Next Article in Journal
The Tepsi Ultrabasic Intrusion, the Northern Part of the Lapland–Belomorian Belt, Kola Peninsula, Russia
Next Article in Special Issue
Telluride Mineralogy of the Kochbulak Epithermal Gold Deposit, Tien Shan, Eastern Uzbekistan
Previous Article in Journal
Early Cretaceous A-Type Acidic Magmatic Belt in Northern Lhasa Block: Implications for the Evolution of the Bangong–Nujiang Ocean Lithosphere
Previous Article in Special Issue
Distribution and Enrichment of Au, Hg, and Tl in the Lanmuchang Deposit, Guizhou, China
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Minerals
Volume 14
Issue 7
10.3390/min14070684
minerals-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Distribution and Enrichment Mechanisms of Selenium in Stibnite from the Xujiashan Sb Deposit, Hubei Province, China

by
Yuhang Liu
1,2,
Dazhao Wang
1,2,*,
Ruolong Huang
3,
Guanzhi Wang
4,5,
Wei Wan
1,2,6 and
Yu Kong
1,2
1
State Key Laboratory of Nuclear Resources and Environment, East China University of Technology, Nanchang 330013, China
2
National Key Laboratory of Prospecting, Mining and Remote Sense Detecting on Uranium Resources, Nanchang 330013, China
3
Forth Geological Team of Hubei Geological Bureau, Xianning 437100, China
4
State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing 100083, China
5
School of Earth Sciences, China University of Geosciences (Beijing), Beijing 100083, China
6
Key Laboratory of Geochemical Exploration, Institute of Geophysical and Geochemical Exploration, CAGS, Langfang 065000, China
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(7), 684; https://doi.org/10.3390/min14070684
Submission received: 27 April 2024 / Revised: 9 June 2024 / Accepted: 27 June 2024 / Published: 29 June 2024
(This article belongs to the Special Issue Selenium, Tellurium and Precious Metal Mineralogy)
Browse Figures
Versions Notes

Abstract

:
The Xujiashan Sb deposit located at the Mufushan fold thrust belt of the Yangtze block is one of the most important Sb deposits in this district. Stibnite in this deposit contains high and various contents of Se, but research on the distribution and enrichment of Se in stibnite remains limited. This paper conducts geochemical composition, C-H-O isotopic composition, and scanning electron microscopy morphology of the Xujiashan deposit to discuss the sources of ore-forming materials and fluid, as well as the distribution and enrichment mechanisms of selenium in stibnite. The results showed that the ores have trace element compositions comparable with the wall rocks, and Sb and Se contents are significantly higher than the average carbonate rocks. The δ13CPDB values of calcite and quartz range from −12.8‰ to 5.5‰, the δ18OSMOW values range from 20.4‰ to 24‰, and the δDV-SMOW values range from −57.8‰ to −86.9‰. Trace element and isotope compositions indicate that the ore-forming materials were mainly derived from the wall rocks (sedimentary–metamorphic rocks) that S, Se, and Sb dissolved during fluid–rock interactions. The ore-forming fluids were metamorphic water produced by metamorphism, which had experienced multistage mixing with meteoric water and organic-rich fluids. Selenium substitutes for sulfur in the stibnite crystal lattice, causing rhythmically distributed Se contents in stibnite, which resulted from multistage physicochemical changes in ore-forming fluids during crystallization. The varied patterns of Se contents are the result of different cross-sections of the stibnite.

1. Introduction

Antimony deposits are commonly found in the continental crusts, with many ultralarge deposits developing around the Pacific Ocean [1]. Antimony deposits in China mainly distribute in four metallogenic belts: the South China, Kunlun–Qinling, Tibet–Yunnan, and Yinshan–Tianshan belts (Figure 1a) [2,3]. Selenium (Se) has four valence states (Ⅵ, Ⅳ, 0, and −Ⅱ) in nature, and the crustal abundance is 0.05 × 10−6 [4]. Generally, Se does not form independent ore deposits but mainly occurs as an associated element in porphyry, epithermal, orogenic, and VMS deposits [5,6]. Selenium often incorporates into the lattice of stibnite to form Sb-S-Se system; this system can further be divided into stibnite [Se/(S + Se) < 0.20], selenium stibnite [0.20 ≤ Se/(S + Se) < 0.50], sulfur antimonselite [0.50 ≤ Se/(S + Se) < 0.80], and antimonselite [Se/(S + Se) > 0.80] [7,8].
The Xujiashan Sb deposit is located at the southern part of the Echeng–Damushan subuplift zone within the E’Dongnan uplift belt, Hubei Province (Figure 1a). It is the largest Sb deposit in this district, is controlled by Doushantuo Formation (carbonate rocks) and fractures [9]. Many studies have been conducted on the genesis, stable isotopes, and fluid inclusions of this deposit [9,10,11,12,13,14,15,16,17,18,19]. For example, Sun studied the geological characteristics of the ore bodies and determined that this deposit is controlled by strata, lithology, and fractures, with evidence of sedimentary modification; Yu investigated the chemical composition, fluid inclusions, and the sulfur, oxygen, and lead isotopic compositions of stibnite, concluding that mineralization underwent hydrothermal alteration and classifying the deposit as a sedimentation–reformation antimony deposit [11,15,16,17]; Shen analyzed various stable isotopes and suggested that the ore-forming fluids exhibited characteristics of low to moderate temperature, low salinity, and moderate density, likely derived from deep-circulating meteoric water [9,12,13,14,18]. This deposit has high Se contents [10], with Se reserves reaching a medium-sized deposit [5,11]; however, the migration, distribution, and enrichment processes of Se are rarely studied.
In this study, we carried out whole-rock trace element analysis, stable isotope analysis, scanning electron microscopy–energy dispersive spectrometer (SEM-EDS) and electron probe microanalysis (EPMA) to investigate the source of ore-forming metals and reveal the distribution, occurrence, and migration mechanisms of Se in the stibnite at Xujiashan.
Minerals 14 00684 g001
Figure 1. (a) Tectonic framework and (b) regional geological map of the Xujiashan Sb deposit (rectangle refers to Figure 2, modified after [15]).
Figure 1. (a) Tectonic framework and (b) regional geological map of the Xujiashan Sb deposit (rectangle refers to Figure 2, modified after [15]).
Minerals 14 00684 g001

