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25 January 2026

A Study of the Trace Element Enrichment Patterns in Sulfides from the Maoping Pb-Zn Deposit, SW China

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1
Kunming General Survey of Natural Resources Center, China Geological Survey, Kunming 650100, China
2
Innovation Base for Metallogenic Regularity and Effective Exploration Technology of Hydrothermal Gold-Copper Polymetallic Deposits, Geological Society of China, Kunming 650100, China
3
Faculty of Metallurgy and Mining, Kunming Metallurgy College, Kunming 650033, China
4
Faculty of Land Resources Engineering, Kunming University of Science and Technology, Kunming 650500, China
Minerals2026, 16(2), 130;https://doi.org/10.3390/min16020130
This article belongs to the Special Issue Editorial Board Members’ Collection Series: "Critical and Strategic Minerals", 2nd Edition
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Abstract

The Sichuan–Yunnan–Guizhou Pb-Zn metallogenic belt (SYG metallogenic belt), a crucial metallogenic unit on the southwestern margin of the Yangtze Block, is a key part of the South China low-temperature metallogenic domain. The incorporation mechanisms and distribution of trace elements (e.g., Ge, Ga, Cd) widely enriched in Pb-Zn sulfides throughout this region remain poorly understood. This study investigates main-ore-stage sulfides (sphalerite and pyrite) from the Maoping Pb-Zn deposit using in situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses and mapping to systematically elucidate the partitioning and occurrence of these trace elements. The key findings are as follows: (1) Sulfides show distinct elemental partitioning: sphalerite preferentially concentrates Cd, Ag, Ge, Ga, and Se, whereas pyrite is significantly enriched in Mn, Ni, As, and Co. (2) Sphalerite is the primary host for many trace elements. Cadmium, Ge, Mn, Cu, and Ag mainly enter the sphalerite lattice by substituting for Zn2+. Coupled substitution mechanisms, such as Zn2+ ↔ Cd2+, 2Zn2+ ↔ Ge2+ + Cu2+, and 2Zn2+ ↔ Ga3+ + Cu+, facilitate the incorporation of Ge and Ga. (3) The sphalerite exhibits a trace element assemblage of high Cd-Ge and low Fe-Mn, which is geochemically similar to typical Mississippi Valley-type (MVT) deposits and differs significantly from sedimentary exhalative (SEDEX) and magmatic–hydrothermal deposits, indicating a medium- to low-temperature metallogenic environment. Based on these geochemical signatures and epigenetic textures, we confirm that the Maoping Pb-Zn deposit exhibits similarities with MVT deposits. Nevertheless, distinct differences in the tectonic setting and metal grades suggest it is a unique SYG-type Pb-Zn deposit.

1. Introduction

The Sichuan–Yunnan–Guizhou Pb-Zn metallogenic belt (SYG metallogenic belt), located on the southwestern margin of the Yangtze Block, accounts for over 27% of China’s total Pb-Zn resources. It is a key component of the South China low-temperature metallogenic domain [1,2]. Over 400 Pb-Zn deposits, including the giant Huize, Maoping, Fule, and Maliping deposits, have been discovered within the SYG metallogenic belt, forming a significant mineral resource base. These deposits commonly exhibit associated trace elements such as germanium (Ge), gallium (Ga), and silver (Ag) and share similar geochemical characteristics [3,4,5,6].
Recently, trace elements like Ge, Ga, and cobalt (Co) are vital for the development of emerging industries. It has been found that the Pb-Zn deposits are enriched in Ge, Ga, and Co in the SYG metallogenic belt. Sphalerite hosts economic trace critical metals such as Ge and Ga, and pyrite hosts Ni and Co [7,8,9,10]. The trace elemental contents and ratios (e.g., Ge, Co, Ga) in the sphalerite and pyrite provide significant information for understanding the mineralization and genetic type of ore deposits [11,12].
The Maoping Pb-Zn deposit, situated in the north–central part of the SYG metallogenic belt (Figure 1b), is a large-scale deposit renowned for its high grades (avg. Zn + Pb > 18 wt%) and is also a representative deposit for the South China low-temperature metallogenic domain. With cumulative proven resources exceeding 3 million tons of Pb-Zn, it is the second-largest deposit in the SYG metallogenic belt, surpassed only by the Huize deposit [13,14]. Several notable studies of trace elements have been carried out on the Maoping deposit; it has been proven that sphalerite from the Maoping deposit is characterized by enrichments in Ga and Ge but depletions in Manganese (Mn), iron (Fe), and Co [15,16]. Despite the significant geochemical research at Maoping, the distribution and occurrence of trace elements are not well understood, and its genetic model remains debated. Several main genetic models have been proposed: Magmatic hydrothermal-type [17,18], sedimentary exhalative (SEDEX) deposit [19], and Mississippi Valley-type (MVT) [20,21]. Conventional analyses of trace element contents in hand-picked mineral separates are often limited by instrumentation and the difficulty of pure mineral selection, so that results can be distorted by micro-inclusions. The development of in situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) techniques, with their low detection limits, provides an effective method for revealing differences in the trace element composition of sulfides from various deposit types [22]. Consequently, researchers are increasingly using in situ analyses and mapping to investigate elemental occurrences and enrichment mechanisms [23].
Figure 1. The tectonic setting of the western Yangtze Block (a), and the sketch geological map of the Sichuan–Yunnan–Guizhou Pb-Zn metallogenic belt (b) (modified after [19]).
This study utilizes systematic LA-ICP-MS analyses of the trace element contents in pyrite and sphalerite from the Maoping Pb-Zn deposit. By integrating mapping imaging techniques and time-resolved depth profiling analyses of elements, it aims to clarify the occurrence patterns of trace elements in sphalerite, decipher the geochemical fingerprint characteristics of trace elements, and provide new geochemical constraints for the genetic model.

