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Sphalerite Records Cd Isotopic Signatures of the Parent
Rocks in Hydrothermal Systems: A Case Study From the
Nayongzhi Zn–Pb Deposit, Southwest China
Wenrui Song
1,2,3
, Chuanwei Zhu
1,2
, Hanjie Wen
1,2,4
, Zhilong Huang
2
, Chen Wei
5
, Yuxu Zhang
2
,
Zhengbing Zhou
6
, Zhen Yang
7
, Xiaocui Chen
8
, Béatrice Luais
9
, and Christophe Cloquet
9
1
School of Earth Sciences and Resources, Chang'An University, Xi'an, China,
2
State Key Laboratory of Ore Deposit
Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, China,
3
State Key Laboratory of
Continental Dynamics, Department of Geology, Northwest University, Xi'an, China,
4
College of Earth and Planetary
Sciences, University of Chinese Academy of Sciences, Beijing, China,
5
Helmholtz–Zentrum Dresden–Rossendorf,
Helmholtz Institute Freiberg for Resource Technology, Freiberg, Germany,
6
State Key Laboratory of Nuclear Resources
and Environment, East China University of Technology, Nanchang, China,
7
School of Earth Resources, China University
of Geosciences, Wuhan, China,
8
Guizhou Institute of Technology, Guiyang, China,
9
Centre de Recherches Petrographiques
et Geochimiques, CNRS/UMR 7358, Vandoeuvre‐les‐Nancy, France
Abstract Metal stable isotopes (e.g., Zn, Cd, and Cu) have been used to track metal sources in different
types of hydrothermal systems. However, metal isotopic variations in sulphides could be triggered by various
factors such as mineral precipitation and fluid mixing. Thus, tracking the metal sources of hydrothermal
systems is still a big challenge for metal isotopes. In this study, we investigated the Cd isotopic systematics of
sphalerite from the Nayongzhi Zn–Pb deposit, which is a Mississippi Valley‐type (MVT) deposit in the
Sichuan–Yunnan–Guizhou mineralization province (SYGMP). We reinterpreted the published S isotope data
for the SYGMP and found that the large S isotopic variations were controlled by Rayleigh fractionation
between sulphide and reduced S. As such, a model that involves mixing of a metal‐rich fluid with a reduced S
pool formed by thermochemical sulfate reduction (TSR) can explain the ore formation in the Nayongzhi
deposit. Based on this model, no Cd isotopic fractionation was observed due to its low solubility in fluids
during mixing, and thus the Cd isotopic variations of sphalerite were inherited from the source rocks. The
large range of Zn/Cd ratios and uniform Cd isotopic compositions of the sulphides are similar to those of
igneous rocks but different from those of sedimentary rocks, indicating that Zn and Cd were derived mainly
from basement rocks (e.g., migmatite, gneiss, and granulite). Our results reaffirm that metal stable isotopes,
particularly Cd isotope compositions of sphalerite, are powerful geochemical tracers for investigating the
formation mechanisms of ore deposits.
Plain Language Summary Metal stable isotopes, particularly Cd isotopes, have been widely used in
investigating the metal sources, fluid evolution, and formation mechanisms of ore deposits. Here, we studied the
Cd isotopic compositions of sphalerite from the Nayongzhi Zn–Pb deposit in the Sichuan–Yunnan–Guizhou
mineralization province. The range of δ
114/110
Cd
NIST‐3108
value is smaller in the Nayongzhi deposit (0.16–
0.21‰), but the published S isotopic composition has significant variation (11.8–33.0‰). We found that the
large S isotopic variations were controlled by Rayleigh fractionation between sulphide and reduced S. Thus, a
mineralization model of the Nayongzhi deposit has been proposed, which involves the mixing of a metal‐rich
fluid with a reduced S pool formed by thermochemical sulfate reduction. Based on this model, no Cd isotopic
fractionation was observed due to its low solubility in fluids during mixing. Therefore, the Cd isotopic variations
of sphalerite were inherited from the source rocks. Combining the Zn/Cd ratios and Cd isotopic composition
characteristics of the sulphides, igneous rocks, and sedimentary rocks, it is indicated that Zn and Cd were
derived mainly from basement rocks (e.g., migmatite, gneiss, and granulite).
1. Introduction
Zinc (Zn) and cadmium (Cd) are group IIB elements in the Periodic Table and are abundant in hydrothermal
sulphide deposits due to their chalcophile nature. As such, Zn/Cd ratios and Cd isotope data can provide
insights into the sources of metals in different hydrothermal systems (Spry et al., 2022; Wang et al., 2021;
Wen et al., 2016; Yang et al., 2022; Zhu et al., 2013,2017,2021). These studies demonstrated that various
RESEARCH ARTICLE
10.1029/2023GC011429
Key Points:
•S isotopic variations caused by
Rayleigh fractionation between
sulphide and reduced S; Cd isotopic
variations inherited from source rocks
•Zn/Cd ratios and Cd isotopic
compositions reveal that Zn and Cd
were dominantly derived from
basement rocks
•The Nayongzhi deposit was formed by
mixing between metal‐rich and
reduced sulfur ore‐forming fluids
Supporting Information:
Supporting Information may be found in
the online version of this article.
Correspondence to:
C. Zhu,
zhuchuanwei@chd.edu.cn;
zhuchuanwei@mail.gyig.ac.cn
Citation:
Song, W., Zhu, C., Wen, H., Huang, Z.,
Wei, C., Zhang, Y., et al. (2024).
Sphalerite records Cd isotopic signatures
of the parent rocks in hydrothermal
systems: A case study from the Nayongzhi
Zn–Pb deposit, southwest China.
Geochemistry, Geophysics, Geosystems,
25, e2023GC011429. https://doi.org/10.
