Ore Geology Reviews 150 (2022) 105153

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Ore Geology Reviews

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Ore‑forming process revealed by sphalerite texture and geochemistry: A

case study at the Kangjiawan Pb–Zn deposit in Qin-Hang Metallogenic Belt,
South China
Hongjie Shen a, b, Yu Zhang a, b, *, Changhu Zuo c, Yongjun Shao a, b, Lianjie Zhao a, b, Jinze Lei a, b,
Guowei Shi d, Ruyu Han a, b, Xiyue Zheng a, b
a
Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitor (Central South University), Ministry of Education, Changsha
410083, China
b
School of Geosciences and Info-Physics, Central South University, Changsha 410083, China
c
Hunan Shuikoushan Nonferrous Metals Group Co., Ltd, Changning 421500, China
d
Hunan Provincial Remote Sensing Geological Survey and Monitoring Institute, Changsha 410114, China

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

Keywords: The origin of the abundant hydrothermal vein-type Pb–Zn deposits in the Qin-Hang Metallogenic Belt (QHMB) in
Sphalerite South China remains disputed due to the poor constraints on the ore-forming process. The Kangjiawan (1.96 Mt
Trace element geochemistry @ 4.70% Zn and 6.02% Pb), is a representative Pb–Zn deposit in the central QHMB, and its mineralization can be
Kangjiawan Pb–Zn deposit
divided into three stages: (I) pre-ore quartz-pyrite, (II) main-ore quartz-pyrite-galena-sphalerite, and (III) Late
Qin-Hang Metallogenic Belt
Fluid boiling
ore calcite-pyrite-galena-sphalerite. Stage II sphalerite (Sp2) commonly coexists with pyrite and chalcopyrite,
Skarn-type mineralization and shows a homogeneous internal texture. Stage III sphalerite (Sp3) comprises two generations of sphalerite,
namely the earlier, texturally homogeneous Sp3a (coexists with “chalcopyrite disease”), and the younger Sp3b
that replaced Sp3a and coexists with galena.
Sp2 is Fe-Mn-Co-In-rich, and characterized by the high In/Ga (avg. 2.6) and Zn/Cd (avg. 242.0), but low Zn/Fe
(avg. 12.2) ratios, suggesting high ore-forming temperature, consistent with the results of the sphalerite GGIMFis
geothermometer (307–314 ℃ with an average of 310 ℃). Sp3a has higher Se, Co, and Ni contents than Sp3b,
implying the possible decline of temperature from Sp3a to Sp3b. Meanwhile, the Kangjiawan sphalerite
geochemistry suggests a decreasing trend of fS2 from Sp2 (lg fS2 = − 10.5 to − 12.4) to Sp3 (lg fS2 = − 17.2 to
− 20.3). These results indicate a dramatic change in the temperature and fS2 from the main-ore to the late-ore
stage, probably caused by the mixing between meteoric water and magmatic-hydrothermal fluids in Stage III, as
supported by published H–O isotope data. The ubiquitous hydrothermal breccias with fine-grained pyrite
cement suggest fluid boiling in Stage II. The Kangjiawan sphalerite geochemistry is similar to that of skarn-type
sphalerite, consistent with the close spatial–temporal link between the Kangjiawan mineralization and the
Shuikoushan granodiorite stock. Therefore, we inferred that the Kangjiawan is a Pb–Zn skarn deposit genetically
related to the Shuikoushan granodiorite, with the ore precipitation caused by fluid boiling and meteoric water
incursion.

1. Introduction decipher ore genesis, such as skarn-type (e.g., Cook et al., 2009; Zhang
et al., 2022), Mississippi Valley-type (MVT) (e.g., Zhuang et al., 2019;
Geochemical composition and internal texture of sphalerite are Liu et al., 2022), volcanogenic massive sulfide (VMS) (e.g., Wei et al.,
widely used to track the physicochemical evolution of hydrothermal ore 2018, 2019; Yuan et al., 2018), sedimentary exhalative (SEDEX) (e.g.,
deposits (Cook et al., 2016; Keith et al., 2016a, b; Tardani et al., 2017; Gu et al., 2000; Ye et al., 2011) and epithermal-type (e.g., Cook and
Keith et al., 2018; Dimitrijeva et al., 2020; Steadman et al., 2021), and to Ciobanu, 2004; Bauer et al., 2019) deposits.

* Corresponding author at: Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitor (Central South University),
Ministry of Education, Changsha 410083, China.
E-mail address: [email protected] (Y. Zhang).

https://doi.org/10.1016/j.oregeorev.2022.105153
Received 1 September 2022; Received in revised form 4 October 2022; Accepted 7 October 2022
Available online 8 October 2022
0169-1368/© 2022 The Author(s). 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. Shen et al. Ore Geology Reviews 150 (2022) 105153

Fig. 1. (a) Location of southern Hunan district in the Qin-Hang Metallogenic Belt (modified after Zhou et al., 2006; Mao et al., 2013); (b) Geologic map of the
Hengyang Basin district (modified after Li et al., 2019).