2. Geological Characteristics of the Mining Area and Deposit

2.1. Regional Geology

The SYG metallogenic belt is situated in the southwestern Yangtze Block, adjacent to the Sanjiang orogenic belt to the west and the Youjiang basin and South China fold belt to the south (Figure 1a) [19,24]. This region possesses a distinctive metallogenic geological setting; as a convergence zone of two globally significant metallogenic domains, the Circum-Pacific metallogenic domain and Tethyan metallogenic domain, Pb-Zn deposits in this region are primarily hosted by carbonate rocks and have a strong spatial association with the Emeishan large igneous province (ELIP) (Figure 1b) [1,2]. This region constitutes a significant area for low-temperature metallogenic Pb-Zn deposits in China, with its metallogenic characteristics intimately linked to regional geological evolution processes [25].
The basement in the western margin of the Yangtze Block exhibits a characteristic “double-layer structure”: the dual-layer basement architecture comprises a lower crystalline basement composed of ancient metamorphic complexes such as the Archean Kongling complex, overlain by an upper fold basement represented by Mesoproterozoic metamorphic rock series including the Huili group and Kunyang group [26]. The sedimentary cover displays a distinct three-layer structure, comprising (from base to top) Paleozoic marine sedimentary strata, late Permian Emeishan flood basalts, and Cenozoic continental sedimentary strata [19,27].
The Pb-Zn deposits in the SYG metallogenic belt are predominantly hosted by carbonate rocks ranging from the Meso- to Neo-Proterozoic and middle Permian sequences. Evaporitic gypsum salt layers and organic matter are widely developed in the Permian sedimentary rocks, likely providing critical sulfur sources and reducing agents for mineralization [4,5,26]. During the late Permian (ca. 260 Ma), large-scale eruptions of the Emeishan mantle plume generated massive flood basalts along the southwestern margin of the Yangtze Block, exhibiting a remarkable spatial correlation with Pb-Zn deposit distribution (Figure 1b) [10,11]. Notably, although Pb-Zn deposits are spatially associated with these flood basalts, most carbonate-hosted ore bodies within the enriched zones are stratigraphically positioned beneath the basaltic units. Precise geochronological studies further indicate that mineralization (226–196 Ma) slightly postdates the basalt eruption; thus, the basalts have been considered to be a partial source of the ore-forming metals [19,25,28,29].
The study area is situated within the fold–thrust depression belt of northeastern Yunnan. Its structural framework is primarily controlled by the NE-striking Luozehe, Fangmaba, and Maoping Faults, alongside the NW-striking Longjie Fault. These structures, characterized by imbricate geometry and polyphase reactivation, exhibit significant dip variations and heterogeneous thicknesses, collectively constituting critical ore-controlling structures for Pb-Zn mineralization [30] (Figure 2).
Figure 2. The sketch geological map of the Maoping area (modified after [27]).
Considering that thermal activity resulted in hydrothermal fluids and the mineralization of ore-forming metals, the Indosinian tectonic evolution of the SYG metallogenic belt was governed by a distinct stress regime that fundamentally controlled mineralization processes [31,32]. During the late Indosinian period, the region experienced dominant E-W-oriented compression, superimposed by northward-directed stress from the Vietnam–Kontum Massif, which collectively generated a series of NE-trending structural zones [33]. This progressive stress field transformation established coupled deformation mechanisms that simultaneously (1) enhanced large-scale ore–fluid circulation through fracture networks, and (2) created structurally favorable traps for metal enrichment and deposition [34].