2. Ore Deposit Geology

The Xujiashan deposit is located at the Mufushan fold thrust belt of the Yangtze block [14,16]. The lithology primarily consists of carbonate rocks, clastic rocks, and mudstone. The lithology of exposed strata includes sandstone (Neoproterozoic Liantuo Formation) and pebbled mudstone (Nantuo Formation), carbonate rocks (Upper Precambrian Doushantuo Formation) and silicalite (Laobao Formation), and carbonate rocks (Cambrian Niutitang Formation, Figure 1b). The Doushantuo Formation is mainly composed of limestone and dolomite with small amount of shale and mudstone, and this formation can be further divided into seven lithological sections, with the Sb orebodies predominantly located in the fifth section.
This region has undergone multiple tectonic events, including the Jinning Movement and the Indosinian–Yanshanian compression and thrusting phases. The district features a complex fault structure, primarily characterized by EW-trending faults, with some NE- and near SN-trending faults. The EW-trending faults primarily control the distribution of deposits. The Xujiashan fault (F1) is the most significant fault in the deposit, extending 18 km and intersecting the Doushantuo Formation. Igneous rocks are rare in this district [11].
Wall rock alterations in this region mainly include silicification, calcification, and baritization [18]. Silicification is widespread and can be categorized into pervasive and vein types. Calcification often overlaps with vein silicification and can be divided into pre-mineralization, syn-mineralization, and post-mineralization stages, with calcite veins present in both the pre-mineralization and syn-mineralization stages. Baritization generally coexists with silicification, calcification, and stibnite mineralization.
Orebodies at Xujiashan are clearly controlled by both faults and strata, and they can be divided into three ore belts: Sb-I, Sb-II, and Sb-III. The Sb-I and Sb-II belts are controlled by the F1 fault, while the Sb-III belt is situated at the contact boundary between the Niutitang and Doushantuo Formations. The orebodies appear as layered, lenticular, and finely veined disseminated aggregates (Figure 2), with EW strikes, northward dips, and dip angles of 52° to 85° [19]. Individual ore bodies vary in length from 20 to 325 m, with thicknesses ranging from 0.6 to 7.84 m and dip extensions of 20 to 230 m [19]. The primary ore mineral is stibnite, accompanied by minor amounts of pyrite, sphalerite, and antimony oxides [18]. Gangue minerals include quartz, calcite, and barite, with zircon, apatite, and feldspar present as accessory minerals [19].
Minerals 14 00684 g002
Figure 2. Geological map of the Xujiasha Sb deposit (modified after [16]). Abbreviations: Sb = Stibnite.
Figure 2. Geological map of the Xujiasha Sb deposit (modified after [16]). Abbreviations: Sb = Stibnite.
Minerals 14 00684 g002

3. Analytical Methods

The samples in this study were primarily collected from outcrops in the Sb-I and Sb-II zones, mainly stibnite ores containing quartz and calcite.
The morphology and composition analysis for stibnite was conducted at the State Key Laboratory of Nuclear Resources and Environment, East China University of Technology (Nanchang, China). The instrument used was a ZEISS Sigma 300 field emission scanning electron microscope equipped with an Oxford Ultim Max 100 energy dispersive spectrometer (EDS). The scanning electron microscope was operated at an acceleration voltage of 20 kV and an emission current of 10 μA [20]. The program AZtecMineral was used to conduct automated EDS mapping over wide areas.
Electron probe microanalysis (EPMA) was performed using a JEOL JXA-8250F electron probe microanalyzer with four wavelength-dispersive spectrometers (WDS) at the State Key Laboratory of Nuclear Resources and Environment, East China University of Technology (Nanchang, China). For detailed methods, see [21,22,23]. The samples were coated with a thin conductive carbon film prior to the analysis. The analytical parameters are as follows: 15 kV accelerating voltage; 20 nA beam current; 5 μm beam diameter; and counting times: 20 s (for Se, Fe, Zn, Co, Cu, S, Sb, W, Mo, and Pb), 50 s (for As), and 100 s (for Ag). Raw X-ray intensities were corrected using a ZAF correction procedure, a correction taking into account the following three effects on the characteristic X-ray intensity when performing quantitative analysis: (1) atomic number (Z) effect, (2) absorption (A) effect, and (3) fluorescence excitation (F) effect. A series of natural and synthetic SPI standards were utilized and changed based on the analyzed minerals [24]. The following standards were used: chalcopyrite (Cu, Fe, and S), synthetic gallium arsenide (As), natural galena (Pb), natural stibnite (Sb), synthetic pure silver (Ag), synthetic pure cobalt (Co), synthetic pure tungsten (W), natural sphalerite (Zn), synthetic cadmium selenide (Se), and natural molybdenite (Mo). The detection limits are 0.01 wt.% (for Se, Fe, Zn, Co, Cu, W, Mo, Pb, As, and Ag) and 0.04 wt.% (for S and Sb). Accuracy and precision are within ±2% relative for major elements.
Trace element analyses of whole-rock samples were completed at the ALS Global (Guangzhou, China) Co., Ltd., using an Agilent 7700x ICP-AES and an Agilent VISTA ICP-MS, with testing accuracies of 5% for rare earth elements and 5–12% for other trace elements.
Samples for C, H, and O isotope analyses were hand-selected and checked under a binocular microscope to ensure a purity of >98%. The C, H, and O isotopes were analyzed using a MAT-253 stable isotope ratio mass spectrometer at Yanduzhongshi Geological Analysis Laboratories Ltd. (Beijing, China). The techniques employed to measure H and O isotopes were according to [25,26]. The analytical precision was ±0.2‰ for δ18O and δ13C and ±2‰ for δD. The δ18O isotopic ratios were reported in standard δ notation (‰) relative to SMOW, and the δ13C isotopic ratios were reported in standard δ notation (‰) relative to PDB.

4. Results

4.1. Morphology and Structure of Ore

The ores of the Xujiashan deposit are primarily hosted within the dolomite and limestone of the Doushantuo Formation, exhibiting distinct banded structures (Figure 3a). The orebodies are stratified and lens-like, with attitudes consisting with the surrounding wall rocks. Stibnite samples are lead-gray in color (Figure 3b), and fine-grained stibnite is observed within the limestone, showing obvious calcitization (Figure 3c). Stibnite commonly coexists with quartz and calcite, and occasionally, calcite veins intersect quartz (Figure 3d). Stibnite displays a white to grayish-white reflective color and often covers and replaces quartz (Figure 3e). It also exhibits schistose textures with common deformation bands, deformation twins, and microfractures (Figure 3e,f).
Under back-scattered electron images, stibnite shows uniform chemical compositions; however, EDS analysis reveals rhythmic variations in Se content within the stibnite (see Figure 4 and Figure 5). Selenium within stibnite contains at least three distribution patterns, including ring-like, triangular, and core–mantle patterns (Figure 4d and Figure 5e). The width of the Se-rich belts varies.

4.2. EPMA Analysis

The main element compositions of stibnite in the Xujiashan deposit are 68.55% to 74.06% for Sb, 21.49% to 28.27% for S, and below detected limits to 2.44% for Se (Table 1). Based on the Se/(S + Se) ratio (atomic ratio), the series of stibnite–antimonselite minerals can be divided into stibnite [Se/(S + Se) < 0.20], selenium stibnite [0.20 ≤ Se/(S + Se) < 0.50], sulfur antimonselite [0.50 ≤ Se/(S + Se) < 0.80], and antimonselite [Se/(S + Se) > 0.80] [7,8,27,28,29].
Based on the average chemical composition obtained by electron microprobe analysis, the chemical formula of stibnite was Sb2.05 (S2.97, Se0.03)3.00, abbreviated as Sb2(S, Se)3, belonging to selenium stibnite. Figure 6 shows that S and Se contents in stibnite vary greatly with S contents decreasing as the Se contents increase.

4.3. Trace Elements

The trace element contents of the ores and wall rocks in the Xujiashan deposit are comparable (Figure 7). Apart from higher concentrations of Ti, Cu, Ge, As, Se, Hf, W, and Pb, the trace element compositions of the ores and wall rocks align with those of average carbonate rocks [30]. The ores exhibit significant enrichment in As (640 × 10−6 to 730 × 10−6), Se (>1000 × 10−6), Sb (>10,000 × 10−6), and Pb (7.00 × 10−6 to 300 × 10−6), while being depleted in Mg, Ca, Mn, Ni, Sr, and Ce (Table 2). The elevated Sb and Se content in both the ore and wall rock suggests that the wall rocks could have contributed materials for mineralization.
Cobalt (Co) is an indicator of oxygen levels in marine environments, typically lower in eutrophic waters and higher in oligotrophic waters [31]. In this study, the Co content in the wall rocks ranges from 1.40 × 10−6 to 1.50 × 10−6, indicating a nutrient-poor environment. Molybdenum (Mo) content, ranging from 0.7 × 10−6 to 1.59 × 10−6, suggests a weakly sulfidic environment [4]. Uranium (U) content in sedimentary rocks is typically low under oxidizing conditions, with concentrations ranging from 1 × 10−6 to 10 × 10−6. The U content of the wall rocks in this study, ranging from 1.11 × 10−6 to 1.79 × 10−6, indicates an oxidizing sedimentary environment [4].
The total rare earth element (REE) content of the ores ranges from 39.9 × 10−6 to 46.8 × 10−6, with light rare earth element (LREE) contents between 36.9 × 10−6 and 43.5 × 10−6 and heavy rare earth element (HREE) content between 2.99 × 10−6 and 3.32 × 10−6. The LREEs/HREEs ratios range from 12.34 to 13.56 and the (La/Yb) ratios from 17.71 to 21.58 (Table 2). The δEu values range from 1.42 to 2.37 and δCe values from 0.08 to 0.14 in the stibnite.