The Qin-Hang Metallogenic Belt (QHMB) is a well-known Mesozoic and clastics, Devonian-Triassic limestone and shale, and Triassic-
Cu–Mo–Pb–Zn polymetallic province in South China, hosting many Neogene sandstone and siltstone (Fig. 1b; Li et al., 2019). The base­
important porphyry-, skarn-, and hydrothermal vein-type deposits ment is composed of Proterozoic and lower Paleozoic low-grade meta­
(Fig. 1a; Mao et al., 2011; Yuan et al., 2018; Zheng et al., 2018; Zhang morphic rocks and the upper Paleozoic limestone, which is
et al., 2018). The Hengyang Basin in the QHMB hosts plenty of (super-) unconformably overlain by Devonian-Permian carbonate sequences
large Pb–Zn deposits, such as the Shuikoushan, Qingshuitang, Liush­ (Ting et al., 2003), which are the main Pb–Zn ore host in the region (Li
utang, Hongshanmiao (Fig. 1b; Li et al., 2016; Li et al., 2019; Liu et al., et al., 2021).
2022). However, the metallogenesis of these deposits is still poorly Multistage tectonic events and associated magmatism may have
constrained and is debated to have had a Yanshanian magmatic- widely occurred in the Hengyang Basin. The Caledonian (Late Silurian-
hydrothermal (Fu et al., 2012; Zuo et al., 2014; Kang et al., 2015; Lu Devonian) orogeny likely formed EW-striking folds and EW-/NE-trend­
et al., 2017) or MVT (Song, 1993; Zou, 1993; Liu et al., 2022) origin. ing faults (Li and Peng, 1996; Liang and Guo, 2002; Zhou et al., 2006).
The Kangjiawan Pb–Zn deposit, with a proven ore reserve of 1.96 Mt Subsequently, a series of NS-striking folds were developed during the
@ 4.70 % Zn and 6.02 % Pb (Ouyang et al., 2020, 2021), is located on Indosinian (Triassic) orogeny, and the regional tectonics was super­
the southern margin of the Hengyang Basin. Its extensive occurrence of imposed by Yanshanian (Jurassic-Cretaceous) NNE-trending basin rifts
multiple sphalerite generations makes it an ideal target for constraining and faults, in response to the Paleo-Pacific subduction rollback (Shu
the mineralization history through sphalerite geochemistry. This study et al., 2004; Mao et al., 2007; Hu et al., 2017). Mesozoic granitoids were
focuses on the trace-element geochemistry of the Kangjiawan multistage emplaced extensively in the Hengyang Basin, which occur as batholiths,
sphalerite using laser ablation inductively coupled plasma-mass spec­ laccoliths, stocks, and dikes (Fig. 1b; Shu et al., 2011; Yuan et al., 2011;
trometry (LA-ICP-MS), coupled with scanning electron microscope Li et al., 2019). These granitoids were emplaced in the Triassic (ca.
(SEM) back-scattered electron (BSE) imaging. We aim to elucidate the 251–201 Ma), e.g., the Zhoujialing biotite granite (203 ± 1.4 Ma; Miao
ore-forming physicochemical conditions and evolution, unravel the ore- et al., 2014), Jiangjunmiao biotite adamellite (229.1 ± 2.8 Ma; Li et al.,
forming process, and provide new constraints on the origin of the veined 2020) and the Guandimiao biotite granite (240–220 Ma; Chen et al.,
Pb–Zn mineralization in the QHMB. 2006); Mid-Late Jurassic (ca. 180–142 Ma), e.g., the Dayishan biotite
adamellite (160–150 Ma; Li et al., 2022), Yagongtang granodiorite
2. Geological setting (156.3 ± 0.6 Ma; Li et al., 2020) and the Xianrenyan monzonite (156.1
± 0.5 Ma; Zhen et al., 2012); and Cretaceous (ca. 140–66 Ma), e.g., the
2.1. Regional geology Baishifeng biotite adamellite (135.4 ± 0.8 Ma; Song et al., 2020).

The Hengyang Basin district (in central QHMB) is situated along the
2.2. Deposit geology
suture zone between the Yangtze and Cathaysia Block (Fig. 1a). Exposed
stratigraphy comprises primarily Neoproterozoic-Silurian carbonates
The Kangjiawan deposit is located on the southern margin of

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Fig. 2. (a) Geologic map (modified after Yang, 1985) and (b) typical geological profile (modified after Li et al., 2021) of the Kangjiawan Pb–Zn deposit.

Hengyang Basin, adjacent to the Shuikoushan and Laoyachao Pb–Zn limestone and dolostone are the secondary ore host (Li et al., 2021;
deposits (Fig. 2a). Local outcropping sequences range from Devonian Liang et al., 2021; Fig. 2a).
(Xikuangshan Formation (Fm.) muddy limestone and sandstone) to The structural framework at Kangjiawan is controlled by a series of
Cretaceous (Dongjing Fm. sandstone). The Lower Permian Dangchong nearly NS-trending folds and faults, notably the Kangjiawan inverted
Fm. muddy limestone and the Qixia Fm. limestone is the primary Pb–Zn anticline and large thrust faults (F22 and F17; Fig. 2a). The Kangjiavan
ore host, whereas the Carboniferous Hutian Group (Gp.) dolomitic inverted anticline is concealed beneath the Cretaceous-Jurassic

Fig. 3. Alteration and mineralization paragenetic sequence at Kangjiawan.