1029/2023GC011429
Received 19 MAR 2024
Accepted 23 MAR 2024
Author Contributions:
Formal analysis: Yuxu Zhang,
Zhengbing Zhou
Funding acquisition: Chuanwei Zhu,
Xiaocui Chen
Investigation: Wenrui Song, Yuxu Zhang,
Zhengbing Zhou
Supervision: Hanjie Wen, Zhilong Huang,
Xiaocui Chen
Validation: Yuxu Zhang, Zhengbing Zhou
© 2024 The Authors. Geochemistry,
Geophysics, Geosystems published by
Wiley Periodicals LLC on behalf of
American Geophysical Union.
This is an open access article under the
terms of the Creative Commons
Attribution‐NonCommercial‐NoDerivs
License, which permits use and
distribution in any medium, provided the
original work is properly cited, the use is
non‐commercial and no modifications or
adaptations are made.
SONG ET AL. 1 of 15
processes, such as fluid migration (Xu et al., 2020), mineral precipitation (Wen et al., 2016; Zhu et al., 2017),
bacterial metabolism (Li et al., 2019; Yang et al., 2022; Zhu et al., 2013), vapor‐liquid partitioning (D. Wang
et al., 2020) and fluid mixing (Schmitt et al., 2009; Zhu et al., 2021) can cause Cd isotopic variations in
sulphides. The deposits formed by special geochemical and/or geophysical processes show large Cd isotope
variations in sulphides, for example, bacterial metabolic activity could result in light Cd isotope enriched in
sulphides, including the Xiaobaliang (0.74 to 0.08‰; Yang et al., 2022), Broken Hill (1.02–2.59‰;
Spry et al., 2022), and Jinding deposits (0.86–0.46‰; Li et al., 2019; Zhu et al., 2013); vaporliquid
partitioning was suggested to explain the large Cd isotope fractionation in sulphides from the Zhaxikang and
Keyue deposits with δ
114/110
Cd
NIST‐3108
values varying from 2.19 to 2.24‰ and from 0.38 to 3.17‰,
respectively (D. Wang et al., 2020; Wang et al., 2021). Excluding the special cases, it is generally considered
that the magnitude of Cd isotopic variations in sulphides is closely related to fluid temperature (Yang
et al., 2015). High‐temperature hydrothermal systems (e.g., skarn and magmatic–hydrothermal deposits)
exhibit smaller Cd isotopic variations than low‐temperature hydrothermal systems (e.g., MVT deposits).
Skarn and magmatic–hydrothermal deposits, such as the Baiyinnuoer (166–480°C; Wang et al., 2018) and
Shagou (157–267°C; Li et al., 2013) deposits, exhibit the range of δ
114/110
Cd
NIST‐3108
values of 0.26 to
0.01‰ and 0.06 to 0.01‰, respectively (Wen et al., 2016). MVT deposits, such as the Fule (93–200°C;
Liang, 2017) and Daliangzi (213–283°C; Wu, 2013) deposits, exhibit greater range of δ
114/110
Cd
NIST‐3108
values of 0.06 to 0.58‰ (Zhu et al., 2017,2018) and 0.22 to 0.32‰ (Xu et al., 2020), respectively
(Table S1). A study of oceanic hydrothermal sulphides also supports this inference, as sulphides from low‐
temperature vents have δ
114/110
Cd
NIST‐3108
values of 0.43–0.41‰, which is larger than that of sulphides
(0.03–0.06‰) from high‐temperature vents (Schmit et al., 2009).
However, some ore deposits with low formation temperatures in the Sichuan–Yunnan–Guizhou minerali-
zation province (SYGMP), such as the Maozu (205–280˚C; Yang et al., 2017) and Jinshachang (114–290˚C;
Liu, 1989) deposits, exhibit small variations in δ
114/110
Cd
NIST‐3108
values ranging from 0.17 to 0.02‰
and 0.04–0.10‰, respectively (Table S1; Xu et al., 2020). In addition, sphalerite from the Dadongla (80–
178˚C; Hu et al., 2020), and Fule (93–200˚C; Liang, 2017) deposits, with similar ore‐forming temperatures,
have distinct δ
114/110
Cd
NIST‐3108
values range from 0.15 to 0.37‰ and 0.06 to 0.58‰, respectively
(Table S1; Wen et al., 2016; Zhu et al., 2017,2018). The aforementioned studies highlight that fluid
temperature is not the sole control on the magnitude of Cd isotopic variations in some hydrothermal systems,
and other potential factors need to be further investigated. The Nayongzhi deposit is located in northwestern
Guizhou Province, China (B. Wang et al., 2020) and is the first large Zn–Pb ore deposit (>1.52 Mt Zn +Pb)
discovered in Guizhou Province (Jin et al., 2016). The homogenization temperatures of sphalerite fluid in-
clusions vary from 95 to 155°C (Wei, 2018), suggesting this deposit formed in a low‐temperature hydro-
thermal system. In situ S isotope analysis revealed the δ
34
S values of sphalerite range from 11.8 to 33.0‰
(Zhou et al., 2018). However, sphalerite in most deposits in the SYGMP exhibits smaller S isotopic vari-
ations of 1.3‰ (i.e., the Shaojiwan deposit, 9.8–11.1‰; Zhang et al., 2011) to 11.7‰ (i.e., the Huize
deposit, 11.8–23.5‰; Han et al., 2007) (Table S1). The Nayongzhi deposit has the largest δ
34
S variations in
the SYGMP, suggesting that the ore formation mechanisms of the deposit differ from other typical deposits
in this area. In this study, published S isotope data for sphalerite and new Cd isotope data were used to
investigate the mechanisms that control Cd and S isotopic variations and metal sources in the Nayongzhi
deposit. We also present a new geochemical model for metal mineralization in the Nayongzhi deposit and
similar hydrothermal systems.