2.2. Geological Characteristics of the Maoping Deposit

The Maoping region exposes a stratigraphic succession spanning from the Silurian to the Triassic period (Figure 2). The exposed strata comprise shallow marine dolomites from the upper Devonian Zaige Formation, sandstones and shales from the lower Carboniferous Datang Formation, limestones and dolomites from the Bazuo Formation, and limestones and dolomites from the upper Carboniferous Weining Formation from oldest to youngest. The periphery is extensively covered by upper Permian Emeishan basalts [35]. The most extensively exposed units in the area are the limestones and dolomites of the upper Devonian Zaige Formation, the upper Carboniferous Weining Formation, and the lower Carboniferous Datang and Bazuo Formations, which constitute the primary host rocks for Pb-Zn ores [36].
The Maoping Pb-Zn deposit is predominantly characterized by the NW-trending Luozehe Fault and NE-trending Maoping Fault. The key ore-controlling fold structure within the Maoping area is the Maomaoshan overturned anticline, situated on the hanging wall of the NE-trending Maoping Fault. The nucleus of anticline consists of dolomites from the Zaige Formation, while the limbs are composed of sandstones and shales from the Datang Formation and carbonate rocks from the Bazuo Formation. There are six significant ore body groups that have been discovered in the Maoping Pb-Zn deposit [16]. The main mineralized sections are identified as ore bodies I, II, and III, which primarily occur as vein-like and lenticular forms within marine carbonate rocks (Figure 3). Ore body I trends SE–NW, as the principal ore body in the deposit, extends over 600 m in length, and has a thickness ranging from several meters to over 30 m. It predominantly dips southeastward, with a steep inclination of approximately 85°. The Zn grade ranges from 3.9% to 30.9% (mean 12.8%), while the Pb grade varies between 2.64% and 13% (mean 5.46%). Additionally, the Maoping deposit is associated with Ag and Ge, including 560 t Ag metals, with an average grade of 75 ppm, and 182 t Ge metals, with an average of 24 ppm [16].
Figure 3. The typical profile comprehensive map of the Maoping Pb-Zn deposit (modified after [27]).
The results of detailed macroscopic observation show that the principal metallic minerals of the Maoping Pb-Zn deposit include sphalerite (Sp), galena (Gn), and pyrite (Py). The gangue minerals are predominantly dolomite (Dol) and calcite (Cal). The ores are characterized by massive, disseminated, vein-like structures. The principal ore textures include metasomatic, granular, and brecciated. The hydrothermal alterations at the Maoping Pb-Zn deposit include silicification, pyritization, baritization, and carbonatization [37,38]. Through detailed field observations and petrographic studies, integrated with previous research findings, the mineralization at Maoping has been recognized as three distinct mineralization stages [16].
Based on the mineral contact relationships, mineral assemblages, and several previous studies, three hydrothermal stages (I, II, III) are distinguished in the Maoping deposit (Figure 4) [16,27]. The early-ore stage (Stage I) is characterized by the precipitation of pyrite and dolomite (Dol); the main metallic mineral is vein-like and massive pyrite (Figure 5a), with minor associated sphalerite and galena mineralization. The Sp-Gn-Py-Dol-Cal stage (Stage II) corresponds to the main-ore stage of the Maoping deposit. This stage is characterized by an abundant sulfide mineralization, dominated by sphalerite and galena, with minor pyrite. The sulfides primarily occur as dense disseminations and vein-like or massive aggregates (Figure 5b,f), while pyrite forms sparse and vein-like, locally distributed disseminations (Figure 5c,e). Pyrite predominantly occurs as euhedral massive aggregates and disseminated grains, which fill and coexist with sphalerite (Figure 5g,k,l). Sphalerite typically replaces galena as irregular disseminations (Figure 5i,l), with local well-developed fractures (Figure 5j). Additionally, galena veinlets are observed replacing sphalerite (Figure 5h), indicating complex replacement relationships between these sulfides. The Dol/Cal stage (Stage III) is the late-ore stage, consisting mainly of abundant calcite with minor vein-like and massive pyrite (Figure 5d).
Figure 4. Mineral sequence and paragenetic association of hydrothermal mineralization period in the Maoping Pb-Zn deposit.
Figure 5. Field photographs and photomicrographs of main-ore-stage sulfides from the Maoping Pb-Zn deposit. (a) Vein-like pyrite and dolomite coexist in massive ore; (b) banded sphalerite cut by late calcite veins; (c) sphalerite, galena, and pyrite coexist in disseminated sulfide ore; (d) a clear boundary between pyrite and galena; (e) pyrite replaced by calcite veins; (f) galena, sphalerite, and pyrite coexist in massive ore; (g) well-formed pyrite is rounded by sphalerite; (h) galena is filled in fine veins and is cut by sphalerite; (i) sphalerite is contained in galena; (j) sphalerite fractures are filled with minor dark minerals; (k) galena coexists with fine-grained pyrite; (l) sphalerite and galena crosscut the fine-grained pyrite. Abbreviations: Gn—galena; Sp—sphalerite; Py—pyrite; Cal—calcite; I—stage number.

3. Sample Sources and Analytical Methods

The samples were collected from the No. I ore body in the main-ore stage (Stage II) Pb-Zn sulfides, encompassing 28 measurement points for sphalerite and 6 measurement points for pyrite (Figure 5g–l), which represent various ore sulfide types including massive, vein, and disseminated ores. Samples MP-IS-Tr1 and MP-IS-Tr2 were massive ores, MP-IS-Tr3 and MP-IS-Tr4 were vein-like ores, and MP-IS-Tr5 and MP-IS-Tr6 were disseminated ores. After detailed macroscopic observations, measurement points were selected from the clean mineral area without inclusion, and then thin sections were used for in situ analyses.
In situ trace element analyses of sulfide minerals were conducted using LA-ICP-MS at Beijing Kehui Testing Technology Co., Ltd., Beijing, China. The analyses were carried out using an Analytik Jena PQMS Elite ICP-MS (Jena, Germany) coupled with a RESolution 193 nm laser ablation system. A laser spot size of 50 μm was employed; the ablation was conducted at a pulse frequency of 6 Hz, with an energy density of 3 J/cm2, and the crater depth was maintained below 30 μm. High-purity helium was used as the carrier gas. Prior to analysis, the instrument was calibrated using NIST 610 as the primary reference material to ensure compliance with analytical requirements. Laser ablation was performed in single-spot mode. The total analysis time per spot was 85 s. Before each ablation, a background signal was collected for 20 s with the laser beam blocked. Subsequently, each measurement point was ablated continuously for a duration of 45 s, followed by a 20 s blank measurement to purge the sample introduction system. To ensure data consistency and analytical accuracy, a set of standard reference materials (NIST 610, NIST 612, BHVO-2G, BCR-2G, BIR-1G, and MASS-1) was analyzed every 10 ablation spots [39,40]. Data were processed offline using ICPMSDataCal 10.9 software.
The in situ element mapping of sulfides was conducted at Beijing Kehui Testing Technology Co., Ltd., Beijing, China. The instruments were the Analytik Jena Plasma Quant MS Elite ICP-MS coupled with the RESolution 193 nm excimer laser ablation system. The laser ablation was performed with a spot diameter of 30 μm, an energy density of approximately 3 J/cm2, a frequency of 10 Hz, a scanning speed of 15 μm/s, and a line spacing of 30 μm, using high-purity He as the carrier gas. Prior to the analysis, the instrument was optimized using NIST 610 standard [39]. The LA-ICP-MS laser ablation was carried out in a line scanning mode for mapping, with MASS-1 serving as the external standard. During the analysis, the laser beam was initially blocked to collect the blank background signal for 20 s, and then the sample was continuously ablated. After the cessation of ablation, the sampling system was purged for an additional 20 s to clean the residual material. Elemental mapping was conducted using continuous line-scan ablation to investigate the spatial distribution of elements on the mineral surfaces; the spacing between adjacent scan lines was set to 30 µm. Data processing for elemental mapping was carried out using Iolite v3.25 [41].