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Fig. 4. Typical alteration and mineralization photos at Kangjiawan: (a) Coarse-grained pyrite (Py1) and quartz; (b) Py1 with cataclastic texture and abundant silicate
inclusions, and fine-grained pyrite (Py2), veined galena, and sphalerite (Sp2) in Stage II; (c) Strong silicic alteration mainly in breccia zone; (d) Py2 around wallrock
breccia; (e) Py2 cementing hydrothermal breccia; (f) Stage II quartz-galena-sphalerite vein cut Py1; (g) Local Stage II muscovite; (h) Porous Py2 intergrown with
sphalerite and galena; (i) Euhedral arsenopyrite with abundant cracks intergrown with porous Py2; (j) Minor pyrrhotite replaced chalcopyrite; (k) Stage II pyrite-
galena-sphalerite vein cut by Stage III calcite-sulfides vein; (l) Calcite coexists with abundant pyrite (Py3), galena and sphalerite (Sp3) in Stage III; (m) Sp3 co­
exists with galena and replaced Py3 (pseudomorphic texture), and abundant “chalcopyrite disease” homogeneously distributed in sphalerite; (n) Galena replaced by
chalcopyrite locally; (o) Galena replaced Py3. Abbreviations: Py = pyrite; Sp = sphalerite; Gn = galena; Apy = arsenopyrite; Ccp = chalcopyrite; Po = pyrrhotite; Qz
= quartz; Cal = calcite; Ms = muscovite.