2. Geological Setting and Samples
2.1. Regional Geology
The South China Block consists of the Yangtze and Cathaysia blocks and is bounded by the Qinling Orogenic Belt
to the north, the Songpan–Ganze Orogenic Belt to the northwest, and the Sanjiang Block to the west (Figure 1a).
The Yangtze Block comprises basement and sedimentary rocks. The basement comprises weakly metamorphosed
late Palaeoproterozoic to early Neoproterozoic strata (Gao et al., 2011; Qiu et al., 2000; Zhou et al., 2002), which
are overlain by Phanerozoic cover rocks (Figure 1b; Zhou et al., 2002).
The SYGMP is located at the southwestern margin of the Yangtze Block and is dominated by the NW–SE‐
trending Yiliang–Shuicheng, N–S‐trending Anninghe, NE–SW‐trending Shizong–Shuicheng, and Xiaojiang
Visualization: Wenrui Song, Chen Wei,
Zhen Yang
Writing – original draft: Wenrui Song
Writing – review & editing:
Chuanwei Zhu, Hanjie Wen,
Zhilong Huang, Béatrice Luais,
Christophe Cloquet
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SONG ET AL. 2 of 15
tectonic belts (Figure 1b; Wei et al., 2018; Zhang, 2008; Zhou et al., 2018). More than 400 Zn–Pb deposits have
been found in the SYGMP, accounting for 27% of the total Zn +Pb resources in China (Figure 1b; Zhang
et al., 2015). The basement rocks consist of high‐grade metamorphosed crystalline basement rocks and medium‐
to low‐grade metamorphosed and folded basement rocks, which are unconformably overlain by Ediacaran strata.
The basement rocks mainly belong to the Archean Kangding (migmatite and gneiss, with localized granulite
occurrences) and Mesoproterozoic Yanbian–Huili–Kunyang (marine volcanic and sedimentary rocks) groups
(Zhang, 2008). The Ediacaran–Quaternary strata are mainly limestones and dolomites (Zhu et al., 2021). In
addition, the late Permian Emeishan flood basalts are widely distributed in the SYGMP over an area of
>250,000 km
2
(Figure 1b; Chung & Jahn, 1995; Jian et al., 2009; Zhou et al., 2002).
The overturned Wuzhishan anticline is a NE–SW‐trending asymmetric anticline, which is located in the south-
eastern part of the mineralization area in northwestern Guizhou Province. The anticline is 16 km long and 4 km
wide (Figure 1c; Wei et al., 2018; Zhou et al., 2018). In the anticline fold axis, Cambrian and Carboniferous strata
are exposed, along with minor occurrences of the Ediacaran Dengying Formation. The anticline limbs have
exposures to Carboniferous, Permian, Triassic, and Cretaceous strata. The major faults include the NE–SW‐
trending Narun normal fault (F
1
), which dips SE at 40°–65°, and the NE–SW‐trending Dujiaqiao reverse fault
(F
2
), which dips SE at 60°–70° (Figure 1c; Jin et al., 2016; Zhou et al., 2018). Igneous rocks are not exposed in the
Wuzhishan area, where several Zn–Pb deposits (i.e., outcrops; e.g., the Dujiaqiao, Nayongzhi, Xinmai,
Figure 1. (a) Simplified tectonic map of the South China Block. (b) Simplified geological map of the Sichuan–Yunnan–Guizhou mineralization province (SYGMP)
showing the location of the Nayongzhi deposit. (c) Geological map of the Wuzhishan anticline showing the location of Zn–Pb ore deposits. The figure was taken and
modified from Wei et al. (2018,2021).
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SONG ET AL. 3 of 15
Gabuchong, Narun, and Yujiaba deposits) are exposed. The Nayongzhi Zn–Pb deposit is the best studied of these
deposits because of its large metal reserves and high grade (Figure 1c).
2.2. Geology of the Nayongzhi Zn–Pb Deposit
The Nayongzhi deposit in the northwestern Guizhou Province is an important part of the SYGMP. Metamorphic
basement rocks have not been observed in the ore district. The sedimentary cover rocks comprise Lower
Cambrian, Carboniferous–Triassic, and Quaternary strata (Figure 2a). The Cambrian strata are underlain by the
Ediacaran Dengying Formation that overlies the Neoproterozoic basement. The Dengying Formation is overlain
by the Lower Cambrian Mingxinsi, Jindingshan, and Qingxudong formations. The Cambrian strata are uncon-
formably overlain by the lower Carboniferous Xiangbai and Dapu formations, the lower Permian Liangshan
Formation, the Lower Triassic Daye Formation, and Quaternary rocks (Figure 2a). The Qingxudong Formation
Figure 2. (a) Geological map of the Nayongzhi Zn–Pb deposit showing sample locations. (b) Cross–section of the Nayongzhi Zn–Pb deposit (A–Aʹ). Figure taken and
modified from Wei et al. (2021).
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SONG ET AL. 4 of 15
can be divided into three members based on lithology, with dolostone being dominant in the first and second
members (Figure 2b; Jin et al., 2016; Wei et al., 2018; Zhou et al., 2018). NW–SE‐trending (e.g., the F
12
fault) and
NE–SW‐trending (e.g., the Xiongchang and Jichangpo faults and the Wuzhishan tectonic belt; Figure 2a)
geological structures are well developed and were important ore‐controlling structures (Jin et al., 2016; Wei
et al., 2021; Zhou et al., 2018). Although the late Permian Emeishan flood basalts are not exposed, the spatial
association between the Zn–Pb deposits and basalts indicates that these were the main igneous rocks in the study
area (Figure 1b; Jin et al., 2016; Zhou et al., 2018).