4.4. C-H-O Isotope Composition

The carbon and oxygen isotopic compositions of calcite and quartz from the Xujiashan deposit are listed in Table 3 and shown in Figure 8. The δ13CPDB values of calcite range from −0.8‰ to 5.5‰, and the δ18OSMOW values range from 20.4‰ to 20.7‰. The δ13CPDB values of quartz range from −12.8‰ to −8.1‰, and the δ18OSMOW values range from 22.6‰ to 24‰.
The hydrogen and oxygen isotope compositions of calcite and quartz are listed in Table 3. The δDV-SMOW values of calcite range from −57.8‰ to −86.9‰, and the δDV-SMOW values of quartz range from −67.4‰ to −67.9‰. According to the fluid inclusion homogenization temperatures obtained by Yu and Cao [11], the calculated δ18OH2O values are 8.78‰ to 10.18‰. The δ18OH2O-δD composition of quartz and calcite are distributed within the range of metamorphic water (Figure 9).
Minerals 14 00684 g008
Figure 8. Plots of δ13C versus δ18O of calcites and quartz from the Xujiashan deposit. For reference, the fields for typical marine carbonates (MC), sedimentary organic matter (Sedim Org), igneous carbonatite and mantle xenoliths (CMX), basic and ultrabasic rocks (BUR), and granite (Gran) are outlined. The arrows show typical isotopic trends resulting from carbonate dissolution (Dis Carb), decarbonation (Dec), decarboxylation of organic matter (Decbx), oxidation of organic matter (Oxid Org), and mixing trend (MT) (modified after [32,33], part of δ13CPDB and δ18OSMOW value after [12,15]).
Figure 8. Plots of δ13C versus δ18O of calcites and quartz from the Xujiashan deposit. For reference, the fields for typical marine carbonates (MC), sedimentary organic matter (Sedim Org), igneous carbonatite and mantle xenoliths (CMX), basic and ultrabasic rocks (BUR), and granite (Gran) are outlined. The arrows show typical isotopic trends resulting from carbonate dissolution (Dis Carb), decarbonation (Dec), decarboxylation of organic matter (Decbx), oxidation of organic matter (Oxid Org), and mixing trend (MT) (modified after [32,33], part of δ13CPDB and δ18OSMOW value after [12,15]).
Minerals 14 00684 g008
Minerals 14 00684 g009
Figure 9. Plot of δD versus δ18OH2O of calcites and quartz for the Xujiashan deposit (range of magmatic water, igneous hornblende, and biotite cited from [34]; Range of granite magma water cited from [35]; The extent of metamorphic water combines data from [34] and [36] (part of δD and δ18OSMOW value after [14], meteoric water value after [37]).
Figure 9. Plot of δD versus δ18OH2O of calcites and quartz for the Xujiashan deposit (range of magmatic water, igneous hornblende, and biotite cited from [34]; Range of granite magma water cited from [35]; The extent of metamorphic water combines data from [34] and [36] (part of δD and δ18OSMOW value after [14], meteoric water value after [37]).
Minerals 14 00684 g009
Table 3. Oxygen, carbon, and hydrogen isotopic compositions of quartz and calcite from the Xujiashan deposit.
Table 3. Oxygen, carbon, and hydrogen isotopic compositions of quartz and calcite from the Xujiashan deposit.
SamplesLithologyδDV-SMOWδ18OV-SMOWδ18OV-PDBδ13CV-PDBTemperatureδ18OH2O
(‰)(‰)(‰)(‰)(°C)(‰)
21XJS-3001Quartz−67.922.6−8.02−12.81708.78
21XJS-3002Quartz−67.424.0−6.66−8.1017010.2
21XJS-3001-CaCalcite−57.820.7−9.90−0.801709.42
21XJS-3003-CaCalcite−86.920.4−10.25.501709.12
δ18OH2O was calculated using the following equilibrium temperature formula: 1000lnQuartz-water = 3.38 × 106/(T + 273.15)2 − 3.40 [38]. 1000lnCalcites-water = 2.78 × 106/(T + 273.15)2 − 3.39 [39].

5. Discussion

5.1. Sources of Ore-forming Fluid

Many models have been established for the genesis of Xujiashan deposits, including syn-sedimentary mineralization [11,15,16,17,18], infill of hydrothermal fluids in interlayer fracture zones [40], and precipitation of low- to medium-temperature hydrothermal fluids [9]. Yu and Cao concluded that the Xujiashan deposit underwent a sedimentary-mineralization stage and a hydrothermal fluid alteration stage, where the latter one precipitated stibnite, quartz, calcite, barite, and pyrite. The wall rocks exhibit antimony (Sb) contents exceeding 10 ppm (Table 4), which is 55–235 times higher than the average crustal value of 0.2 ppm. Moreover, the trace element compositions of the ores and wall rocks are similar (Figure 7), indicating that the metals for mineralization originated from the wall rocks, with the deposition of Sb in the ore-hosting strata serving as the initial enrichment stage [11]. Marine sediments and carbonate-bearing rocks are enriched in Te and Se [41,42], and organic matter is an important host for Se [43], accounting for the high Se contents in the organic matter-rich black shales of the Cambrian Niutitang Formation [44,45,46]. Therefore, the Niutitang Formation is a potential source for Se mineralization at Xujiashan.
Yu [11,15] studied the sulfur isotopic compositions of stibnite ranging from +12.1 to +14.4, coincident with the sedimentary sulfur, indicating the origin of wall rocks or the earlier sedimentary deposits. The author also tested the oxygen, carbon, and hydrogen isotopic compositions of quartz and calcite; the δ13CPDB values of calcite range from −0.3‰ to −2.6‰, and the δ18OSMOW values range from 9.1‰ to 11.6‰. These isotopic compositions are consistent with those of marine carbonates and align with pre-mineralization calcite measurements by Shen [12], indicating a common source. The combined δ13CPDB and δ18OSMOW isotopic compositions of calcite suggest an evolutionary trend indicating a mixture of carbon sources. Quartz exhibits δ13CPDB values between −12.8‰ and −8.1‰, and δ18OSMOW values between 22.6‰ and 24‰ (Figure 8), differing from those of calcite. This discrepancy suggests distinct carbon isotope sources: carbon isotopes in calcite are primarily derived from CaCO3, reflecting the source of ore-forming materials, while those in quartz are derived from fluid inclusions, indicating the C isotope composition of ore-forming fluids. Therefore, it is inferred that the ore-forming materials originated from the wall rocks. The hydrothermal fluids dissolved the wall rocks (carbonates) and underwent water–rock interactions, with some carbon in the fluids possibly derived from the decarboxylation of organic matter [47].
The δ18OH2O values of calcite range from −1.06‰ to 1.57‰ [11], and the δ18OH2O values of the ore-forming fluids exhibit regular variations during mineralization, indicating continuous oxygen isotope exchange between the hydrothermal fluids and the wall rocks. Kinetic fractionation causes the δD-δ18OH2O values to skew towards higher δ18OH2O values, deviating from the meteoric water line (Figure 9). Combining the δD and δ18OH2O isotopic compositions with the regional meteoric water line shows a continuous evolutionary trend, suggesting that the fluid originated from a mixture of metamorphic water and meteoric water. Differences in the extent of meteoric water influence at various mineralization stages result in different positions on the diagram, but the overall evolutionary trend remains consistent. In addition, the fluid inclusions are mainly liquid inclusions with homogenization temperature ranging from 158 ℃ to 189 ℃, significantly lower compared with the magmatic fluids but coincident with the meteoric and metamorphic fluids [11]. Thus, the ore-forming fluids are primarily deep-circulating meteoric water mixed with organic-rich fluids.
The C-H-O isotope compositions and mineral trace element compositions presented in this study indicate that the ore-forming materials were derived from sedimentary–metamorphic rocks, and the ore-forming fluids were metamorphic water produced by metamorphism. The ore-forming fluids experienced multistage mixing of meteoric water and organic-rich fluids.