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unconformity (Yang et al., 1985). Its core consists of the Qixia Fm. Table 1
limestone and the Hutian Gp. dolostone, and its two limbs are composed Descriptions of representative sphalerite samples at Kangjiawan.
of the Douling Fm. sandstone and shale and the Dangchong Fm. muddy Sample No. Stage Mineral assemblages Orebody No.
limestone. Fractures are developed in the anticlinal axis, which repre­
K2-6-1 II Qz-Py-Gn-Sp I-3
sents a favorable ore-fluid conduit (Li et al., 2021). The regional F22 fault K2-10-2 II Qz-Py-Gn-Sp III-2
(primary ore-conducting structure) extends for > 6 km in the mining K3-1-3 II Qz-Py-Gn-Sp I-3
district, strikes N–S, and dips to the west at an angle of 30–40◦ (Fig. 2; K5-1-4 II Qz-Py-Gn-Sp I-3
Yang, 1985). Fault F17 is NE-trending, >20 km long, and concealed K8-5-5 II Qz-Py-Gn-Sp III-2
K7-1-6 III Cal-Py-Gn-Sp IV-1
beneath the Cretaceous sandstone and shale. The fault dips mainly to the K7-2-7 III Cal-Py-Gn-Sp IV-1
west (locally to the east) with an angle of 25–30◦ . These major thrust K7-3-8 III Cal-Py-Gn-Sp IV-1
faults have a series of NE-striking secondary faults (e.g., F8 and F47;
Fig. 2b).
The Shuikoushan granodiorite stock (158.8 ± 1.8 Ma; Huang et al., is mostly subhedral to anhedral (Fig. 4m, o), and is locally replaced by
2015) was emplaced in the core of the Kangjiawan inverted anticline or chalcopyrite (Fig. 4n). Calcite occurs locally as euhedral grains (Fig. 4l)
along the F22 fault (Fig. 2a), whereas the barren Laomengshan and forms large geodes (Li et al., 2021).
porphyritic dacite (156.7 ± 1.6 Ma; Zuo, 2015) and Xinmengshan
rhyolite porphyry (158.8 ± 0.4 Ma; Li, 2012) intruded mainly into the 4. Sampling and analytical methods
eastern side of the inverted anticline and fault (Fig. 2a). The Shui­
koushan granodiorite stock (outcrop size: 1.2 × 1.6 km) intruded into 4.1. Samples
the Carboniferous-Permian sedimentary sequences (Yang et al., 2016).
In addition, many small plutons (outcrop size: 0.05 × 0.25 km2) occur A total of 35 samples were collected from drill cores and under­
locally as composite stocks, dikes, and sills (Ouyang et al., 2020). ground stopes. Among them, eight sphalerite-rich ore samples were
A total of 61 Pb–Zn vein-type/lensoidal orebodies have been delin­ selected for sphalerite textural and geochemical analyses. Detailed
eated at Kangjiawan, among which seven are more important (I–VII) (Li sample descriptions are listed in Table 1. Accordingly, these samples
et al., 2021; Liang et al., 2021). Orebodies I–V were developed in the were selected for petrographic observation under reflected and trans­
silicified breccia zones in/near the Jurassic-Permian unconformity, mitted polarized light microscopy and BSE imaging. Subsequently, six
while orebodies VI and VII occur along the F22 hanging-wall in the samples were selected for EPMA analysis (K2-6, K2-10, K3-1, K7-1, K7-2,
Lower Permian argillaceous limestone (Fig. 2b). The orebodies generally K7-3), and eight for LA-ICP-MS trace element spot analysis (K2-6, K2-10,
strike N–S and are mainly west-dipping (locally east-dipping) with an K3-1, K5-1, K8-5, K7-1, K7-2, K7-3).
angle of 15–40◦ (Zhang, 1990). Orebody IV-3, the largest orebody at
Kangjiawan (0.443 Mt contained Pb + Zn metal, accounting for 50.6 % 4.2. SEM-BSE imaging
of the total metal reserve at Kangjiawan; Ouyang et al., 2020, 2021), is
859 m long, 33–174 m wide, and 0.14–19.43 m (avg. 6.0 m) thick (Zuo Prior to the EPMA and LA-ICP-MS analyses, polished thin sections
et al., 2014; Zuo, 2015). were prepared for each sample. SEM-BSE imaging of Stage II and III
sphalerite grains was performed on a Sirion200 FE-SEM, at the School of
3. Paragenetic sequence of mineralization and alteration Materials Science and Engineering, Central South University. The FE-
SEM was operated under 30 kV accelerating voltage and 15nA beam
Based on the mineral assemblages and textural relationships, the current.
mineralization/alteration paragenetic sequence at Kangjiawan can be
divided into three stages: (I) quartz-pyrite, (II) quartz-pyrite-galena- 4.3. EMPA sphalerite major element analysis
sphalerite, and (III) calcite-pyrite-galena-sphalerite (Fig. 3).
Stage I is dominated by euhedral-subhedral coarse-grained pyrite The analysis was performed at the School of Geoscience and Tech­
(Py1) and quartz (Fig. 4a, b). Py1 (size: 5 mm to 3 cm, locally up to 5 cm) nology, Southwest Petroleum University (Chengdu, China), using a
(Fig. 4a, b) has abundant silicate inclusions (Fig. 4b), and is associated JEOL JXA-8230 EPMA. Before the analysis, the samples were uniformly
with strong silicification (Fig. 4c). Py1 is commonly cut by later galena carbon-coated (20 nm thick). Analytical conditions include 20 kV
veins/veinlets (Fig. 4b). accelerating voltage, 20nA beam current, and 30 μm spot size. Matrix
Stage II (main ore stage) is characterized by fine-grained pyrite (Py2) correction was carried out with the ZAF correction program, yielding a
wrapping and/or cementing wall rock breccia (Fig. 4d, e). The euhedral- precision of better than 1 %. The measured elements are S, Pb, Fe, Zn,
subhedral Py2 (mainly 0.5–10.0 mm) is intergrown commonly with As, Mn, Cu, Ga, Sn, and Cd, which were calibrated with the following
quartz, sphalerite, and galena (Fig. 4f-h), and locally with muscovite standards: FeS2 (for Fe and S), ZnS (for Zn), CuFeS2 (for Cu), Cd (for Cd),
(Fig. 4g), chalcopyrite, and euhedral arsenopyrite (0.2–5 mm) with FeAsS (for As), SnO2 (for Sn), GaAs (for Ga) and PbS (for Pb).
abundant cracks (Fig. 4i) and pores (Fig. 4h, i). Stage II quartz-galena-
sphalerite vein (commonly 0.3–1.5 cm wide) cut Py1 (Fig. 4f), and the 4.4. LA-ICP-MS sphalerite trace element analysis
sphalerite (Sp2) of this stage is subhedral (size: 0.5–3 mm) and
commonly coexists with galena (Fig. 4h). Chalcopyrite is distributed in The analysis was performed on an NWR 193 nm ArF Excimer laser-
Sp2 with the “chalcopyrite disease” texture (Fig. 4h). Meanwhile, galena ablation system coupled to an iCAP RQ (ICPMS), at the Guangzhou
is mostly euhedral to subhedral (size: 0.2–1.0 mm; Fig. 4h), and some Tuoyan Analytical Technology Co. ltd. (Guangzhou, China). The ICPMS
pyrrhotite replaced chalcopyrite locally (Fig. 4j). was tuned with NIST 610 standard glass to yield low oxide production
Stage III is dominated by the calcite-sulfide assemblage, which oc­ rate. 0.7 l/min He carrier gas was fed into the cup, and the aerosol was
curs mainly as veins (2.0–5.0 cm wide). These sulfides include primarily subsequently mixed with 0.89 l/min Ar make-up gas. The laser fluence is
sphalerite (Sp3), galena, pyrite (Py3), and chalcopyrite (Fig. 4k), and the 3.5 J/cm2, with 6 Hz repetition rate, 30 μm spot size. Each analysis
veins commonly cut Stage II pyrite-galena-sphalerite veins (Fig. 4k, l). consisted of 40 s of background measurement and 40 s of sample mea­
Sp3 (size: 500 μm to 3 mm) commonly coexists with galena (Fig. 4m-o) surement. Raw isotope data were reduced using the “TRACE ELE­
and replaced Py3 (size: 0.2–3.0 mm), displaying pseudomorphic texture MENTS” data reduction scheme (DRS). The DRS runs in the freeware
(Fig. 4m). Furthermore, a large amount of “chalcopyrite disease” is IOLITE package of Paton et al. (2011). In IOLITE, user-defined time
homogeneously distributed in Sp3 (Fig. 4m, n). Galena (size: 0.5–5 mm) intervals are established for the baseline correction procedure to

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Fig. 5. Representative BSE images of the Kangjiawan sphalerite grains: (a-b) dark-gray Sp2 with homogeneous (no zoning or replacement) texture; (c) dark-grey
Sp3a with homogeneous texture, and replaced by Sp3b along cracks; (d) light-grey Sp3b replaced Sp3a in patches. Abbreviations: Sp = sphalerite; Py = pyrite;
Gn = galena; Ccp = chalcopyrite.

Fig. 6. Box and whisker plot for trace element contents of the three sphalerite types from Kangjiawan.