The Nayongzhi Zn–Pb deposit (26°25′N, 105°38′E) is located in the central part of the southeastern limb of the
Wuzhishan anticline and consists of the Lumaolin, Jinpo, Shayan, and Yuhe ore blocks (Figure 2a). By 2015, 1
steeply dipping veined and 20 stratiform or lentiform ore bodies had been discovered (Figure 2b; B. Wang
et al., 2020). The former are located along the F
12
fault and are 20–50 m in length, 0.5–3 m in width, and 200 m
thick, with Zn grades of >10 wt.% (Figure 2b). Based on the lithology of the ore‐bearing rocks, the stratiform and
lentiform ore bodies can be divided into three similar groups (I, II, III), although group II is the largest (Zhou
et al., 2018). The group II ore bodies are hosted by dolomite and limestone. The ore bodies are lenticular or
stratiform, strike NE–SW, and dip to the SE. The major ore body in group II, which is the largest in the Nayongzhi
deposit, is 2725 m in length, 250–775 m in width, and 1.0–29.6 m thick, with total Zn and Pb reserves of >0.5 Mt
at average grades of 4.03 wt.% Zn and 0.45 wt.% Pb (Zhou et al., 2018).
The ores consist mainly of primary minerals, including sphalerite, galena, and minor pyrite, and the gangue
minerals are mainly dolomite and calcite with minor quartz (Figure 3). Sulphide ores have massive, veined, and
brecciated structures and granular, fragmented, and replacement textures (Zhou et al., 2018). Wall‐rock alteration
is extensive and involves predominantly dolomitization, calcification, and silicification (Chen et al., 2017; Zhou
et al., 2018).
We collected 25 ore‐bearing hand specimens from the Nayongzhi deposit, of which 15 sulphide‐rich samples
were taken from different ore bodies, and four sulphide‐rich (TJZ‐1150‐8 and ‐1150‐8‐1, SY‐32 and ‐21) and six
sulphide‐poor (JP‐1 to 4 and W‐B1 to ‐B2) samples were collected from the ore tailings. Sampling locations are
shown in Figure 2a. After washing and air drying, the sulphide‐rich samples were crushed to 40–60 mesh and then
handpicked under a binocular microscope. The sphalerite was then washed with deionized water, air‐dried, and
crushed to ∼200 mesh for subsequent analysis. Sulphide‐poor samples were crushed to ∼200 mesh for
geochemical and Cd isotope analysis.
Figure 3. (a, b) Photographs of hand specimens, (c, d) transmitted light photomicrographs, and (e–h) reflected light photomicrographs of sulphides from the Nayongzhi
Zn–Pb deposit. (a) Dense disseminated sphalerite (Sp) and (b) sparse disseminated sphalerite cement between fragments of dolomite (Dol). (c) Subhedral sphalerite
surrounded by dolomite. (d) Coarse‐grained dolomite enclosed by sphalerite. (e) Fine‐grained pyrite (Py) and galena (Gn) in fractures in sphalerite, which coexist with
dolomite. (f) Fine‐grained pyrite and galena coexisting with sphalerite, which are both cemented by dolomite. (f–h) Anhedral–subhedral pyrite coexists with sphalerite,
which is both cemented by dolomite.
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SONG ET AL. 5 of 15
3. Analytical Techniques
Due to the complex elemental composition of geological samples, Cd has to be chemically separated from the
sample matrix for accurate Cd isotope analysis, in order to avoid interferences and matrix effects (Zhu
et al., 2015). Approximately 100 mg of sphalerite was weighed, placed in a Teflon capsule, reacted with 6 mL of
concentrated HCl at 110˚C for >24 hr, and then evaporated to dryness on a hot plate. Subsequently, 5 mL of 2%
HNO
3
was added and the solution was transferred into a 15 mL centrifuge tube. After centrifugation (4000 r/min
for 10 min), 0.5 mL of the supernatant was diluted to within the range (1–10 ppm) of the test standard curve and
used for major and trace element analysis (Zhu et al., 2013). Another aliquot of the supernatant containing 600 ng
of Cd was mixed with a double spike solution (600 ng) at a sample /spike ratio of ∼1, evaporated to dryness at
110˚C, and then digested in 3 mL of 2 N HCl. The method for the chemical purification of Cd was described by
Zhu et al. (2013). This method has a Cd recovery of 99.82% (Zhu et al., 2013).
Trace element contents of the sulphides were measured by inductively coupled plasma optical emission spec-
trometry (ICP‐OES) at the State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry,
Chinese Academy of Sciences, Guiyang, China. Cadmium isotope ratios were determined at the State Key
Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang,
China, using a Thermo‐Scientific Neptune multiple‐collector‐ICP‐mass spectrometer (MC‐ICP‐MS; Neptune
Plus). The samples and standards were diluted to 200 ng mL
1
, and the
114
Cd signal was ∼3.5 V at an uptake rate
of ∼50 μL min
1
. An in‐house sulphide standard (J‐Zn‐1; Japan) was processed along with the samples to monitor
the data quality.
The double‐spike technique was used to correct for instrumental mass fractionation during Cd isotope analysis,
and details of the analytical procedures and instrumental parameters are given in Zhu et al. (2021) and Zhang
et al. (2018). The Cd isotopic composition was calculated using a MATLAB‐based script using an iterative
double‐spike correction algorithm (Zhu et al., 2021). Secondary standards, including Nancy Spex and JMC Cd
standards, were measured after each set of five unknowns to monitor the data accuracy and precision.
In this study, all data are reported relative to the NIST SRM 3108 Cd isotopic reference standard proposed by
Abouchami et al. (2013), and are given in per mil (‰) notation based on the following equation:
δ114/110CdNIST3108 (‰)=[(114 Cd /110Cd)sample
/(114Cd /110 Cd)NIST3108
– 1]×1000.