4. Results

4.1. Major and Trace Element Compositions of Sphalerite and Pyrite

The major and trace element compositions of sphalerite and pyrite from the Maoping deposit are presented in Table 1, with a summary in Figure 6. The results for major and trace elements are as follows:
Table 1. Major and trace elements (ppm) in main-ore-stage sulfides from the Maoping Pb-Zn deposit.
Figure 6. Box-and-whisker plots showing trace elements of main-ore-stage sphalerite and pyrite from the Maoping Pb–Zn deposit.
(1)
Sphalerite exhibits relatively moderate iron (Fe) contents (1800 to 48,200 ppm, mean 24,600 ppm, n = 28), though significantly lower than those of the iron-rich sphalerite standards (Fe > 10 wt%).
(2)
There are notable enrichments of copper (Cu), cadmium (Cd), germanium (Ge), silver (Ag), gallium (Ga), mercury (Hg), and tin (Sn) in sphalerite. The copper contents in sphalerite exhibit a considerable variability, with values ranging from 8.80 to 4918 ppm (mean 460 ppm, n = 28); in contrast, the pyrite shows lower Cu contents, which range from 1.27 to 98.0 ppm (mean 22.4 ppm, n = 6). Similarly, cadmium is highly enriched in sphalerite (797 to 2202 ppm, mean 1111 ppm, n = 28) compared to pyrite (0.05 to 12.6 ppm, mean 3.71 ppm, n = 5). Germanium is notably enriched in sphalerite (5.94 to 373 ppm, mean 68.8 ppm, n = 28) compared to pyrite (11.5 to 12.5 ppm, mean 11.9 ppm, n = 6). The silver contents in sphalerite (10.0 to 1005 ppm, mean 73.0 ppm, n = 28) are significantly higher than in pyrite (0.1 to 8.1 ppm, mean 3.2 ppm, n = 6). The gallium contents in sphalerite (0.09 to 49.4 ppm, mean 7.17) are higher than pyrite (0.02 to 0.39, mean 0.11). The mercury contents of sphalerite are relatively high, ranging from 60.5 to 433 ppm (mean 151 ppm), which are higher than those of pyrite (0.03 to 1.36, mean 0.50). The tin contents are higher in sphalerite, between 0.32 and 213 ppm (mean 26.7 ppm, n = 28), while the Sn contents in pyrite are extremely low, with a variation range from 0.01 to 0.19 ppm (mean 0.08 ppm, n = 6).
(3)
The lead contents in pyrite range from 31.4 to 16,163 ppm, with a mean value of 3289 ppm, and are obviously higher than those of sphalerite (137 to 3167 ppm, mean 137 ppm). The arsenic (As) contents in sphalerite vary widely (0.38 to 4131 ppm, mean 162 ppm, n = 27), whereas pyrite exhibits higher but more variable As levels (45.6 to 2160 ppm, mean 772 ppm, n = 6). The manganese contents (0.02 to 361 ppm, mean 72.6 ppm, n = 5) in pyrite are higher than in sphalerite (9.95 to 49.1 ppm, mean 24.1 ppm, n = 28). The cobalt contents (0.05 to 9.18 ppm, mean 2.95 ppm, n = 4) and Ni contents (0.73 to 50.4, mean 9.95) are slightly enriched in pyrite; both elements are nearly undetectable in sphalerite, with all measurements below 6 ppm.
(4)
The antimony (Sb), selenium (Se), tellurium (Te), and thallium (Tl) contents in sphalerite and pyrite are relatively low. The antimony contents in sphalerite show a range of 0.07 to 89.6 ppm (mean 20.2 ppm, n = 28), and the Sb contents in pyrite are ranging from 7.66 to 44.8 ppm (mean 21.7 ppm, n = 6). The selenium, tellurium, and thallium contents in pyrite and sphalerite are relatively low, with some contents below the detection limit.

4.2. LA-ICP-MS Element Mapping

Elemental mapping was conducted over the area shown in Figure 7a, with each map covering a scale of 1200 µm × 960 µm. The elemental mapping images of the Maoping deposit (Figure 7) reveal distinct spatial associations among trace elements, with Cd, Ga, and Ge showing a strong enrichment in sphalerite, while As, Ni, and Co are predominantly concentrated in pyrite. Notably, Fe exhibits a characteristic zonation pattern, with higher contents in central zones, whereas Zn displays a complementary distribution, with preferential enrichment along the periphery surrounding Fe-rich domains. These distribution patterns provide important insights into the mineralogical controls of trace element partitioning during ore formation.
Figure 7. Mapping images of main-ore-stage sulfides from the Maoping deposit. (a) Reflected light photomicrograph of sphalerite and pyrite; (b–l) LA–ICP–MS trace element mapping images of sphalerite and pyrite.