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Fig. 7. Representative LA-ICP-MS time-resolved depth profiles for the Kangjiawan sphalerite.

calculate session-wide baseline-corrected values for each isotope. Blocks types of sphalerite, including Sp2 (n = 7), Sp3a (n = 10), and Sp3b (n =
of two standards (NIST 610 and GSE-2G) and one MASS-1 sulfide 6), with the results listed in Appendix I.
standard analysis were followed by 5 to 8 unknown samples. For The three sphalerite types have similar average Zn and S contents.
sphalerite, the following 32 isotopes were measured: 34S, 47Ti, 51V, 53Cr, However, Sp2 has higher Fe (avg. 5.13 wt%) than Sp3 (avg. 4.16 wt%),
55
Mn, 57Fe, 59Co, 60Ni, 65Cu, 66Zn 71Ga, 74Ge, 75As, 77Se, 85Rb, 88Sr, but lower Cd (avg. 0.25 wt%) and Mn (avg. 0.80 wt%) contents than Sp3
93
Nb, 97Mo, 107Ag, 111Cd, 115In, 118Sn, 121Sb, 126Te, 184W, 185Re, 197Au, (avg. 0.30 and 1.05 wt%, respectively). Furthermore, Sp3b has higher
202
Hg, 205Tl, 208Pb, 209Bi and 238U corresponding to a total dwell time of average Cd (0.34 wt%) and Mn (1.09 wt%) contents than Sp3a (avg.
320 ms. The MASS-1 sulfide standard (15.6 wt% Fe; Wilson et al., 2002) 0.27 and 1.03 wt%, respectively) but lower Fe (avg. 3.70) content than
was used as the primary standard for calibrating 34S, 51V, 53Cr, 55Mn, Sp3a (avg. 4.42).
57
Fe, 59Co, 65Cu, 66Zn 71Ga, 74Ge, 75As, 77Se, 97Mo, 107Ag, 111Cd, 115In,
118
Sn, 121Sb, 126Te, 184W, 185Re, 197Au, 202Hg, 205Tl, 208Pb and 209Bi. 5.3. Trace element geochemistry
47
Ti, 60Ni,85Rb, 88Sr, 93Nb, and 238U were corrected with GSE-2G (7.55
wt% Fe) synthetic basaltic glass standard, which was prepared using the LA-ICP-MS spot analysis was performed on eight sphalerite samples
material developed by Myers et al. (1976). EMPA-measured Zn content (60 spots each for Sp2, Sp3a, and Sp3b). The results are presented in
was used as the internal standard. Appendix I and Fig. 6.
Cobalt, Ag, In, and Pb contents are higher in Sp2 (avg. 1.97, 20.0,
5. Results 7.76, and 6.54 ppm, respectively) than in Sp3 (avg. 0.457, 3.48, 0.425,
and 0.587 ppm, respectively). On the contrary, Ga and Sn contents are
5.1. Internal texture of sphalerite lower in Sp2 (avg. 6.78 and 1.36 ppm, respectively) than in Sp3 (avg.
9.15 and 8.23 ppm, respectively). Sp3b has higher Cu (344 ppm), Ga
Under BSE imaging, Sp2 is dark-gray (Fig. 5a, b) and commonly (11.2 ppm), Cd (4048 ppm), Ag (7.38 ppm), Sn (12.0 ppm) Sb (3.79
shows homogeneous (no zoning or replacement) internal texture. ppm), and Pb (2.75 ppm), but lower In (0.254 ppm) than Sp3a (Cu: 159
Meanwhile, Sp3 can be subdivided into the earlier Sp3a and the later ppm; Ga: 9.15 ppm; Cd: 2825 ppm; Ag: 3.42; Sn: 8.41 ppm; Sb: 0.303
Sp3b (Fig. 5c, d). Sp3a is dark-grey in BSE image and is texturally ho­ ppm; Pb: 0.242 ppm; In: 0.942 ppm). The contents of V, Cr, Ni, Mo, Rb,
mogeneous (Fig. 5c), while Sp3b (light-grey under BSE) clearly replaced Sr, Au, and U are below the detection limit.
Sp3a along cracks (Fig. 5c) or in patches (Fig. 5d).

5.2. Major element geochemistry

A total of 23 EMPA spot analyses were conducted on the different

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Fig. 8. Binary plots of (a) Zn vs (Fe + Cd + Mn); (b) Ag vs Sb; (c) Cu vs Sn; (d) (Cu + Ag) vs (Ga + In + Sn + Sb) for the Kangjiawan sphalerite.

