quartz veins and breccia systems at the Axi deposit,
which constitute most of the Au reserves, are controlled by hydraulic
Z. Liu et
al.
fracturing and/or seismic movement along fault zones. Fracture zones
typically surrounded by pyrite-sericite-quartz wall rocks, serve as effi-
cient channels for gold transport into shallow epithermal domains, due
to the limited loss of auriferous complexes in the relatively nonreactive
pathways in deeper levels (Heinrich et al., 2004; Williams-Jones and
Heinrich, 2005; İmer et al., 2016). The formation of structural fracture
zones can result in the hydrothermal eruption and fluid boiling, ac-
companied by an intense liquid-vapor separation involving a very rapid
and total loss of volatiles to the vapor phase, thereby resulting in major
gold deposition events. The occurrence of boiling events is also sup-
ported by fluid inclusion characteristics (Feng, 2005; Zhai et al., 2009),
the presence of adularia (Jia et al., 1999; Zhai et al., 2009) and platy
calcite (Zhai et al., 2009). It follows that the silicic alteration and/or
breccia zones at the Axi deposit are proximal to fluid conduits that
allow gold precipitation throughout the deposit. This mechanism can
explain both the formation of native gold and the high gold grade in
quartz veins (e.g., Canet et al., 2011), suggesting that boiling is a more
important gold depositional mechanism than sulfidation in the Axi
deposit.
5.4. Evolution model of hydrothermal processes and its implications
Our studies of hydrothermal processes at the Axi LS epithermal
deposits indicate a two-stage mineralization history: the early ore stage
(Stage I) intimately associated with pyrite-sericite-quartz alteration in
magmatic hydrothermal systems, while the later ore stage (Stages II and
III) is related to silicification and large input of meteoric fluid. During
the early ore stage (Stage I), magmatic fluid at depth migrated upward
along foundational faults, shallow faults or cracks, (Fig. 18a), and ex-
tracted minor amounts of CO2 and organic gas from the basement
strata. Meanwhile, the infiltration and diff usion of meteoric water oc-
curred along fracture zones, leading to propylitic alteration in sur-
rounding rock, which increased the content of K+, H+, and Si in the
fluid. Gold was transported as Au-bearing chloride- and sulfur- com-
plexes in hydrothermal fluids (An and Zhu, 2017; and references
therein). Due to the destabilization of Au–bearing complexes during
sulfidation, gold and py1 deposition occurred in pyrite-sericite-quartz
alteration around flow paths (Fig. 18a).
During the later ore stage (Stages II and III), ore-forming fluids were
composed of minor magmatic water and much meteoric water. There
was a deep, wide, and persistent hydrothermal fluid circulation
(Fig. 18b), accompanied by acid weakened, temperature and sulfur
fugacity decreased, and oxygen fugacity increased. The components of
2−
the ore-forming fluid were rich in Si, K+, Cl−, and CO3 . It is notable
that ore-forming metals, such as Au, As, Ag, Cu, Pb, Zn, and Sb, while
depleted in Stage II, are remarkably enriched in Stage III. In addition,
the primary pyrites are typically replaced by the late sulfides (Fig. 7n)
and the rims of all generations of pyrite are enriched in Au and As
(Fig. 15), with high Au/As ratios. Moreover, the Au vs. Au/As and Au/
Ag vs. Au/As plots discriminate diff erent types of pyrite (Fig. 14f and
g). These geochemical characteristics indicate that metamorphic de-
volatilization in Stage III mobilized some gold into the circulating ore-
forming fluids from multiple sources (Fig. 18b) (e.g., Large et al., 2007;
Zhang et al., 2014). Due to liquid-vapor separation resulting from hy-
draulic fracturing and/or seismic activity, the hydrothermal fluids
concentrated in and around flow channels in which the major gold
precipitated.