5. Discussion

5.1. Enrichment Patterns of Trace Elements

Previous studies have established that the trace element contents differ significantly between sulfide minerals in Pb-Zn deposits. Generally, sphalerite is enriched in Ga, Ge, and Cd, whereas pyrite is enriched in Se, Te, and Tl [18,19,42,43,44]. The sulfides from the Maoping Pb-Zn deposit exhibit a similar partitioning. The most notable difference is observed in Cd, which is strongly enriched in sphalerite. The Cd contents in sphalerite are high and extremely variable (mean 1111 ppm), suggesting a possible enrichment from different ore-forming fluids over time. In contrast, the Cd contents in pyrite are very low (mean 3.71 ppm), even falling below the detection limit. This represents a content in sphalerite approximately two orders of magnitude higher than in pyrite. Furthermore, sphalerite is significantly enriched in several other elements, such as Cu, Ag, Ge, Ga, and Hg, compared to pyrite. The copper contents are substantially higher in sphalerite (mean 460 ppm) than in pyrite (mean 22.4 ppm). Similarly, the silver contents are over ten times higher in sphalerite (mean 72.9 ppm) than in pyrite (mean 3.17 ppm). The germanium contents are more enriched in sphalerite, though their distributions are uneven (5.94 to 373 ppm). The gallium contents are slightly more enriched in sphalerite (mean 7.16 ppm) than in pyrite (mean 0.11 ppm).
In contrast, other trace elements in the Maoping deposit show different partitioning behaviors, with several being preferentially enriched in pyrite. The lead contents in pyrite (mean 3289 ppm) are higher than in sphalerite (mean 137 ppm). Pyrite is also highly enriched in Ni, Co, and As, with average contents of 9.95 ppm, 2.95 ppm, and 772 ppm, respectively. In contrast, sphalerite contains very significantly low Ni (mean 0.53 ppm), low Co (mean 0.06 ppm), and moderate As (mean 157 ppm). This partitioning clearly indicates that Ni and Co are preferentially incorporated into pyrite. This distribution pattern indicates that Ni and Co have a distinct preference for enrichment in pyrite.
In summary, the trace elements in the Maoping sulfides exhibit a highly uneven distribution, with sphalerite mainly enriched in Cd, Cu, Ag, Ge, Ga, and Hg, while pyrite is relatively enriched in Pb, Ni, As, and Co.

5.2. Mechanism of Trace Element Occurrence and Geochemical Information of Mineralization

The elemental mapping images of the Maoping deposit show a strong spatial association between trace elements. These associations indicate that Cd, Ga, and Ge are enriched in sphalerite, whereas As, Ni, and Co are enriched in pyrite (Figure 7). This differential partitioning of trace elements between the sulfides is likely related to their respective crystal structures. The results confirm that sulfides such as sphalerite and pyrite are important carriers of trace elements. Iron and zinc have similar ionic radii. In the Maoping deposit, Zinc shows near-vertical variation trends with both Fe and the (Fe + Mn + Cd) sum in sphalerite, but near-horizontal trends in pyrite, corresponding to a relatively weak negative correlation (Figure 8a,b). In addition, the time-resolved depth profiles of Fe and Zn in sphalerite are largely coherent, supporting the dominant isomorphic incorporation of Fe. A subset of profiles, however, display anomalous irregular serrations with sharp peaks, which are interpreted as evidence for sporadic pyrite micro-inclusions (Figure 9). The correlation plot for Fe and Cu shows a weak positive trend in sphalerite but a vertical distribution in pyrite (Figure 8e), suggesting the presence of chalcopyrite micro-inclusions in the pyrite. This interpretation is supported by the stellate (star-shaped) distribution of Cu in the pyrite elemental map (Figure 7h), which provides further evidence that Cu exists mainly as micro-inclusions in pyrite. The correlation plot for Ag and Ge reveals no correlation in pyrite (evidenced by a near-vertical, concentrated distribution) but a slightly positive correlation in sphalerite (Figure 8c). This suggests that Ag and Ge likely enter the sphalerite lattice together via isomorphic substitution. In the time-resolved depth profile, the spectral lines for Ag and Zn are closely parallel (Figure 9a), further confirming that Ag is incorporated as a solid solution within the sphalerite.
Figure 8. The diagrams of Zn vs. Fe + Mn + Cd (a), Zn vs. Fe (b), Ge vs. Ag (c), Ga vs. Cu (d), Fe vs. Cu (e), and Cu vs. Ge (f) for main-ore-stage sulfides from the Maoping Pb-Zn deposit.
Figure 9. Time-resolved depth profiles of main-ore-stage sphalerites from the Maoping Pb-Zn deposit. (a) The spectral lines for Ag and Zn are closely parallel; (b) Pb exhibits distinct peak–trough features in specific zones; (c) Cadmium runs parallel to the Zn profile; (d) Copper runs parallel to the Zn profile.
In the time-resolved depth profile analyses of sphalerite, Pb exhibits distinct peak–trough features in specific zones, suggesting its potential occurrence as microscopic inclusions (Figure 9b,c). Given the similar ionic radii of Cd and Zn, the distribution of Cd in sphalerite is particularly notable. Its time-resolved depth profile runs parallel to the Zn profile (Figure 9a,d), and their distributions show significant overlap in element mapping images (Figure 7b,c). This reflects a strong correlation between the trace elements Cd and Zn, indicating that Cd primarily enters the sphalerite lattice via isomorphism, substituting for Zn, possibly substitution mechanism: Zn2+ ↔ Cd2+.
The study reveals that many trace elements are relatively enriched in sphalerite, with Cd and Ge being prominent, alongside minor Tl and Te, while the Ga contents are relatively low. Notably, Cu2+ shares similar tetrahedral covalent radii with Ge2+ and Zn2+, and Ga has ionic radii comparable to Zn, Cu, and Fe. Sphalerite from the Maoping deposit shows positive correlations between Cu, Ge, and Ga, along with Ge/Cu and Ga/Cu ratios close to 1 (Figure 8d,f). The strong correlations between Cu, Ge, and Ga indicate coupled substitutions. This pattern is consistent with that observed in other Pb-Zn deposits of the Sichuan–Yunnan–Guizhou region [18]. The time-resolved depth profile analyses further confirm that the profiles of Cu, Ge, and Ga align with those of Zn and S, displaying parallel trends (Figure 9c,d). Although, in Figure 9a, the profiles of Cu, Ga, and Ge show complex trends that include intervals of parallel variation with Zn and S, despite overall opposite trends, minor spiky signals can be found in the profiles of Cu and Ga, and these spiky signals suggest that Cu and Ga may be present as micro-inclusions within the sphalerite structure, in addition to isomorphic substitution. Meanwhile, the mapping image (Figure 7f,i) also shows that, in the same sphalerite, the distributions of Ge and Ga are extremely uneven, but they basically coincide with the Cu enrichment area, and some smaller Cu and Ge enrichment areas basically overlap; this indicates that Ge, Ga, and Cu mainly enter the sphalerite lattice in the form of isomorphic substitution. Thus, abundant Cu, Ga, and Ge may exist in sphalerite through isomorphic substitution, while minority occurred as micro-inclusions in the sphalerite structure. This significant positive correlation indicates that Cu, Ge, and Ga primarily exist in sphalerite through isomorphic substitution, conforming to the coupled substitution mechanisms 2Zn2+ ↔ Ge2+ + Cu2+ and 2Zn2+ ↔ Ga3+ + Cu+.