The measured Cd isotopic compositions of the Nancy Spex and JMC standards are 0.13‰ ±0.03‰ (2SD;
n=3) and 1.69‰ ±0.07‰ (2SD; n=3), respectively, consistent with previously reported values for these
standards (Nancy Spex δ
114/110
Cd
NIST‐3108
= 0.13‰ ±0.07‰; JMC δ
114/110
Cd
NIST‐3108
= 1.73‰ ±0.08‰;
Yang et al., 2022; Nancy Spex δ
114/110
Cd
NIST‐3108
= 0.10‰ ±0.07‰; JMC δ
114/110
Cd
NIST‐3108
= 1.71‰ ±
0.06‰; Zhang et al., 2018). The δ
114/110
Cd
NIST‐3108
value of J‐Zn‐1 sulphide was 0.06‰ ±0.06‰, which is
consistent well with literature values (0.05‰ ±0.08‰; Yang et al., 2022).
4. Results
The Cd isotope data are listed in Table 1. The δ
114/110
Cd
NIST‐3108
values of 25 sphalerite samples vary from 0.16
to 0.21‰ (mean =0.03‰), with an overall variation range of 0.37‰. This range is similar to that of continental
sphalerites (0.34‰; Schmitt et al., 2009), but smaller than the data published by C. W. Zhu et al. (2013,2016,
2017,2018,2021; the Huize [0.53‰], Shanshulin [0.47‰], Tianbaoshan [0.56‰], Fule [0.64‰] Zn–Pb de-
posits), Xu et al. (2020; the Daliangzi [0.54‰] and Fusheng [0.46‰] Zn–Pb deposits) and Song et al. (2023; the
Zhugongtang Zn–Pb deposits [0.49‰]) (Table S1).
The Zn, Fe, and Cd content data are listed in Table 1. The sulphide standard J‐Zn‐1 has major and trace element
errors of <±10% (relative). For the sphalerite‐rich samples, the average Zn, Fe, and Cd contents are 55.13 ±5.84
wt.% (1SD; n=19), 1.06 ±0.37 wt.%, and 890.37 ±452.86 ppm, respectively; In contrast, the sphalerite‐poor
samples have much lower Zn and Cd but higher Fe contents, with Zn, Fe, and Cd contents of 16.78 ±8.37 wt.%
(1SD; n=6), 2.86 ±0.67 wt.%, and 561.33 ±759.18 ppm, respectively. These differences may be due to the
presence of impurities, possibly in the form of small numbers of other minerals such as calcite and pyrite.
Sphalerite is the dominant Cd‐bearing mineral in this deposit, and other sulphide and gangue minerals (e.g., pyrite
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SONG ET AL. 6 of 15
and galena) have extremely low Cd contents (mostly <10 μg g
1
) compared with sphalerite (Wei et al., 2021). As
such, impurities in the sphalerite would not change its Cd isotopic composition and Zn/Cd ratio. Therefore, Zn /Cd
ratios better reflect changes in Cd contents in the sphalerite, and the mean Zn/Cd ratio is 688 ±275 (2SD; n=25).
5. Discussion
5.1. Reinterpretation of Published Sulfur Isotope Data
Previous studies have reported bulk S isotopic compositions of sphalerite from the Nayongzhi deposit, which
have δ
34
S=17.2–25.5‰ (Jin et al., 2016; Zhou et al., 2018), whereas the in situ S isotopic compositions of
different colored sphalerite zones vary from 22.3 to 27.9‰ (Wei et al., 2021). In contrast, Zhou et al. (2018)
obtained much larger S isotopic variations by nanoscale secondary ion mass spectrometry on the intra‐crystal
scale, with δ
34
S=11.8–33.0‰. Microbial sulfate reduction (MSR) is unlikely to have occurred during the
formation of the Nayongzhi deposit owing to a lack of geological and geochemical evidence for this process, and
thus thermochemical sulfate reduction (TSR) has been suggested as the dominant mechanism that generated
reduced S and the δ
34
S variations (Wei et al., 2021). This mechanism has been proposed to explain S isotopic
Table 1
Sulfur–Cd Isotopic Compositions and Selected Major and Trace Element Data for Sulphides in the Nayongzhi Deposit
Sample No. Sample Info.
δ
114/110
Cd
NIST‐3108
2SD δ
34
S
CDT
a
Fe Zn Cd
Zn/Cd(‰) (‰) (‰) (wt.%) (wt.%) (ppm)
YH‐15‐3 Yuhe ore block 0.10 0.11 25.5 1.44 47.91 482 994
16‐YH‐8 0.08 0.06 24.4 1.07 48.96 612 799
SY‐36 Shayan ore block 0.18 0.11 24.2 0.37 61.58 1,158 532
SY‐6 0.20 0.11 22.4 0.45 59.66 1,142 522
SY‐9 0.01 0.09 22.4 1.46 48.51 705 688
LML‐8‐2‐1 Lumaolin ore block 0.10 0.06 26.4 1.64 50.10 641 781
LML‐8‐2 0.00 0.03 24.2 1.22 59.92 838 715
LML‐2‐4 0.00 0.11 24.0 1.54 61.26 808 758
LML‐9‐1 0.11 0.06 17.2 1.31 61.25 845 725
LML‐1270‐8 0.06 0.01 22.8 1.14 59.30 675 879
JP‐11 Jinpo ore block 0.07 0.04 22.6 0.56 57.11 1,891 302
2 Drill hole 0.14 0.10 23.0 1.27 62.10 2,190 284
14 0.06 0.03 23.9 0.70 48.46 1,116 434
23 0.06 0.04 19.9 0.64 54.37 853 638
15 0.12 0.02 23.4 1.03 43.78 297 1,473
SY‐32 Ore tailings 0.16 0.10 25.3 1.28 58.53 743 788
SY‐21 0.08 0.08 26.7 1.17 58.18 768 757
TJZ‐1150‐8 0.06 0.09 22.0 1.18 47.88 443 1,080
TJZ‐1150‐8‐1 0.21 0.02 21.2 0.68 58.65 710 826
JP‐1 0.04 0.07 ‐ 2.68 12.92 282 458
JP‐2 0.02 0.05 ‐ 2.60 14.48 298 485
JP‐3 0.16 0.06 ‐ 3.36 6.14 110 558
JP‐4 0.02 0.01 ‐ 1.59 33.63 2,253 149
W‐B1 0.15 0.06 ‐ 3.57 17.93 233 769
W‐B2 0.08 0.02 ‐ 3.35 15.56 192 812
J‐Zn‐1 Zn ore standard 0.06 0.06 ‐ 11.36 2.26 112 202
Reference values
b,c
0.05
d
0.08
d
/ 11.8 2.22 121* /
Note. “/”, no reference value; “‐”, not measured; “*”, the reference Cd content of J‐Zn‐1 is from 114 to 121 ppm.