5.2. Genesis and Growth Modeling of Selenium Stibnite

Stibnite (Sb2S3) and antimonselite (Sb2Se3), with the general formula A2VB3VI (where A = Sb and B = S, Se), are layer-structured semiconductors with orthorhombic crystal structure. In these compounds, each Sb atom is bonded to three S or Se atoms, and each S or Se atom is bonded to three Sb atoms, with the layers held together by weak secondary bonds (Figure 10) [48,49]. The chemical bonds within the ribbons are strong, whereas the bonds between the ribbons are much weaker due to the concentration of electron density within the ribbons.
The valence electron configurations of Sb, S, and Se are 5s25p3, 3s23p4, and 4s24p4, respectively. The Se atom is larger than the S atom, and the inner atoms (closer to the center of the ribbons) have smaller volumes than the outer atoms (closer to the edges of the ribbons) [50]. Selenium substitutes for sulfur in the stibnite crystal lattice, causing lattice expansion. However, this expansion is minor at low Se concentrations, similar to the mechanism of arsenic substitution for sulfur in pyrite [51].
Rhythmic bands and chemical zoning in minerals indicate physicochemical changes in ore-forming fluids during crystallization, including pressure, temperature, and chemical compositions, which are also controlled by kinetic factors and hydrothermal alteration after precipitation. Therefore, banded minerals could reveal crystallization when processed or after subsequent alteration events. For example, zircon in the Namcha Barwa Formation comprises a magmatic core and a metamorphic rim, reflecting early magmatic and subsequent metamorphic events [52,53,54,55]. Ring-banding pyroxene from the Yaojiazhuang pluton reveals multistage crystallization during magmatic mixing [56,57,58]. Variations in element compositions in pyrite at the Zijinshan Cu-Au deposit indicate changes in temperature and the geological environment during the precipitation of ore-forming fluids [59,60].
Stibnite from Xujiashan has Sb contents of 68.55% to 74.06% and S contents of 25.74% to 28.27% and Se contents up to 2.44% with an average value of 0.68%. The Se contents in stibnite are approximately five orders of magnitude higher than the crustal value and much higher than those in the Xikuangshan Sb deposit (9.2 × 10−6 [61]). Owing to the similar geochemical characteristics of Se and S, Se can replace S easily in sulfides and is less likely to form selenides [62,63]. EDS analyses reveal that Se is distributed rhythmically in stibnite grains, reflecting physicochemical changes during crystallization (Figure 4 and Figure 5). Based on the distributed patterns of Se in stibnite and the origin of metals, the formation model for selenium stibnite has been established.
Hydrothermal fluids, derived from heated meteoric and metamorphic water dissolve S, Se, and Sb from wall rocks, forming ore-forming fluids. Initially, f (O2) and f (Se2) are relatively low, while f (S2) is high, favoring the precipitation of stibnite (Figure 11a). Due to the consumption of S during stibnite crystallization or mixing with Se-rich fluids, selenium stibnite precipitates and covers the early formed stibnite (Figure 11b). As the Se content decreases, stibnite precipitates again. These processes could occur multiple times and result in the rhythmically banded textures in stibnite (Figure 11c).
The Se-bearing bands in the stibnite have various patterns (Figure 4 and Figure 5), which may have resulted from different cross-sections of the stibnite. The different cross-sections of the stibnite will form different shapes of Se-bearing ring bands. If the cross-section is the crystal’s transverse section (Figure 12, a-a’), a ring-shaped band will appear. If the cross-section is the crystal’s surface (Figure 12, b-b’), a core–mantle ring band will appear. If the cross-section is an oblique cut crystal (Figure 12, c-c’), a rhombic or triangular ring band will appear.

6. Conclusions

(1) The chemical formula of stibnite in Xujiashan stibnite deposit is Sb2.05 (S2.97, Se0.03)3.00, abbreviated as Sb2(S, Se)3, belonging to selenium stibnite.
(2) The ore-forming materials were mainly derived from the wall rocks (sedimentary–metamorphic rocks). Hydrothermal fluids derived from heated meteoric and metamorphic water, which dissolved S, Se, and Sb from wall rocks, and formed ore-forming fluids. Ore-forming fluids experienced multistage mixing of meteoric water and organic-rich fluids.
(3) Selenium substitutes for sulfur in the stibnite crystal lattice, causing rhythmically distributed Se contents in stibnite, which resulted from multistage physicochemical changes in ore-forming fluids during crystallization.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/min14070684/s1, Table S1: EPMA analyses and chemical formulae of stibnite from the Xujiashan deposit.

Author Contributions

Conceptualization and methodology, D.W. and Y.L.; Investigation, D.W., G.W. and R.H.; Experimental analysis, Y.L., W.W. and Y.K.; Writing—original draft preparation, Y.L. and D.W.; Writing—review and editing, D.W.; Plotting, Y.L. and D.W. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by China National Natural Science Foundation, grant numbers 92062219, the National Key R&D Program of China, grant number 2023YFC2906801, and the National Nonprofit Institute Research Grant of IGGE, grant number AS2022P03.

Data Availability Statement

Data available on request due to restrictions eg privacy or ethical: The data presented in this study are available on request from the corresponding author due to (specify the reason for the restriction).