5.3. Ore Genesis Indication of Trace Elements in Sphalerite

The trace element composition of sphalerite can be used to estimate the information about ore fluid temperature [45]. Several studies have proven that the trace element content of sphalerite can be used to estimate the formation temperature [46,47,48,49,50]. Based on the content of trace elements in sphalerite, we calculated the ore-forming temperatures, respectively [45,51]. The application of the GGIMFis geothermometer to trace element compositions yields a temperature range of 141–222 °C for the Maoping sphalerite, with a mean of 186 °C (excluding one outlier at 82 °C). The mineralization temperature of the Maoping deposit, constrained to 141–222 °C by the GGIMFis geothermometer, signifies a medium- to low-temperature hydrothermal system. This range is consistent with published fluid inclusion homogenization temperatures from the Maoping deposit (e.g., 180–218 °C). It is also comparable to the mineralization temperatures of other deposits within the SYG belt, such as Qilinchang (164–221 °C) and Chipu (114–195 °C) [6,52].
We clarify the distribution characteristics of trace elements (Ga, Ge, and Cd) with temperatures and their potential use in the exploration of different types of Zn-Pb deposits. The gallium distribution shows a variable range and is negatively correlated to temperature (Figure 10a). Compared to other deposits, high gallium contents appear to be more common in sphalerite from MVT deposits. Similarly, the germanium contents show a negative correlation with temperature and display that Ge-rich sphalerites tend to occur mainly in MVT deposits (Figure 10b). Temperature serves as a principal factor controlling the enrichment of Ga and Ge in sphalerite. Most deposits have high Cd contents, while the MVT deposits yield highly variable Cd values (Figure 10c).
Figure 10. Correlation plots of (a) Ga vs. temperature, (b) Ge vs. temperature, and (c) Cd contents vs. temperature. The temperatures of the Maoping deposit are calculated using GGIMFis geothermometer T = − 54.4 × ln ( ∁ 0.22 G a ∁ 0.22 G e ∁ 0.37 F e ∁ 0.20 M n ∁ 0.10 I n ) + 208 [45]. In content data come from [16]. Other data come from [48].
Comparative analyses reveal significantly lower Fe (mean 24,600 ppm) and Sn (mean 26.6 ppm) contents in Maoping sphalerite compared to SEDEX deposits (e.g., Yunnan Bainiuchang: Fe 11,400 to 154,500 ppm, Sn 116 to 2910 ppm) (Figure 11a) [53]. Moreover, the mean Mn content in Maoping sphalerite (24.1 ppm) is significantly lower than the skarn deposits (e.g., 1254–5485 ppm in Hetaoping) but is consistent with the range for MVT Pb-Zn deposits (Figure 11b) [18].
Figure 11. Box plots of seven trace elements in sphalerite from the Maoping Pb-Zn deposit, showing the element variations for four types of Pb-Zn deposits (data for other type deposits from [8,9]). (a) Iron contents align with MVT Pb-Zn deposits; (b) Manganese contents align with typical MVT Pb-Zn deposits. (c) Cadmium contents exhibit lower than skarn deposits. (d) Silver variations are consistent with MVT deposit characteristics. (e) Germanium contents are higher than MVT deposits. (f) Gallium contents demonstrate comparable to MVT deposits; (g) Copper contents are higher than MVT deposits.
The elemental contents in Maoping sulfides show a limited trace element diversity, with several elements below detection limits (Table 1). Sphalerite Cd contents (mean 1111 ppm) align with those from the Maozhachang deposit (mean 1205 ppm) but are lower than those from the skarn, epithermal, and SEDEX deposits (Figure 11c). The germanium contents (mean 68.8 ppm) are consistent with the average range (106 to 192 ppm) for sphalerite from Maozhachang and Banqiao. Similarly, the Ga contents (mean 7.17 ppm) match the typical deposit range (4.64 to 8.05 ppm), confirming shared Cd-Ga-Ge enrichment characteristics with regional Pb-Zn deposits in the SYG metallogenic belt [4,5]. Furthermore, the distributions of Ag, Ge, Ga, and Cu more closely resemble those in the MVT deposits and are distinct from skarn, epithermal, and SEDEX types (Figure 11).
The Maoping deposit is characterized by a mineral assemblage of sphalerite, galena, and minor pyrite, which are closely associated with calcite and dolomite [6,14,54,55]. This typical mineral assemblage is corroborated by ore-forming temperatures ranging from 141 to 222 °C, collectively indicating that the Maoping Pb-Zn deposit formed in a medium- to low-temperature hydrothermal environment. The lack of skarn rocks and coeval magmatic activity in the Maoping area, coupled with its regional geological context, precludes genetic models involving skarn or epithermal deposits. Additionally, the main ore-hosting stratigraphic units of the Maoping Pb-Zn deposit are the upper Carboniferous Weining Formation and the lower Carboniferous Datang and Banzuo Formations, which do not exhibit typical characteristics of SEDEX deposits. Instead, the deposit is mainly controlled by the Indosinian tectonic stress field, with structural control being the dominant factor [56], thereby excluding the possibility of SEDEX deposits.
The enrichment patterns, modes of occurrence, and spatial distribution characteristics of trace elements in sulfides can effectively record the genetic information of multiple mineralization events (Figure 11). Different ore geneses often exhibit distinct elemental enrichment patterns [8,9]. Therefore, systematic analyses of trace element enrichment features can provide important evidence for interpreting mineralization processes and discriminating the genetic types of Pb-Zn deposits.
The trace element distributions in Pb-Zn deposits of different genetic types exhibit significant differences. Skarn deposits are enriched in Mn and Co, and depleted in As, Sb, and Se. Epithermal deposits are enriched in Fe, Mn, Sn, and Co, and depleted in Cd, Ge, and Ga. The MVT deposits are enriched in Cd, Ge, and Ga, and depleted in Fe, Mn, In, Sn, and Co [8,9,43,53,57,58]. A comparative analysis reveals that the Mn (mean 24.1 ppm) and Fe (mean 24,600 ppm) contents in sphalerite from the Maoping Pb-Zn deposit are significantly lower than those in the skarn deposits (Fe > 30,000 ppm, Mn > 1000 ppm). In the Mn vs. Fe, Mn vs. Cd, and Ge vs. Mn diagrams (Figure 12), sphalerites from the Maoping deposit are distinctly different from those of the skarn and epithermal Pb-Zn deposits, but closely align with the distribution range of MVT deposits. The relationship between Mn and Fe (Figure 12a) exhibits no clear overall trend, but there is a weak positive correlation between the two elements in the Maoping deposit. Meanwhile, Cd and Mn show a weak positive correlation (Figure 12b), both being generally low. The dataset reveals a weak negative correlation between the Mn and Ge contents in sphalerite (Figure 12c), with those specimens or ore types enriched in Mn being deficient in Ge. Our data plot predominantly within the field defined by global MVT deposits, with the exception of epithermal, skarn, and SEDEX deposits. This geochemical distinction is primarily manifested in the significantly lower Mn contents of the Maoping deposit compared to skarn, SEDEX, and epithermal Pb-Zn deposits, as well as its strong consistency with MVT deposits.