a
Wei
et al. (2023).
b
Terashima et al. (2003).
c
Okai et al. (2002).
d
Yang et al. (2022).
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variations in different hydrothermal systems (Cai et al., 2022, and references therein). However, multiple S
reservoirs or Rayleigh‐type fractionation have been invoked to explain the large S isotopic variations in the
Nayongzhi deposit (Zhou et al., 2018). The dominant process controlling the S isotopic variations in this deposit
needs to be further constrained.
Some fluid inclusions in transparent minerals in the Nayongzhi deposit are rich in CO
2
, CH
4
, and organic
compounds (Wei, 2018; L. Y. Zhu et al., 2016). As such, TSR was likely the dominant mechanism that generated
reduced S by the following reactions (Cai et al., 2022, and references therein):
CaSO4+CH4+2H+→ H2S+CaCO3+H2O+CH3SH, (1)
SO2
4+1.33(CH2)+0.66H2O → H2S+1.33CO2+2OH.(2)
In general, S isotopic fractionation during TSR is characterized by reduced S that is rich in light S isotopes, with
the S isotopic fractionation was considered as negligible in most petroleum‐related sour gas settings (Cai
et al., 2022). Experimental studies have shown that similar S isotopic fractionation occurs under excess sulfate
conditions, but much greater fractionation occurs under limited sulfate conditions with Δ
34
S
initial sulphate–reduced
sulphur
up to 7.1‰ (CaSO
4
) and 12.4‰ (Na
2
SO
4
) (Meshoulam et al., 2016). When the oxidizable hydrocarbons
are consumed, the fractionation between reduced sulfur and sulfate is only ∼17‰ (Meshoulam et al., 2016). In
situ measurements have shown that δ
34
S values decrease from core to rim in sphalerite crystals (33.0–11.8‰;
Zhou et al., 2018; 27.9–23.6‰; Wei et al., 2021). If TSR generated the S isotopic variations during the trans-
formation of sulfate to sulphide, then the early formed sphalerite should be enriched in lighter S isotopes, which
differs from the observed δ
34
S variations. In addition, because of the limited isotopic fractionation during TSR
either under excess or limited sulfate conditions, we suggest that TSR was not the factor that resulted in the large S
isotopic variations in the Nayongzhi deposit (21.2‰; Zhou et al., 2018). Multiple S reservoirs can potentially
explain the S isotopic variations in different hydrothermal systems, such as the Navan (Gagnevin et al., 2012) and
Zhulingou (Luo et al., 2022) deposits. In the study area, reduced S was likely derived from sedimentary sulfate as
there is no evidence for bacteriogenic or magma‐related S in the Nayongzhi deposit.
We suggest that S isotopic variations in the deposit were likely caused by Rayleigh fractionation. Cambrian
marine sulfate has δ
34
S=28–32‰ (Claypool et al., 1980), similar to the observed sulfate (barite) in Cambrian
strata from the SYGMP where the Nayongzhi deposit is located (32.1–35.3‰; Bai et al., 2013; Zhou et al., 2015).
Experimental studies have obtained the S isotopic fractionation factors between sulphides and different S species
at various temperatures (Kajiwara & Krouse, 1971; Sakai, 1968). Due to the large number of Zn–Pb deposits in
the ore district, the total S content of the sediments is likely to be much larger than that of the Nayongzhi deposit.
As such, S isotopic fractionation between reduced S and sulfate was negligible due to the excess sulfate during
TSR (Cai et al., 2022; Meshoulam et al., 2016), and the δ
34
S values of the reduced S are similar to those of the
sulfate (34‰; Zhou et al., 2015) in the SYGMP area. Large S isotopic fractionations can be generated by
Rayleigh fractionation between S
2
and sphalerite (17.1‰; f=90%; 150°C; Figure 4a), but the fractionation is
minor between HS
and sphalerite (2.4‰; f=90%; 150°C; Figure 4b). These models can theoretically explain
why early formed sphalerites have heavier S isotopes than later formed sphalerite, and the observed magnitude of
S isotopic variations on an intra‐crystal scale (Wei et al., 2021; Zhou et al., 2018). In nature, S
2
is negligible in
hydrothermal fluids compared with other S species (e.g., HS
) because it is only dominant at a pH of 14.5
(Williams‐Jones & Migdisov, 2014). However, minor S
2
could exist (Equations 3and 4) if the pH of the ore‐
forming fluid is >5. For example, the S
2–
/H
2
S ratio could be 10
7
at pH =6 (Szaran, 1996). In addition, several
other S species (e.g., S
3
and S
n
S
2
) are potentially important ligands in hydrothermal fluids (Equations 5and 6;
Eldridge et al., 2021; Truche et al., 2014; Williams‐Jones & Migdisov, 2014). For example, Barré et al. (2017)
confirmed that S
3
and S
n
2
exist in fluid inclusions in natural transparent minerals (quartz, fluorite, and
anhydrite).