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Yi, J.B. Basic characteristics of global antimony ore deposits and the background of mega antimony deposits. Geotecton. Metallog. 1994, 18, 199–208, (In Chinese with English Abstract). [Google Scholar]
  2. Zhang, G.L.; Yao, J.Y.; Gu, X.P. Time and spatial distribution regularities and deposit types of antimony in China. Miner. Resour. Geol. 1998, 12, 19–25, (In Chinese with English Abstract). [Google Scholar]
  3. Xiao, Q.M.; Zeng, D.R.; Jin, F.Q.; Yang, M.Y.; Yang, Z.F. Time-Space Distribution Feature and Exploration Guide of China’s Sb-Deposits. Geol. Explor. 1992, 12, 9–14, (In Chinese with English Abstract). [Google Scholar]
  4. Zhang, G.; Jiang, X.; Fan, H.F.; Wen, H.J. Selenium Enrichment in the Ediacaran Doushantuo Formation from Yichang Region, South China and Its Geology Implications. Acta Miner. Sin. 2017, 37, 258–268, (In Chinese with English Abstract). [Google Scholar]
  5. Chen, B.H.; Ding, J.H.; Ye, H.S.; Yin, J.N.; Liu, J.N. Metallogenic regularity of selenium ore in China. Miner. Deposits. 2020, 39, 1063–1077, (In Chinese with English Abstract). [Google Scholar]
  6. Li, J.X.; Liu, J.J. Advances in selenium resource study. Resour. Ind. 2014, 16, 90–97, (In Chinese with English Abstract). [Google Scholar]
  7. Heropoulos, C.; Seeley, J.L.; Radtke, A.S. Spectrographic Determination of Selenium in Stibnite. Appl. Spectrosc. 1984, 38, 451–454. [Google Scholar] [CrossRef]
  8. Liu, J.J.; Li, Z.M.; Liu, J.M.; Wang, J.P.; Feng, C.X.; Lu, W.Q. Mineralogy of the Stibnite-Antimonselite Series in the Nature. J. Jilin Univ. (Earth Sci. Ed.) 2005, 35, 545–553, (In Chinese with English Abstract). [Google Scholar]
  9. Shen, N.P.; Peng, J.T.; Yuan, S.D.; Zhang, D.L.; Hu, R.Z.; Wang, G.Q. Characteristics of fluid inclusions in Xujiashan antimony deposit of Hubei Province and its implications. Miner. Dep. 2008, 27, 570–578, (In Chinese with English Abstract). [Google Scholar]
  10. Zhang, D.; Wang, S.J. Mineralogical Characteristics and Geological Significance of Se, Te-Rich Stibnite in Sb Ore Belt, Southern Anhui Province. Earth Sci. J. Chn. Univ. Geosci. 1994, 19, 169–173, (In Chinese with English Abstract). [Google Scholar]
  11. Yu, H.L.; Cao, W. The geological characteristics and stable isotope composition of the xujiashan antimony deposit in Hubei province and its mechanism of ore formation. Geol. Rev. 1986, 32, 264–275+322, (In Chinese with English Abstract). [Google Scholar]
  12. Shen, N.P.; Peng, J.T.; Yuan, S.D.; Zhang, D.L.; Fu, Y.Z.; Hu, R.Z. Carbon, oxygen and strontium isotope geochemistry of calcites from Xujiashan antimony deposit, Hubei Province. Geochimica 2007, 36, 479–485, (In Chinese with English Abstract). [Google Scholar]
  13. Shen, N.P.; Peng, J.T.; Yuan, S.D.; Zhang, D.L.; Hu, R.Z.; Wang, G.Q. Sm-Nd isotope system of calcite from Xujiashan antimony deposit, Hubei, China-Possibility of its Caledonian mineralization. In Proceedings of the 12th Annual Conference of Mineralogy, Petrology and Geochemistry Society of China, Guiyang, China, 2009. (In Chinese with English Abstract). [Google Scholar]
  14. Shen, N.P.; Peng, J.T.; Yuan, S.D.; Zhang, D.L.; Hu, R.Z. Lead isotope compositions and its significance for ore-form ingmaterial of the xujiashan antimony deposit, Hubei province. Acta Mneral. Sin. 2008, 02, 169–176, (In Chinese with English Abstract). [Google Scholar]
  15. Yu, H.L. The material source of and the properties of ore-forming solutions responsible for strata bound Sb deposits in carbonate rocks at xujiashan, Hubei province. Geochimica 1987, 2, 167–175, (In Chinese with English Abstract). [Google Scholar]
  16. Sun, H.Z.; Lei, L. Geological characteristics of the xujiashan stratified antimony deposit in Hubei province. Miner. Depos. 1988, 7, 49–54, (In Chinese with English Abstract). [Google Scholar]
  17. Yu, H.L. Typomorphic characteristics of stibnite from Xujiashan. Hubei province with a discussion on its genesis. Acta Petrol. Miner. 1988, 7, 361–367, (In Chinese with English Abstract). [Google Scholar]
  18. Shen, N.P.; Peng, J.T.; Hu, R.Z.; Liu, S.; Coulson, I.M. Strontium and Lead Isotopic Study of the Carbonate-hosted Xujiashan Antimony Deposit from Hubei Province, South China: Implications for its Origin. Resour. Geol. 2011, 61, 52–62. [Google Scholar] [CrossRef]
  19. The fourth geological Brigade, Hubei Geological Bureau. (Tongshan County, Hubei Province, China). Personal communication, 2023.
  20. Shen, Q.W.; Wang, D.Z.; Leng, C.B.; Yu, H.J.; Zhang, C.Y.; Su, X.Y.; Mao, J.W.; Liang, F. Discovery of Telluride and Selenide in the Giant Pulang Porphyry Cu-Au Deposit, Yunnan Province. Rock Min. Anal. 2023, 42, 643–646, (In Chinese with English abstract). [Google Scholar]
  21. Guo, G.L.; Xu, X.Z.; Li, J.Y. The character and genesis of anorthite as inclusions in spinel of mantle peridotites from the Purang ophiolite (Southwestern Tibetan Plateau). Acta. Petrol. Sin. 2011, 27, 3197–3206, (In Chinese with English abstract). [Google Scholar]
  22. Liu, C.Z.; Wu, F.Y.; Wilde, S.A.; Yu, L.J.; Li, J.L. Anorthitic plagioclase and pargasitic amphibole in mantle peridotites from the Yungbwa ophiolite (southwestern Tibetan Plateau) formed by hydrous melt metasomatism. Lithos 2010, 114, 413–422. [Google Scholar] [CrossRef]
  23. Xu, X.Z.; Yang, J.S.; Guo, G.L.; Li, J.Y. Lithological research on the Purang mantle peridotite in western Yarlung-Zangbo suture zone in Tibet. Acta. Petrol. Sin. 2011, 27, 3179–3196, (In Chinese with English abstract). [Google Scholar]
  24. Hu, H.; Wang, R.C.; Xie, L.; Zhang, W.L.; Tian, E.R.; Xu, Y.T.; Fan, H.R. High Precision Analysis of Chemical Composition of SPI Monazite Standard on Large Spectrometer of 140 mm Rowland Circle. Geol. J. Chn. Uni. 2021, 27, 317–326, (In Chinese with English Abstract). [Google Scholar]
  25. Coleman, M.L.; Sheppard, T.J.; Durham, J.J.; Rouse, J.E.; Moore, G.R. Reduction of water with zinc for hydrogen isotope analysis. Anal. Chem. 1982, 54, 993–995. [Google Scholar] [CrossRef]
  26. Clayton, R.N.; Mayeda, T.K. The use of bromine pentafluoride in the extraction of oxygen from oxides and silicates for isotopic analysis. Geochim. Cosmochim. Acta 1963, 27, 43–52. [Google Scholar] [CrossRef]