During the post-mineralization stage (Stage IV), the circulating
hydrothermal fluids were composed mostly of meteoric water
2−
(Fig. 18c), enriched in Ca, Mg, CO32− and SO4 , and the pH changed
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Ore Geology Reviews 102 (2018) 368–
385
with porphyry deposits. But several co-occurring porphyry and LS
epithermal deposits have been observed, such as the Zhilingtou,
Jinjiyan, Yueyang Au-Ag ( ± Cu) deposits in South China (Li and Jiang,
2017; Zhong et al., 2017a, 2017b) and the Ladolam Au deposit in Lihir
Island (Müller et al., 2002). The Tulasu basin hosts numerous porphyry
and epithermal deposits, which likely formed during two major epi-
sodes as discussed above. Recently, Zhong et al. (2017b) proposed a
two-stage mineralization model for the Yueyang deposit in the Zijin-
shan district, including early porphyry-type Cu mineralization related to
magmatic water and late LS epithermal Ag-Au-Cu mineralization related
to meteoric water. Only one sericite-quartz-pyrite ± chlorite alteration
event was recognized in the Yueyang deposit, which is clo- sely associated
with porphyry Cu mineralization. Notably, the early gold mineralization
in the Axi deposit and porphyry Au ± Cu miner- alization in the Abiyindi
deposit both have the close genetic association with the magmatic water
and show disseminated-style mineralization related to the sericite-quartz-
pyrite alteration. The potential porphyry mineralization within the Axi
district must be further explored.
6. Conclusions
(1) There are four diff erent types of hydrothermal pyrite in the para-
genetic sequence of mineralization at the Axi deposit. Py1 was
mostly formed in sulfidation reactions during pyrite-sericite-quartz
alteration. Py2 and py3 formation occurred in a mixed hydro-
thermal environment and were deposited together with quartz
during silicification.
(2) Two types of ore, i.e., disseminated type and silicified vein type
have been distinguished in the Axi gold deposit. Gold was mainly
deposited in solid solution in pyrite grains. Sulfidation was the
mineralization mechanism of disseminated ore while boiling by
hydraulic fracturing and/or seismic movement resulted in more
gold deposition in silicified vein type ores.
(3) The Axi LS epithermal deposit had a two-stage mineralization his-
tory during which gold mineralization occurred under acidic/near-
neutral and reducing conditions. The ore-forming fluids in the early
ore stage had a relatively high proportion of magmatic water,
which contained a high concentration of Cu, Co, Ni, Mn, Cl-, HS-,
K+, and H+. The fluids in the later ore stage and post-ore stage
were mostly composed of meteoric water enriched in As, Si, Cl−,
HS−, CO3 , and Ca, Mg, CO3 , SO4 , respectively.
2− 2− 2−
Acknowledgments
We thank the Editor-in-Chief Franco Pirajno and Associate Editor
Alexander Yakubchuk for their editorial assistance and supportive
comments. We are very grateful to three anonymous reviewers for their
critical and constructive comments to improve our paper. We thank
Prof. Jianfeng Gao, Dr. Jianping Liu, and Dr. Renyu Zeng for their as-
sistance in this study. We appreciate Prof. Jeff rey M. Dick and Syed
Muzyan Shahzad for their linguistic assistance. Thanks are given to
Jianmin Han, Hongxi Fan, and Xudong Han for their support during
fieldwork. This study is supported by projects from National Key R&D
Program of China (No. 2017YFC0601503, No. 2017YFC0602402),
National Natural Science Foundation of China (No. 41472301, No.
41772349, No. 41702073), and Innovation Driven Plan of Central
South University (No. 2015CX008).
Appendix A. Supplementary data
Z. Liu et Ore Geology Reviews 102 (2018) 368–
al. 385
from weakly acid to near neutral. A reductant infiltrated into the hy- Supplementary data to this article can be found online at https://
drothermal system because of the deep convective circulation. Possibly doi.org/10.1016/j.oregeorev.2018.09.009.
associated with the elevated setting and frequent tectonic movements in
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