6. Discussions sphalerite lattice via coupled substitution. This is demonstrated by the

apparent positive Ag vs Sb (R2 = 0.75; Fig. 8b), Cu vs Sn (R2 = 0.73;
6.1. Trace element occurrence in sphalerite Fig. 8c) and (Cu + Ag) vs (Ga + In + Sn + Sb) (R2 = 0.87; Fig. 8d)
correlations.
Sphalerite is commonly observed to contain micro-/nano-inclusions
(Johan et al., 1983; Cook et al., 2016; Wei et al., 2019; Liu et al., 2022), 6.2. Physicochemical conditions of the Kangjiawan mineralization
which could mask the host-mineral geochemical compositions (Keith
et al., 2022). Therefore, it is important to evaluate the effect of these 6.2.1. Temperature
nano-inclusions on the overall sphalerite geochemical composition. LA- Sphalerite trace element composition (e.g., Mn, Fe, Cu, Ga, Ge, Cd,
ICP-MS time-resolved signal spectra can provide information on the In, Sn) can be used to estimate the mineralization temperature and
trace element occurrence in sphalerite (Belousov et al., 2016). Iron, Mn, sulfidation state (Cook et al., 2009; Ye et al., 2011; Frenzel et al., 2016,
Cd, In, and Sb in the representative time-resolved signal spectra for Sp2, 2022). High-temperature sphalerite is commonly Fe-Mn-Cu-Co-In-sn-
Sp3a, and Sp3b are smooth and flat, suggesting the absence of corre­ rich with a high In/Ga (>1) ratio, whereas low-temperature sphalerite
sponding micro-inclusions in the Kangjiawan sphalerite (Fig. 7a, c). is Ga-Ge-Cd-rich with low In/Ge (<1) ratio (Liu et al., 1984; Ye et al.,
However, outliers in box-and-whisker plots may be indicative of evenly- 2011, 2016; Bauer et al., 2019). Sp2 is Fe-Mn-Co-In-rich (Fig. 6a), and
distributed nano-inclusions that cannot be resolved by LA-ICP-MS (Keith has a high In/Ga ratio (avg. 2.6). This suggests high crystallization
et al., 2022; Zhang et al., 2022). Therefore, the high contents (outliers) temperature, as supported also by its low Zn/Fe (avg. 12.2) (Dai et al.,
for Cu, Ga, Ag, Sn, and Pb in Sp2, Cu, Sn, and Pb in Sp3a, and Co, Cu, Ga, 2016) and high Zn/Cd (avg. 242.0) (Wen et al., 2016) ratios. Sp3 has
Ge, and Pb in Sp3b (Fig. 6) demonstrate that these sphalerite types may high Ga-Ge-Cd but low Fe-Mn-In-sn-Co (Fig. 6a) contents, reflecting low
contain nano-inclusions of the afore-mentioned elements. This is also crystallization temperature. Meanwhile, the magmatic fluids commonly
reflected by local signal peaks of Cu, Ag (Fig. 7b, d), and Pb (Fig. 7a, b). have higher Se (Li et al., 2018; Zhang et al., 2022), Co, and Ni (Bralia
Meanwhile, the wide Cu-Pb concentration ranges of Sp2 and Sp3 (Fig. 6) et al., 1979; Chen et al., 1987) concentrations than meteoric water. The
further support the micro-inclusion occurrence (Zhang et al., 2022), decreasing contents of Se (avg. 3.69 ppm for Sp3a, 3.08 ppm for Sp3b),
which is consistent with their coexistence with galena and chalcopyrite Co (avg. 0.467 ppm for Sp3a, below the detection limit for Sp3b), and Ni
and “chalcopyrite disease” (Fig. 4h, m, n). (avg. 4.36 ppm for Sp3a, below the detection limit for Sp3b) suggest that
Previous studies have proposed that bivalent cations (e.g., Fe, Mn, Sp3b may have been linked to the waning magmatic-hydrothermal
Cd, and Co) directly substitute for Zn in the lattice (e.g., Cook et al., system and increasing meteoric fluid influx, coupled with the possible
2009; Ye et al., 2011; Frenzel et al., 2020). The incorporation of trivalent decline of temperature from Sp3a to Sp3b.
and tetravalent cations, such as Ga, In, Ge, and Sn, is achieved mainly Sphalerite crystallization temperature was also evaluated using the
via coupled substitution of Zn by Cu+ and/or Ag+ (Cook et al., 2012; GGIMFis geothermometer (Frenzel et al., 2016). The results show that
Belissont et al., 2016; George et al., 2016; Wei et al., 2019). After Sp2 was formed under medium–high temperature (307–314 ℃ with an
filtering the geochemical outliers of the sphalerite samples, the positive average of 310 ℃), consistent with fluid inclusion microthermometric
(Mn + Fe + Cd) vs Zn correlation (R2 = 0.89; Fig. 8a) suggests that Mn, results (Stage II: avg. 324 ± 13 ℃; Li et al., 2021). Germanium con­
Fe, and Cd are readily incorporated into the sphalerite lattice via the centration in Sp3 is mostly below the detection limit and lower than that
replacement of Zn, whereas Ga-In-Sb-Sn may be incorporated into the in Sp2, suggesting that Sp3 may have formed at a lower temperature

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H. Shen et al. Ore Geology Reviews 150 (2022) 105153

than Sp2 (Belissont et al., 2014; Bauer et al., 2019), in accordance with
the afore-discussed temperature evolution.

6.2.2. Sulfur fugacity

Iron incorporation into the sphalerite crystal lattice is influenced by
both temperature and fS2 (Scott and Barnes, 1971; Keith et al., 2014;
Frenzel et al., 2016, 2022), and the latter can be estimated by the
sphalerite formation temperature (by GGIMFis geothermometer) and
FeS mol% (Scott and Barnes, 1971).
Despite the uncertainties in the absolute formation temperatures,
there are clear differences between the two sphalerite generations. The
calculated fS2 (lg fS2 = − 10.5 to − 12.4) for Sp2 (Stage II) lies well
within the intermediate-sulfidation field (Fig. 9). Germanium content is
all below the detection limit in Sp3, hence published fluid inclusion
microthermometric data (Stage III: 137.2–144.3 ℃; Li et al., 2021) was
used to calculate fS2. Accordingly, Sp3 (Stage III) lies within the low-
sulfidation field (lg fS2 = − 17.2 ~ − 20.3; Fig. 9), revealing a clear
fS2 drop from Stage II to III.