  27. Li, J.J. Analysis of a series of artificially synthesized Sb2S3 (pyroxene)-Sb2Se3 (selenoantimonite) solid solutions. In Proceedings of the 9th National X-ray Diffraction Conference and International Centre for Diffraction Data (ICDD) Symposium, Hangzhou, China, 15–17 October 2006. (In Chinese with English Abstract). [Google Scholar]
  28. Liu, J.J.; Liu, J.M.; Xie, H.; Feng, C.X.; Wang, J.P.; Zhang, N.; Li, J.L.; Oi, F. An experimental study on the synthesis ofstibnite-antimonselite series. Miner. Petrol. 2006, 26, 16–23, (In Chinese with English Abstract). [Google Scholar]
  29. Liu, J.J.; Zheng, M.H. First discovery of a selenium-sulfur compound series of antimony. Chn. Sci. Bull. 1992, 37, 864, (In Chinese with English Abstract). [Google Scholar]
  30. Turekian, K.K.; Wedepohl, K.H. Distribution of the Elements in Some Major Units of the Earth’s Crust. GSA Bull. 1961, 72, 175–192. [Google Scholar] [CrossRef]
  31. Large, R.R.; Gregory, D.D.; Steadman, J.A.; Tomkins, A.G.; Lounejeva, E.; Danyushevsky, L.V.; Halpin, J.A.; Maslennikov, V.; Sack, P.J.; Mukherjee, I.; et al. Gold in the oceans through time. Earth Planet. Sci. Lett. 2015, 428, 139–150. [Google Scholar] [CrossRef]
  32. Liu, J.M.; Liu, J.J. Basin fluid genetic model of sediment-hosted micro disseminated gold deposits in the gold-triangle area between Guizhou, Guangxi and Yunnan. Mineral. Sin. 1997, 17, 448–456, (In Chinese with English Abstract). [Google Scholar]
  33. Sun, J.G.; Hu, S.X.; Liu, J.M.; Shen, K.; Ling, H.F. Nd, Sr, O isotope study of potassium-rich dark-coloured dyke swarms in the Late Mesozoic gold-mining area, Jiaodong, China. Acta Geol. Sin. 2001, 75, 553, (In Chinese with English Abstract). [Google Scholar]
  34. Taylor, H. The application of oxygen and hydrogen isotope studies to problems of hydrothermal alteration and ore deposition. Econ. Geol. 1974, 69, 843–883. [Google Scholar] [CrossRef]
  35. Sheppard, S. Identification of the origin of oreforming solutions by the use of stable isotopes. Geol. Soc. Lond. Spec. Publ. 1977, 7, 25–41. [Google Scholar] [CrossRef]
  36. Sheppard, S.M.F. Stable isotope geochemistry of fluids. Phys. Chem. Earth 1981, 13–14, 419–445. [Google Scholar] [CrossRef]
  37. Zhang, H.P. The background values of the precipitation stable isotopes of China. Site Investig. Sci. Technol. 1989, 6, 6–13. [Google Scholar]
  38. Clayton, R.N.; O’neil, J.R.; Mayeda, T.K. Oxygen isotope exchange between quartz and water. Geophys. Res. 1972, 77, 3057–3067. [Google Scholar] [CrossRef]
  39. O’neil, J.R.; Clayton, R.N.; Mayeda, T.K. Oxygen isotope fractionation in divalent metal carbonates. Chem. Phys. 1969, 51, 5547–5558. [Google Scholar] [CrossRef]
  40. Luo, X.S. Geological characteristics, mineralisation and direction of searching for antimony ore in E’nan area. Resour. Environ. Eng. 2013, 27 (Suppl. S1), 69–75+80, (In Chinese with English Abstract). [Google Scholar]
  41. Keith, M.; Smith, D.J.; Jenkin, G.R.T.; Holwell, D.A.; Dye, M.D. A review of Te and Se systematics in hydrothermal pyrite from precious metal deposits: Insights into ore-forming processes. Ore Geol. Rev. 2018, 96, 269–282. [Google Scholar] [CrossRef]
  42. Schirmer, T.; Koschinsky, A.; Bau, M. The ratio of tellurium and selenium in geological material as a possible paleo-redox proxy. Chem. Geol. 2014, 376, 44–51. [Google Scholar] [CrossRef]
  43. Wen, H.; Carignan, J. Selenium isotopes trace the source and redox processes in the black shale-hosted Se-rich deposits in China. Geochim. Cosmochim. Acta 2011, 75, 1411–1427. [Google Scholar] [CrossRef]
  44. Guo, Q.; Shields, G.A.; Liu, C.Q.; Strauss, H.; Zhu, M.Y.; Pi, D.H.; Goldberg, T.; Yang, X.L. Trace element chemo stratigraphy of two Ediacaran–Cambrian successions in South China: Implications for organ sedimentary metal enrichment and silicification in the Early Cambrian. Palaeogeogr. Palaeoclimatol. Palaeoecol. 2007, 254, 194–216. [Google Scholar] [CrossRef]
  45. Lehmann, B.; Nagler, T.F.; Holland, H.D.; Wille, M.; Mao, J.W.; Pan, J.Y.; Ma, D.S.; Dulski, P. Highly metalliferous carbonaceous shale and Early Cambrian seawater. Geology 2007, 35, 403–406. [Google Scholar] [CrossRef]
  46. Xu, L.G.; Lehmann, B.; Mao, J.W. Seawater contribution to polymetallic Ni–Mo–PGE–Au mineralization in Early Cambrian black shales of South China: Evidence from Mo isotope, PGE, trace element, and REE geochemistry. Ore Geol. Rev. 2013, 52, 66–84. [Google Scholar] [CrossRef]
  47. Liu, J.M.; Gu, X.X.; Liu, J.J.; Zhen, M.H. Giant metallogenic Sb belt in south China and its constraints. Acta. Geogr. Sin. 1998, 41 (Suppl. S1), 206–215, (In Chinese with English Abstract). [Google Scholar]
  48. Koc, H.; Mamedov, A.M.; Deligoz, E.; Ozisik, H. First principles prediction of the elastic, electronic, and optical properties of Sb2S3 and Sb2Se3 compounds. Solid State Sci. 2012, 14, 1211–1220. [Google Scholar] [CrossRef]
  49. Madelung, O. Semiconductors: Group IV Elements and III–V Compounds; Springer Science & Business Media: Berlin/Heidelberg, Germany, 1991. [Google Scholar]
  50. Caracas, R.; Gonze, X. First-principles study of the electronic properties of A2B3 minerals, with A = Bi, Sb and B = S, Se. Phys. Chem. Miner. 2005, 32, 295–300. [Google Scholar] [CrossRef]
  51. Fu, M.S.; Chen, L.X.; Li, C.Y.; Xu, J.; Chai, D.; Li, Y.Q. Density Functional Theory Study on Crystal Structure and Properties of Arsenicbearing Pyrite. Conserv. Utili. Min. Resour. 2022, 42, 112–118, (In Chinese with English Abstract). [Google Scholar]
  52. Vavra, G.; Schmid, R.; Gebauer, D. Internal morphology, habit and U-Th-Pb microanalysis of amphibolite-to-granulite facies zircons: Geochronology of the Ivrea Zone (Southern Alps). Contrib. Mineral. Petrol. 1999, 134, 380–404. [Google Scholar] [CrossRef]
  53. Zhang, Z.M.; Wang, J.L.; Shen, K.; Shi, C. Paleozoic circum-Gondwana orogens: Petrology and geochronology of the Namche Barwa Complex in the eastern Himalayan syntaxis, Tibet. Acta Petrol. Sin. 2008, 24, 1627–1637, (In Chinese with English Abstract). [Google Scholar]
  54. Miller, C.F.; Hatcher, R.D., Jr.; Mark, H.T.; Coath, C.D.; Gorisch, E.B. Cryptic crustal events elucidated through zone imaging and ion microprobe studies of zircon, southern Appalachian Blue Ridge, North Carolina–Georgia. Geology 1998, 26, 419–422. [Google Scholar] [CrossRef]