Figure 12. Binary plots of Mn vs. Fe (a), Ge vs. Mn (b), and Mn vs. Cd (c) in sphalerite from the Maoping and other Pb-Zn deposits (other deposit data are from [8,9]).
Moreover, the Co/Ni ratios (0.02 to 0.57) in pyrite are less than 1 and exhibit a narrow distribution, a feature consistent with the typical range of basin brine-derived Pb-Zn deposits [59]. This further supports the view that the Maoping deposit shares a highly similar sedimentary source contribution during its formation, akin to that of MVT Pb-Zn deposits [60]. The trace element characteristics of the Maoping Pb-Zn deposit indicate a close genetic affinity with typical MVT Pb-Zn deposits, yet there are fundamental differences in their ore-forming backgrounds and geochemical features (Table 2).
Table 2. A comparison between the Maoping deposit, SYG-type Pb-Zn deposits, and typical MVT Pb-Zn deposits.
Traditional MVT Pb-Zn deposits are characterized by the following key attributes. (1) They primarily form within post-orogenic, intracontinental extensional tectonic settings, and typical MVT deposits in the central–eastern US form in foreland basins during convergent orogenic events. (2) Ore-forming fluids are characterized by low temperatures (90–150 °C) and a high salinity (10%–30% NaCl eqv.). (3) Mineralization is unrelated to magmatic activity and exhibits no significant magmatic input. (4) The total Pb-Zn grades are relatively low (Pb + Zn < 10%). (5) They are enriched in the associated metal Cu, Ge, and Ga, but depleted in the trace elements Fe and Cd [61,62,63].
In contrast, the SYG-type Pb-Zn deposits have the following main distinctions. (1) They occur mainly in compressional settings. (2) The ore-forming fluids are characterized by moderate to low temperatures (usually below 180–250 °C) and a low salinity (NaCl eqv. < 20%). (3) They are closely related in space and time to the Emeishan flood basalts, with the basalts contributing some of the mineralizing materials. (4) They are characterized by high grades of lead and zinc (usually Pb + Zn > 10%). (5) They are enriched in trace metals Cu, Ag, Ge, and Cd [4,5].
The Rb-Sr isochron age of sphalerite from the Maoping deposit is 202.5 ± 8.5 Ma [64]. Additionally, unpublished data from the Zhou Jiaxi indicate that the U-Pb concordia age of calcite from the mineralization stage is 214 Ma. The Sm-Nd isochron ages of hydrothermal calcite from the Maozu and Jinshachang deposits in northeastern Yunnan are 196–201 Ma [26,65], and the Rb-Sr dating of sphalerite from the Huize Pb-Zn deposit indicates mineralization ages of 225.1 ± 2.9 Ma and 225.9 ± 3.1 Ma [66]. These geochronological data suggest that the Maoping and similar Pb-Zn deposits in the SYG metallogenic belt were mostly formed during the late Triassic to early Jurassic period (approximately 226–196 Ma), corresponding to the transition from compression to extension following the Indosinian orogeny.
Previous studies have suggested that the Pb-Zn deposits in SYG (e.g., Huize, Maoping, Fule, Tianqiao, and Maozu) are conspicuously associated with the Emeishan flood basalts. Consequently, many researchers have proposed a genetic relationship between Emeishan basalts and Pb-Zn mineralization [4,5,26,27]. In addition, based on in situ Pb isotopic data in the Fule Pb-Zn deposit, the Emeishan basalts contributed part of the metal Pb. Importantly, during ore formation, the Emeishan basalt sequence acted as an impermeable and protective layer, and even as an ore-hosting rock, facilitating the large-scale accumulation of metals in the western Yangtze Block [4,5]. Although the Emeishan flood basalts (~260 Ma) are spatially associated with the Maoping deposit, the significantly younger mineralization age (202.5 ± 8.5 Ma) challenges a direct genetic link [64]. This apparent contradiction may be resolved by thermal simulations, which indicate that such basaltic provinces can commence releasing metal-bearing fluids within 5–10 Ma after eruption and continue this process for over 50 Ma [67]. The metallogenic depth of the Maoping Pb-Zn deposit primarily ranges from 0.20 to 1.10 km. Given a typical geothermal gradient of 30 °C/km, the theoretical mineralization temperature would be below 100 °C, which is significantly lower than the measured fluid inclusion (180–218 °C) and geothermometer mineralization temperature (141–222 °C). Meanwhile, based on previous studies of in situ Pb isotopic data from the Maoping Pb-Zn deposit, the Emeishan basalts contributed part of the metalllic Pb [27]. Therefore, we propose that the Emeishan basalts contributed the majority of the thermal energy and a portion of the ore-forming fluids and materials.
In addition to these features, the Maoping Pb-Zn deposit has the following characteristics: (1) The ore-forming fluids are characterized by moderate to low temperatures (141–222 °C) and a low salinity (4%–10% NaCl eqv.). (2) The mineralization is closely related in space to the Permian Emeishan basalts. (3) The deposit is characterized by exceptionally high grades of Pb + Zn (>18%), which are higher than typical MVT deposits (<10%). (4) Sphalerite is moderately enriched in trace elements such as Ge, Ga, and Cd [10,13,26,50]. These characteristics are slightly different from typical MVT deposits [5].
In conclusion, the trace element composition of sphalerite from the Maoping deposit exhibits partial similarities to that of MVT deposits. However, compared to MVT deposits, the unique tectonic setting and distinct geological characteristics of mineralization of the Maoping Pb-Zn deposit may represent a unique SYG-type Pb-Zn deposit hosted in carbonate rocks.