6.3. Pb–Zn ore precipitation mechanism

Fluid cooling, mixing, boiling (phase separation), fluid-rock inter­

action, acidification, and replenishment could trigger hydrothermal
Fig. 9. Temperature vs lg fS2 diagram adapted from Einaudi et al. (2003).
sulfide precipitation as they could influence many fluid physicochemical
Calculated temperatures in Stage II from the GGIMFis geothermometry (Frenzel
parameters (incl. temperature, salinity, pH, fO2, and fS2) (Kouzmanov
et al., 2016) and Stage III fluid inclusion microthermometric data are compared
with the sphalerite FeS content. The blue and green areas denote the fS2 field
et al., 2010; Deditius et al., 2014; Revan et al., 2014; Fontboté et al.,
for Sp2 and Sp3, respectively. Abbreviations: Cv = covellite; Dg = digenite; Py 2017; Wu et al., 2018; Schaarschmidt et al., 2021).
= pyrite; Bn = bornite; Ccp = chalcopyrite; Po = Pyrrhotite; Apy = arseno­ Previous studies stated that the Stage II (main-ore) Pb–Zn minerali­
pyrite; Lo = löllingite; Fe = native iron. zation at Kangjiawan occurred via fluid boiling, as supported by the
coexisting vapor- and liquid-rich, and hypersaline fluid inclusions with
similar homogenization temperature (Li et al., 2021). This inference is
also supported by the ubiquitous Py2-cemented hydrothermal breccias
(Fig. 4e). In addition, the abrupt change from stable to fluctuated
physicochemical conditions (as revealed by the transition from coarse-
grained Py1 to fine-grained porous Py2) further indicates boiling in

Fig. 10. Plots of (a) Mn vs Fe; (b) Mn vs In; (c) Ag vs Mn; (d) Cd/Fe vs Mn. Data are compiled from Sundblad. (1994), Cook and Ciobanu. (2004), Grammatikopoulos
et al. (2006), Cook et al. (2009), Ye et al. (2011), George et al. (2015), Wei et al. (2018), Yuan et al. (2018), Zhuang et al. (2019) and Liu et al. (2022).

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H. Shen et al. Ore Geology Reviews 150 (2022) 105153

Huang et al., 2015), and the garnet (garnet U–Pb age: 158.8 ± 2.5 Ma;
Qin et al., 2022) in the deep skarn zone have the similar ages. The
combined information suggests that the Kangjiawan is a distal skarn-
type deposit.
Trace elements in sphalerite (e.g., Mn, Fe, Co, Ga, Ge, Cd, and In)
have been used to distinguish deposit types (Cook et al., 2009; Ye et al.,
2011, 2016; Wei et al., 2019; Liu et al., 2022). Skarn-type sphalerite is
Co-Mn-rich but In-sn-Fe-poor (Cook et al., 2009; Ye et al., 2011),
whereas MVT sphalerite is Cd-Ga-Ge-rich and Fe-Mn-In-sn-Co-rich (Ye
et al., 2011, 2016; Hu et al., 2020; Liu et al., 2022). The Kangjiawan
sphalerite is generally featured by being Fe-In-sn-poor and Mn-Co-poor,
resembling skarn-type sphalerite. In the Fe–Mn (Fig. 10a), In–Mn
(Fig. 10b), Mn–Ag (Fig. 10c), and Mn–Cd/Fe (Fig. 10d) deposit-type
discrimination plots, the Kangjiawan sphalerite plots into the skarn-
type field. This is consistent with the skarn-type ore features (Fig. 2b),
and skarn-type ore mineral assemblage (incl. sphalerite, galena, pyrite,
arsenopyrite, chalcopyrite, and pyrrhotite) (Fig. 4). These features are
distinct from typical MVT deposits, which are featured by the lack of
clear magmatic link, low ore-forming temperature (75–200℃), and
dolomitization (main alteration style) (Leach and Sangster, 1993; Leach
et al., 2005, 2010).
Accordingly, we propose the following metallogenic process for the
Kangjiawan deposit (Fig. 11):
The magma-derived hydrothermal fluids were likely related to the
Shuikoushan granodiorite stock (~158 Ma; Huang et al., 2015; Zuo,
2015; Li et al., 2021), and percolated along the Kangjiawan inverted
anticline and the large-scale F22 fault (Yang, 1985; Fig. 11a), and
entered the interlayer fracture zones between the Lower Permian
Dangchong Fm. muddy limestone and Qixia Fm. limestone. The fluid
deposited coarse-grained Py1 with abundant silicate inclusions via
intensive water–rock interaction (Fig. 11a; Ma et al., 2022). With the
continuous ore-fluid injection, the fluid pressure increased gradually.
When fluid pressure exceeded the lithostatic load, shear stress accu­
mulation may have caused extensive hydraulic fracturing (Sibson et al.,
1988) and sudden fluid pressure drop. This, coupled with fluid boiling
(Zhang et al., 2020, 2022), may have induced the main-stage mineral­
ization (Fig. 11b). Finally, the meteoric water percolated along F22 fault
and mixed with the magmatic-hydrothermal fluid (Zuo, 2015; Zhang,
Fig. 11. Schematic diagram for the ore formation at Kangjiawan. See text 2018; Li et al., 2021), further triggering Stage III mineralization
for details. (Fig. 11c).