  55. Schaltegger, U.; Fanning, C.M.; Gunther, D.; Maurin, J.C.; Schulmann, K.; Gebauer, D. Growth, annealing and recrystallization of zircon and preservation of monazite in high-grade meta morphism: Conventional and in-situ U-Pb isotope, cathodoluminescence and microchemical evidence. Contrib. Mineral. Petrol. 1999, 134, 186–201. [Google Scholar] [CrossRef]
  56. Liu, X.; Tang, Y.J. The characteristics and implication of the zonation in clinopyroxene phenocrysts from the Yaojiazhuang ultramafic-syenitic complex, northwestern Hebei Province. Acta Petro. Sin. 2018, 34, 3315–3326, (In Chinese with English Abstract). [Google Scholar]
  57. Nisbet, E.G.; Pearce, J.A. Clinopyroxene composition in mafic lavas from different tectonic settings. Contrib. Mineral. Petrol. 1977, 63, 149–160. [Google Scholar] [CrossRef]
  58. Dobosi, G. Clinopyroxene zoning patterns in the young alkali basalts of Hungary and their petrogenetic significance. Contrib. Mineral. Petrol. 1989, 101, 112–121. [Google Scholar] [CrossRef]
  59. Zhang, W.Y.; Wang, C.Z.; Sun, Y.C.; Qiu, Z.Z.; Cu, Y.B. Characteristics of zonal pyrite in Zijinshan Cu-Au Deposit. Nonferrous Met. (Min. Sec). 2014, 66, 36–42, (In Chinese with English Abstract). [Google Scholar]
  60. Zhang, D.Q.; Li, D.X.; Zhao, Y.M.; Chen, J.H.; Li, Z.L.; Zhang, K.Y. The Zijinshan deposit: The first example of quartz-alunite type epithrmal deposits in the continent of China. Geol. Rev. 1991, 37, 481–491, (In Chinese with English Abstract). [Google Scholar]
  61. Liu, H.P.; Zhang, Y.L.; Hu, W.Q. On the origin of the stibnite deposit of Shikuangshan mine, Hunan. Hunan Geol. 1985, 4, 28–39+83, (In Chinese with English Abstract). [Google Scholar]
  62. Simon, G.; Essene, E.J. Phase relations among selenides, sulfides, tellurides, and oxides; I, Thermodynamic properties and calculated equilibria. Eco. Geol. 1996, 91, 1183–1208. [Google Scholar] [CrossRef]
  63. Simon, G.; Kesler, S.E.; Essene, E.J. Phase relations among selenides, tellurides, and oxides; II, Applications to selenide-bearing ore deposits. Eco. Geol. 1997, 92, 468–484. [Google Scholar] [CrossRef]
Minerals 14 00684 g003
Figure 3. Photographs and photomicrographs of Xujiashan stibnite deposit: (a) The gray limestone of Doushantuo Formation; (b) Photograph of lead-gray stibnite ore, showing massive texture; (c) The limestone contains fine-grained stibnite, showing obvious calcitization; (d) Quartz is associated with calcite (e) Anisotropy of stibnite due to deformation twins in reflected light microscopy; (f). Typical en echelon deformation twins (gray) in reflected light microscopy. Abbreviations: Ls = Limestone, Cal = Calcite, Qtz = Quartz, Stb = Stibnite.
Figure 3. Photographs and photomicrographs of Xujiashan stibnite deposit: (a) The gray limestone of Doushantuo Formation; (b) Photograph of lead-gray stibnite ore, showing massive texture; (c) The limestone contains fine-grained stibnite, showing obvious calcitization; (d) Quartz is associated with calcite (e) Anisotropy of stibnite due to deformation twins in reflected light microscopy; (f). Typical en echelon deformation twins (gray) in reflected light microscopy. Abbreviations: Ls = Limestone, Cal = Calcite, Qtz = Quartz, Stb = Stibnite.
Minerals 14 00684 g003
Minerals 14 00684 g004
Figure 4. Microscope and scanning electron microscope images of ores from the Xujiashan deposit: (a) Back-scattered electron images; (b) Reflected light photographs of antimony ore; (c) EDS mapping of Sb contents in stibnite; (d) EDS mapping of Se contents in stibnite. Abbreviations: Qtz = Quartz, Stb = Stibnite.
Figure 4. Microscope and scanning electron microscope images of ores from the Xujiashan deposit: (a) Back-scattered electron images; (b) Reflected light photographs of antimony ore; (c) EDS mapping of Sb contents in stibnite; (d) EDS mapping of Se contents in stibnite. Abbreviations: Qtz = Quartz, Stb = Stibnite.
Minerals 14 00684 g004
Minerals 14 00684 g005
Figure 5. Microscope and scanning electron microscope images of ores from the Xujiashan deposit: (a) Back-scattered electron images of stibnite; (b) Reflected light photographs of stibnite; (c) EDS mapping of Sb contents in stibnite; (d) EDS mapping of S contents in stibnite; (e) EDS mapping of Se contents in stibnite and locations of line scanning; (f) EDS line scanning show changes in Se contents in stibnite. Abbreviations: Qtz = Quartz, Stb = Stibnite.
Figure 5. Microscope and scanning electron microscope images of ores from the Xujiashan deposit: (a) Back-scattered electron images of stibnite; (b) Reflected light photographs of stibnite; (c) EDS mapping of Sb contents in stibnite; (d) EDS mapping of S contents in stibnite; (e) EDS mapping of Se contents in stibnite and locations of line scanning; (f) EDS line scanning show changes in Se contents in stibnite. Abbreviations: Qtz = Quartz, Stb = Stibnite.
Minerals 14 00684 g005
Minerals 14 00684 g006
Figure 6. Composition of selenium stibnite from the Xujiashan deposit. (The red rectangles represent analysis sample).
Figure 6. Composition of selenium stibnite from the Xujiashan deposit. (The red rectangles represent analysis sample).
Minerals 14 00684 g006
Minerals 14 00684 g007
Figure 7. Trace element concentrations of wall rocks and ores from the Xujiashan deposit, ores and wall rocks normalized to the average carbonates [30].
Figure 7. Trace element concentrations of wall rocks and ores from the Xujiashan deposit, ores and wall rocks normalized to the average carbonates [30].
Minerals 14 00684 g007
Minerals 14 00684 g010
Figure 10. Crystal structure of A2VB3VI (A = Sb and B = S,Se).
Figure 10. Crystal structure of A2VB3VI (A = Sb and B = S,Se).
Minerals 14 00684 g010
Minerals 14 00684 g011
Figure 11. Crystallization processes of Se-bearing bands in stibnite: (a) precipitation of stibnite; (b) selenium stibnite precipitates and covers the early formed stibnite; (c) stibnite precipitates again.
Figure 11. Crystallization processes of Se-bearing bands in stibnite: (a) precipitation of stibnite; (b) selenium stibnite precipitates and covers the early formed stibnite; (c) stibnite precipitates again.
Minerals 14 00684 g011
Minerals 14 00684 g012
Figure 12. Various Se-bearing bands shapes of different cross-sections of stibnite: (a) The cross-section of the stibnite crystal; (b) The longitudinal section of the stibnite crystal; (c) The oblique section of the stibnite crystal.