H2S↔H++HS,(3)
HS↔H++S2,(4)
HS+(x1)S0→ S2
x+H+(x=2–8),(5)
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HSO
4+2H2S=S3+0.75O2+2.5H2O.(6)
Experimental studies have determined the S isotopic fractionation between multiple S species and shown that
polysulphides are enriched in heavy S isotopes (Amrani et al., 2006). Theoretical calculations have suggested that
Δ
34
S values between S species (S
3
and S
3
) and HS
at 298 K for inner S atoms are 15.8 and 10.5‰, respectively
(Tossell, 2012), suggesting that these S species could potentially result in large S isotopic fractionations during
formation of sulphides. Therefore, a model in which metal‐rich ore‐forming fluids migrated through faults and
then mixed with reduced S (e.g., S
2
and S
3
), resulting in sulphide precipitation, could explain the Rayleigh‐type
S isotopic fractionation.
Based on our interpretation of the S isotopic compositions of sphalerite, the Nayongzhi deposit was likely formed
by two‐fluid mixing, with one being enriched in reduced S and the other enriched in metals. This model has also
been proposed for the Lisheen Mine (Wilkinson et al., 2005), and both Nayongzhi and Lisheen are carbonate‐
hosted‐type deposits. Recent experimental studies have shown that the solubility products of CdS in H
2
S–
bearing solutions at 25–80°C were small (Bazarkina et al., 2023). The measured solubility constants demon-
strated that CdS is the most stable mineral phase with the low solubility (Bazarkina et al., 2023), and CdS pre-
cipitation can occur even with low Cd concentrations in the ore‐forming fluid due to its low Ksp (Ksp =10
27.94
;
Sillén & Martell, 1964). In the presence of excess reduced S during fluid mixing, all Cd
2+
would be precipitated in
the sphalerite lattice by directly substituting for Zn
2+
to form a Cd–S compound, which results in no Cd isotopic
fractionation. As such, the Cd isotopic variations in sphalerite record those of the source rocks, implying that the
Cd isotope data can directly trace the metal source(s) of the Nayongzhi deposit.
5.2. Cadmium Isotopic Composition and Its Significance
Owing to the similar geochemical characteristics of Cd and Zn, Cd isotopic compositions and Zn/Cd ratios may
be used to track the sources of ore‐forming materials (Li et al., 2019; Wang et al., 2021; Zhu et al., 2021).
However, as elucidated above, the deposits formed by bacterial metabolism and vapor‐liquid partitioning show
large Cd isotope variations in sulphides, and thus, Zn/Cd ratios and Cd isotopic compositions of sulphide may not
be efficient to investigate the metal source of these deposits with special ore‐forming processes (Spry et al., 2022).
In the SYGMP, most deposits have similar mineralization ages (250–200 Ma) and geochemical signatures (e.g.,
δ
34
S
CDT
, salinity and mineralization temperature) (Table S1). Previous studies have proven that bacterial
metabolism and vapor‐liquid partitioning were unlikely to occur during the formation of these deposits. It is thus
that Zn/Cd ratios and Cd isotopes could be used to track the metal sources of the deposits from the SYGMP.
Figure 4. Rayleigh fractionation model of the S isotopic composition of sphalerite precipitated from the ore–forming fluids over a range of temperatures. (a) Rayleigh
fractionation model between sphalerite and S
2
. (b) Rayleigh fractionation model between sphalerite and HS
. The gray area is the observed δ
34
S values of the
sulphides, and the yellow stars are the mean δ
34
S values of reduced S formed by TSR. The fractionation factors between sphalerite and different S species were taken
from Sakai (1968) and Kajiwara and Krouse (1971).
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Geological observation demonstrates that the local potential source rocks in the study area are sediments and
igneous rocks (detailed information see the geological setting section). The Cd isotopic variations of igneous
rocks are small or near zero, with δ
114/110
Cd
NIST‐3108
= 0.21–0.15‰ (Liu et al., 2020; Palk et al., 2018; Tan
et al., 2020; Wiggenhauser et al., 2016; Zhu et al., 2021). However, the Cd isotope compositions of sediments are
largely varied in comparison with igneous rocks. Hohl et al. (2017) used Cd isotopes to investigate the Xiaofenghe
section of the Ediacaran Doushantuo–Dengying formations and showed that the δ
114/110
Cd
NIST‐3108
values of the
carbonates varied substantially (0.68–0.21‰). Due to low Cd concentrations in igneous rocks, sediments in the
SYGMP have lower Zn/Cd ratios than igneous rocks (Huang et al., 2004; Zhu et al., 2021). Therefore, igneous
rocks have more uniform Cd isotopic compositions and higher Zn/Cd ratios (515–1319; Braukmüller et al., 2020;
Chen et al., 2016; Gladney & Roelandts, 1988; Liu et al., 2020; Zhu et al., 2021) compared with sedimentary
rocks (Zn/Cd =13–367; Zhu et al., 2021). Based on different geochemical signatures of sediments and igneous
rocks, Zhu et al. (2021) determined that the Zn/Cd ratios (235–635) and Cd isotopic compositions (0.17–
0.36‰) of sphalerite in the Huize deposit are mostly intermediate between those of sedimentary rocks (Zn /
Cd =13–367; δ
114/110
Cd
NIST‐3108
= 0.25–0.82‰) and the Emeishan basalts (Zn/Cd =756–900; δ
114/110
Cd
NIST‐
3108
= 0.22‰ to 0.13‰), indicating that the Zn and Cd were derived from mixing of the Emeishan basalts and
sedimentary rocks. Although no magmatically related deposits were identified in the SYGMP, previous studies
have shown that magma‐related deposits without special geochemical and/or geophysical processes have similar
Cd isotope compositions to igneous rocks. Wen et al. (2016) determined the Zn/Cd ratios and Cd isotopic
compositions of sphalerite from different types of Zn–Pb deposits, and found that metals in high‐temperature
systems (e.g., skarns and volcanogenic massive sulphide [VMS] deposits) are closely associated with magmas.