Stage II, because the porous texture is typical for boiling-related rapid 7. Conclusions
crystal growth (Román et al., 2019).
Additionally, previous studies suggested the fluid mixing between (1) The Kangjiawan mineralization can be divided into three stages:
magmatic-hydrothermal and meteoric water in Stage III, as supported by (I) pre-ore quartz-pyrite, (II) main-ore quartz-pyrite-galena-
H–O isotopes (Zhang, 2018; Li et al., 2021). The Kangjiawan sphalerite sphalerite, and (III) late ore calcite-pyrite-galena-sphalerite.
geochemistry suggests a clear fS2 drop from Sp2 (lg fS2 = − 10.5 to − (2) The Kangjiawan sphalerite geochemistry suggests a decreasing
12.4) to Sp3 (lg fS2 = − 17.2 to − 20.3), also demonstrating meteoric ore-forming temperature trend and fS2 (lg fS2 = − 10.5 to − 12.4
water incursion in Stage III. More importantly, Se, Co, and Ni contents (Sp2) and − 17.2 to − 20.3 (Sp3)) from Sp2 to Sp3.
are lower in Sp3 (avg. 4.40, 0.457, and 4.36 ppm, respectively) than in (3) Stage II and III Pb–Zn precipitation at Kangjiawan may have been
Sp2 (avg. 6.00, 2.89, and 11.1 ppm, respectively), supporting that Stage caused by fluid boiling and meteoric water incursion,
III Pb–Zn ore precipitation was related to meteoric water incursion given respectively.
that the magmatic fluids commonly have higher Se (Huston et al., 1995; (4) The Kangjiawan is best classified as a distal skarn-type Pb–Zn
Rowins et al., 1997, Fitzpatrick, 2008; Li et al., 2018; Zhang et al., deposit associated with the Shuikoushan granodiorite stock.
2022), Co, and Ni (Loftus-Hills and Solomon, 1967; Bralia et al., 1979;
Chen et al., 1987) concentrations than meteoric water. Declaration of Competing Interest

The authors declare that they have no known competing financial

6.4. Ore genesis and Metallogenic implications interests or personal relationships that could have appeared to influence
the work reported in this paper.
The Kangjiawan deposit shows a close spatial relationship with the
Shuikoushan granodiorite stock (Fig. 2a), and the skarn (esp., garnet) Data availability
alteration zone has also been recently found at a depth of 1000 m at
Kangjiawan (Qin et al., 2022). More importantly, the Kangjiawan Data will be made available on request.
mineralization (sphalerite Rb–Sr age: 154.6 ± 2.1 Ma; Zuo, 2015), the
Shuikoushan granodiorite stock (zircon U–Pb age: 158.8 ± 1.8 Ma;

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H. Shen et al. Ore Geology Reviews 150 (2022) 105153

Acknowledgments Frenzel, M., Voudouris, P., Cook, N.J., Ciobanu, C.L., Gilbert, S., Wade, B.P., 2022.
Evolution of a hydrothermal ore-forming system recorded by sulfide mineral
chemistry: a case study from the Plaka Pb–Zn–Ag Deposit, Lavrion, Greece. Miner.
This research was funded by the Postgraduate Research Innovation Deposita 57 (3), 417–438.
Project of Hunan Province (CX20220207) and the Science and Tech­ Fu, G.G., Xu, D.R., Xu, Y.M., Chen, G.H., Zhang, Y.J., 2012. Discussion on ore-controlling
nology Innovation Program of Hunan Province (2021RC4055). The conditions and genesis of the Zongshuban Pb–Zn–Ag deposit in southern Hunan.
Mineral Deposits 31, 275–276 in Chinese with English abstract.
authors thank Prof. Xiangping Gu (Central South University), Dr. Xi George, L., Cook, N.J., Ciobanu, C.L., Wade, B.P., 2015. Trace and minor elements in
Chen (Southwest Petroleum University), and Mr. Yubo Yang (Guangz­ galena: a reconnaissance LA-ICP-MS study. Am. Mineral. 100 (2-3), 548–569.
hou Tuoyan Analytical Technology Co. Ltd.) for helping with the in-situ George, L., Cook, N.J., Ciobanu, C.L., 2016. Partitioning of trace elements in co-
crystallized sphalerite–galena–chalcopyrite hydrothermal ores. Ore Geol. Rev. 77,
XRD, EPMA, and LA-ICP-MS analyses, respectively. 97–116.
Grammatikopoulos, T.A., Valeyev, O., Roth, T., 2006. Compositional variation in Hg-
Appendix A. Supplementary data bearing sphalerite from the polymetallic Eskay Creek deposit, British Columbia,
Canada. Geochemistry 66 (4), 307–314.
Gu, L.X., Hu, W.X., He, J.X., 2000. Regional variations in ore composition and fluid
Supplementary data to this article can be found online at https://doi. features of massive sulfide deposits in South China: Implications for genetic
org/10.1016/j.oregeorev.2022.105153. modeling. Episodes 23, 110–118.
Hu, X.L., Gong, Y.J., Pi, D.H., Zhang, Z.J., Zeng, G.P., Xiong, S.F., Yao, S.Z., 2017.
Jurassic magmatism related Pb–Zn–W–Mo polymetallic mineralization in the central
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