6. Conclusions

Integrated trace element analyses of the Maoping deposit yield the following key insights:
Sphalerite in the Maoping Pb-Zn deposit is mainly enriched in Cd, Cu, Ag, Ge, Ga, and Hg, while pyrite is relatively enriched in Pb, Ni, As, and Co. Sphalerite serves as the primary host for Ge, Cd, Ag, and Ga, whereas pyrite is the main host for Ni and Co.
Minor pyrite micro-inclusions are inferred to be present within sphalerite, and chalcopyrite also may occur as micro-inclusions within pyrite. Cadmium, Ge, Ag, and Cu may substitute for Zn in the sphalerite lattice through isomorphous substitution. Notably, Cu and Ge, along with Ga, exhibit significant co-substitution features, with the following possible substitution mechanisms: 2Zn2+ ↔ Ge2+ + Cu2+, 2Zn2+ ↔ Ga3+ + Cu+, and Zn2+ ↔ Cd2+.
Sphalerite in the Maoping Pb-Zn deposit is characterized by a typical enrichment in Cd and Ge and a depletion in Mn, Co, and Sn. This geochemical signature is distinctly different from that of SEDEX and magmatic–hydrothermal deposits. Although the trace element composition shows some similarities to MVT deposits and the mineralization temperature falls within the moderate- to low-temperature range, significant differences are observed in the tectonic setting and metal grades. Integrating the geological and geochemical characteristics of the deposit, it can be concluded that the Maoping deposit should be classified as a unique SYG-type Pb-Zn deposit.

Author Contributions

Conceptualization, K.L. (Kaijun Lan) and Y.M.; experiments, Y.M. and S.L.; field investigation, K.L. (Kai Luo) and Y.Z.; writing—original draft preparation, K.L. (Kaijun Lan) and Y.M.; writing—review and editing, K.L. (Kaijun Lan), Y.M., J.Z., L.W. and M.L. All authors have read and agreed to the published version of the manuscript.

Funding

This project was jointly funded by the National Natural Science Foundation of China (U2344204), Science and Technology Plan Project of Yunnan Provincial Department of Science and Technology (202401AW070002), the New Round of Mineral Exploration Breakthrough Strategic Action and Geological Exploration Fund Project of Yunnan Province (Y202401), and the Project of China Geological Survey (DD20240207101).

Data Availability Statement

The data presented in this study are openly available in [Yu Miao] at [https://doi.org/10.1016/j.oregeorev.2023.105648], reference number [27].

Acknowledgments

We are grateful to Beijing Kehui Testing Technology Co., Ltd. for its support in the experiments. We also extend our thanks to the staff of Yunnan Chihong Zinc & Germanium Co., Ltd. for their assistance during the field investigations. Additionally, we express our sincere gratitude to the anonymous editor and reviewers for their meticulous review of this paper and the constructive suggestions for revisions.

Conflicts of Interest

The authors declare no conflicts of interest.

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