The mean δ
114/110
Cd
NIST‐3108
values of magmatically related deposits (0.08‰; i.e., the Baiyinnuoer, Gacun,
Shagou, and Dabaoshan deposits; Wen et al., 2016) and basalts (0.02‰; Liu et al., 2020; Tan et al., 2020; Zhu
Figure 5. Plot of Zn/Cd versus δ
114/110
Cd
NIST‐3108
for the sulphides and sedimentary rocks in the Nayongzhi deposit and igneous rocks. Data for the sedimentary rocks
are from
a
Zhu et al. (2021) and
i
Zhu et al. (2017). Cadmium contents and δ
114/110
Cd
NIST‐3108
values for the igneous rocks are from
a
Zhu et al. (2021),
b
Liu et al. (2020),
c
Tan et al. (2020),
d
Wiggenhauser et al. (2016), and
e
Palk et al. (2018). Zinc contents for the igneous rocks are from
f
Chen et al. (2016),
g
Gladney and Roelandts (1988),
and
h
Braukmüller et al. (2020). The Zn/Cd ratios and δ
114/110
Cd
NIST‐3108
values for the upper continental crust were estimated using loess by
j
Pickard et al. (2022).
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et al., 2021) are similar. Zhao et al. (2023) investigate Cd isotope compositions of sphalerite from the Xitieshan
deposit formed by magmatic hydrothermal fluids, and δ
114/110
Cd
NIST‐3108
values are varying from 0.10 to
0.02‰. These studies demonstrated that sphalerite records the Cd isotopic composition of its source rocks.
Here, the Nayongzhi deposit has high Zn/Cd ratios (688 ±275; 2SD) and uniform Cd isotopic compositions
(δ
114/110
Cd
NIST‐3108
= 0.16–0.21‰; Table 1). Data for most sphalerite samples plot in the igneous rock field
and are markedly different from those of sedimentary rocks (Figure 5). Based on the distribution of igneous and
Figure 6. Conceptual model of mineralization and S reduction in the Nayongzhi deposit. (a) Stage I: reduced S formed by
TSR of marine sulfate. (b) Stage II: metal‐bearing ore‐forming fluids (e.g., containing Cd
2+
and Zn
2+
) derived from
basement rocks infiltrated faults and then mixed with reduced S to form the deposit.
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ore‐hosting rocks in the deposit, we suggest that the ore‐forming fluid enriched in Zn and Cd was dominated by
contributions from basement rocks, which consisted mainly of migmatite and gneiss with local occurrences of
granulite. However, the contribution from the ore‐hosting rocks was negligible due to their large Cd isotopic
variations (Hohl et al., 2017). This conclusion is also supported by Pb isotope data for the deposit and potential
source rocks (Jin et al., 2016; Zhou et al., 2018).
Therefore, we conclude that the Cd isotopic variations in sphalerite in the Nayongzhi deposit are due to mixing
between a metal‐rich ore‐forming fluid derived from the basement rocks and a reduced S pool derived from the
ore‐hosting strata.
5.3. Implications
Based on the Cd and S isotopic variations, we propose a new mineralization model for the Nayongzhi deposit in
the SYGMP. Ediacaran strata were covered by thick younger strata, and the increased geothermal gradient and/or
tectonism could have resulted in sulfate reduction that formed reduced S pools, which were trapped in karst caves
or fracture zones with little to no S isotopic fractionation (Figure 6). The tectonism reactivated regional fractures
and faults, which resulted in the ascent of ore‐forming fluids from the basement rocks (e.g., the F
12
reverse fault),
which then mixed with the reduced S pools to form sulphides. Consumption of the reduced S pools resulted in
Rayleigh‐type fractionation between sulphide and reduced S. Heavier S isotopes were enriched in the early
formed sphalerite. CdS precipitated immediately owing to its low solubility. As such, all Cd
2+
was bonded into
the sphalerite lattice owing to the excess reduced S, and no Cd isotopic fractionation occurred during sphalerite
precipitation. With continued reactions, the sulphides became enriched in favorable sites and formed steeply
dipping veined and stratiform or lentiform ore bodies (Figure 6b).
6. Conclusions
In the present study, we found that the Cd isotopic variations of sphalerite in the Nayongzhi MVT Zn–Pb deposit
are limited (δ
114/110
Cd
NIST‐3108
= 0.16–0.21‰) and smaller than in other deposits (e.g., the Fule deposit) with
similar mineralization temperatures in the SYGMP. In contrast, S isotopic compositions vary by up to 21.2‰
(Zhou et al., 2018). We reinterpreted these S isotope data and suggest that the significant S isotopic fractionation
was not caused by TSR but instead resulted from Rayleigh‐type fractionation between metal‐bearing fluid and a
reduced S‐rich fluid pool. Owing to the low solubility of CdS, it was entirely incorporated into sphalerite, and no
Cd isotopic fractionation occurred during sphalerite precipitation during fluid mixing. As such, the sphalerite
inherited the Cd isotopic compositions of the source rocks. The Cd isotopic compositions (δ
114/110
Cd
NIST‐
3108
= 0.16–0.21‰) and high Zn/Cd ratios (688 ±275) of the sphalerite indicate that Zn and Cd were
derived dominantly from basement rocks (e.g., migmatite, gneiss, and granulite). We propose a new minerali-
zation model to explain the ZnS mineralization involving fluid mixing between metal‐bearing and reduced S‐rich
fluids (Figure 6). This new model provides an explanation for the significant S and lack of Cd isotopic variations
in a low‐temperature hydrothermal system.
Conflict of Interest
The authors declare no conflicts of interest relevant to this study.
Data Availability Statement
All relevant isotopic data are provided within the text of this manuscript in Table 1. Table S1 is available at
Zhu (2024).
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