Figure 12. Various Se-bearing bands shapes of different cross-sections of stibnite: (a) The cross-section of the stibnite crystal; (b) The longitudinal section of the stibnite crystal; (c) The oblique section of the stibnite crystal.
Minerals 14 00684 g012
Table 1. EPMA analyses and chemical formulae of stibnite from the Xujiashan deposit.
Table 1. EPMA analyses and chemical formulae of stibnite from the Xujiashan deposit.
Samples ZnCuSbSFeMoAgWAsCoPbSeMolecular Formulas
ωt/%
1004(16)max1.060.0573.1127.640.050.350.050.180.470.040.080.04Sb 2.05–2.13 S 3.00
min----71.2726.84--0.20----0.30------
median0.910.0472.2327.380.010.290.030.120.390.030.050.04
1013(10)max0.050.0371.0828.270.030.240.010.170.410.020.080.10Sb 1.98–2.00 S 3.00
min----70.3427.90--0.20----0.20------
median0.040.0370.7128.020.020.220.010.100.300.010.030.03
1019(10)max0.070.0670.4927.950.020.230.030.010.400.010.110.08Sb 1.98–2.03 S 3.00
min----69.0527.21--0.19----0.18------
median0.030.0470.2027.630.010.210.010.070.340.010.050.05
1028(21)max0.9450.0772.6327.180.070.400.060.130.600.030.112.26Sb 2.04–2.10 (S 2.90–2.97, Se 0.03–0.10) 3.00
min----70.7426.18--0.20----0.40----0.74
median0.070.0371.3326.640.030.310.030.060.480.020.031.33
1030(19)max0.990.0871.6126.660.050.380.050.100.620.030.112.44Sb 2.04–2.09 (S 2.90–2.94, Se 0.06–0.11) 3.00
min----70.2725.74--0.21----0.37----1.35
median0.480.0471.0126.290.030.270.030.060.420.020.041.93
1032(10)max0.070.0670.9728.030.010.260.030.120.340.020.150.18Sb 1.98–2.00 (S 2.99–3.00, Se 0.00–0.01) 3.00
min----70.3027.65--0.18----0.23----0.06
median0.050.0270.5127.850.010.210.010.060.310.010.120.14
1035(16)max1.060.0874.0627.900.060.360.090.140.600.040.070.31Sb 2.01–2.10 (S 2.99–3.00, Se 0.00–0.01) 3.00
min----68.5526.72--0.21----0.30----0.01
median0.100.0372.7427.550.040.310.040.090.460.010.020.13
-- represents below detection limit. The complete EPMA data are presented in Supplementary Material Table S1.
Table 2. Comparation the trace elements of ores, wall rocks and strata(rocks) from the Xujiashan deposit (×10−6).
Table 2. Comparation the trace elements of ores, wall rocks and strata(rocks) from the Xujiashan deposit (×10−6).
SamplesDetection LimitXJS-2001XJS-2002XJS-2003XJS-2004XJS-2005XJS-2006Turekian and Wedepohl [30]
Wall RockWall RockWall RockOreOreOreShalesCarbonatesClay
Li0.2014.3014.101.7010.07.002.0066.05.0057
Be0.050.140.300.200.500.500.503.00--2.60
Mg10020,20067,20045,5001000100017,00015,00047,00021,000
Al10026002900220010001000100080,000420084,000
P10.0840126046010020010007004001500
K1001000100090010001000100026,600270025,000
Ca100215,000191,000230,0003000400037,00022,100302,30029,000
Sc0.101.101.001.101.001.001.0013.01.0019.0
Ti50.015010070.050050050046004004600
V5.005.0011.05.0010.010.010.013020.0120
Cr1.0010.018.010.010.010.010.090.011.090.0
Mn5.0020744748850.050.070.085011006700
Co0.101.501.501.40------19.00.1074.0
Ni0.202.205.502.502.002.002.0068.020.0225
Cu0.207.306.909.6088.030.037.045.04.00250
Zn2.006.0064.07.0020.020.020.095.020.0165
Ga0.051.161.040.720.501.000.6019.04.0020.0
Ge0.050.090.160.0928.76.605.001.600.202.00
As0.206.8031.511.473072064013.01.0013.0
Se1.001.006.003.00>1000>1000>10000.600.080.17
Rb0.203.103.002.601.002.001.001403.00110
Sr0.2056148685410.017.072.0300610180
Y0.106.305.606.501.001.002.0026.030.090.0
Zr2.004.004.003.005.005.005.0016019.0150
Nb0.100.400.300.301.001.001.0011.00.3014.0
Mo0.050.721.590.611.200.701.202.600.4027.0
Ag0.010.060.060.041.201.100.500.07--0.11
Cd0.020.020.360.040.400.600.200.300.0350.42
In0.0050.0050.0050.0110.080.05--0.10--0.08
Sn0.2------2.002.002.006.00--1.50
Sb0.0559.3220078>10,000>10,000>10,0001.500.21.00
Cs0.050.630.660.32------5.00--6.00
Ba0.50209626151.5100.00100.00100.0058010.02300
La0.104.105.507.5034.0040.0034.0092.0--115
Ce0.105.88.4011.51.001.602.6059.011.5345
Pr0.020.981.261.460.300.300.605.601.1033.0
Nd0.104.005.005.101.001.003.0024.04.70140
Sm0.030.871.010.960.300.300.606.401.3038.0
Eu0.020.270.360.600.300.300.301.000.206.00
Gd0.050.820.970.890.500.500.706.401.3038.0
Tb0.010.130.140.140.100.100.101.000.206.00
Dy0.050.780.770.840.500.500.504.600.9027.0
Ho0.010.160.150.170.100.100.101.200.307.50
Er0.030.460.390.420.300.300.302.500.5015.0
Tm0.010.070.050.060.100.100.100.200.041.20
Yb0.030.410.290.320.300.300.302.600.5015.0
Lu0.010.060.040.050.100.100.100.700.204.50
Hf0.100.100.100.101.001.001.002.800.304.10
Ta0.05------------0.80----
W0.10.300.200.101.001.001.001.800.60--
Tl0.020.040.110.020.500.401.101.40--0.80
Pb0.501.307.804.903007.0010020.09.0080.0
Th0.050.370.330.300.100.200.3012.01.707.00
U0.051.121.791.11----1.003.702.201.30
Hf/Sm--0.110.100.103.333.331.67------
Nb/La--0.100.050.040.030.030.03------
Th/La--0.090.060.04--0.010.01------
ΣREE--18.824.530.139.946.844.1------
LREE--16.021.527.136.943.541.1------
HREE--2.782.932.932.993.323.03------
LREE/HREE--5.767.359.2612.313.113.6------
LaN/YbN--9.809.3914.918.917.721.6------
δEu--0.981.111.982.372.371.42------
δCe--0.710.780.850.080.110.14------
-- indicates that it did not reach the detection limit.
Table 4. Antimony contents of strata in the Damushan district [19].
Table 4. Antimony contents of strata in the Damushan district [19].
PositionAntimony ContentCrustal Antimony Abundance Value
Lengjiaxi Formation11 ppm0.2 ppm
Nantuo Formation28 ppm
Liantuo Formation23 ppm
Doushantuo Formation47 ppm
Laobao Formation39 ppm
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Liu, Y.; Wang, D.; Huang, R.; Wang, G.; Wan, W.; Kong, Y. Distribution and Enrichment Mechanisms of Selenium in Stibnite from the Xujiashan Sb Deposit, Hubei Province, China. Minerals 2024, 14, 684. https://doi.org/10.3390/min14070684

AMA Style

Liu Y, Wang D, Huang R, Wang G, Wan W, Kong Y. Distribution and Enrichment Mechanisms of Selenium in Stibnite from the Xujiashan Sb Deposit, Hubei Province, China. Minerals. 2024; 14(7):684. https://doi.org/10.3390/min14070684

Chicago/Turabian Style

Liu, Yuhang, Dazhao Wang, Ruolong Huang, Guanzhi Wang, Wei Wan, and Yu Kong. 2024. "Distribution and Enrichment Mechanisms of Selenium in Stibnite from the Xujiashan Sb Deposit, Hubei Province, China" Minerals 14, no. 7: 684. https://doi.org/10.3390/min14070684

APA Style

Liu, Y., Wang, D., Huang, R., Wang, G., Wan, W., & Kong, Y. (2024). Distribution and Enrichment Mechanisms of Selenium in Stibnite from the Xujiashan Sb Deposit, Hubei Province, China. Minerals, 14(7), 684. https://doi.org/10.3390/min14070684

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop