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<front>
<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Earth Sci.</journal-id>
<journal-title>Frontiers in Earth Science</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Earth Sci.</abbrev-journal-title>
<issn pub-type="epub">2296-6463</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="publisher-id">1104631</article-id>
<article-id pub-id-type="doi">10.3389/feart.2023.1104631</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Earth Science</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>Trace element composition and genesis mechanism of the Fuli Pb-Zn deposit in Yunnan: LA-ICP-MS and <italic>in situ</italic> S-Pb isotopic constraints</article-title>
<alt-title alt-title-type="left-running-head">Liang et al.</alt-title>
<alt-title alt-title-type="right-running-head">
<ext-link ext-link-type="uri" xlink:href="https://doi.org/10.3389/feart.2023.1104631">10.3389/feart.2023.1104631</ext-link>
</alt-title>
</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname>Liang</surname>
<given-names>Xingyu</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/2079314/overview"/>
</contrib>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Li</surname>
<given-names>Bo</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Zhang</surname>
<given-names>Xinyue</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Qin</surname>
<given-names>Huaikun</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Li</surname>
<given-names>Gao</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Zhang</surname>
<given-names>Chengnan</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
</contrib>
</contrib-group>
<aff id="aff1">
<sup>1</sup>
<institution>Faculty of Land Resource Engineering</institution>, <institution>Kunming University of Science and Technology</institution>, <addr-line>Kunming</addr-line>, <country>China</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Kunming Geological Prospecting Institute</institution>, <institution>China Metallurgical Geological Bureau</institution>, <addr-line>Kunming</addr-line>, <country>China</country>
</aff>
<aff id="aff3">
<sup>3</sup>
<institution>Fuli Lead-Zinc Mine Co., Ltd.</institution>, <addr-line>Fuyuan</addr-line>, <country>China</country>
</aff>
<aff id="aff4">
<sup>4</sup>
<institution>Yunnan Tin Industry Group (Holding) Company Limted R&#x26;D Center</institution>, <addr-line>Kunming</addr-line>, <country>China</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>
<bold>Edited by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/2045112/overview">Antonio Simonetti</ext-link>, University of Notre Dame, United States</p>
</fn>
<fn fn-type="edited-by">
<p>
<bold>Reviewed by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/1987173/overview">Sean McClenaghan</ext-link>, Trinity College Dublin, Ireland</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/958594/overview">Wei Chen</ext-link>, China University of Geosciences Wuhan, China</p>
</fn>
<corresp id="c001">&#x2a;Correspondence: Bo Li, <email>libo1964@sina.com</email>
</corresp>
<fn fn-type="other">
<p>This article was submitted to Geochemistry, a section of the journal Frontiers in Earth Science</p>
</fn>
</author-notes>
<pub-date pub-type="epub">
<day>10</day>
<month>03</month>
<year>2023</year>
</pub-date>
<pub-date pub-type="collection">
<year>2023</year>
</pub-date>
<volume>11</volume>
<elocation-id>1104631</elocation-id>
<history>
<date date-type="received">
<day>21</day>
<month>11</month>
<year>2022</year>
</date>
<date date-type="accepted">
<day>28</day>
<month>02</month>
<year>2023</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2023 Liang, Li, Zhang, Qin, Li and Zhang.</copyright-statement>
<copyright-year>2023</copyright-year>
<copyright-holder>Liang, Li, Zhang, Qin, Li and Zhang</copyright-holder>
<license xlink:href="http://creativecommons.org/licenses/by/4.0/">
<p>This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.</p>
</license>
</permissions>
<abstract>
<p>The Fuli Pb-Zn deposit in Yunnan is located in the southeast of the Sichuan-Yunnan-Guizhou (SYG) Pb-Zn metallogenic province in South China. Lead and zinc reserves total approximately 0.3 million tons with an average grade of 18.68% Pb&#x2b;Zn. The stratiform ore occurs in the interlayer fracture zone of the middle Permian Yangxin formation dolomite. The main sulfides of the Fuli Pb-Zn deposit consist of sphalerite, galena, and pyrite, while dolomite and calcite are the main gangue minerals. Mineralization exhibits massive, disseminated, vein and breccia textures. Sphalerites of two colors (black and red) have been identified in the Fuli deposit. LA-ICP-MS analysis revealed that the black and red sphalerites were enriched in Cd, Cu, Ga, and Ge and depleted in Fe, Mn, and In to varying degrees. The aforementioned elements exhibit homogeneous patterns in the LA-ICPMS time resolution profiles, which is consistent with variations in the concentrations of major elements like Zn and S. This indicates that these elements may occur in sphalerite as a result of isomorphous substitution. However, elements such as As, Sb, Pb, and Ag fluctuate greatly in the LA-ICPMS time resolution profiles, suggesting that these elements may exist as fine inclusions. Thus, the different colors of the Fuli sphalerite may be attributed to various elements such as Ni, Cu, and Ga; Ni and Cu result in purple Sp, Cu renders sphalerite red, and Ga imparts a yellow color. The sulfur isotope compositions of the two sphalerites exhibit little variation, with &#x3b4;<sup>34</sup>S values ranging from 15.57&#x2030; to 16.91&#x2030;, indicating the enrichment of <sup>34</sup>S. These results are consistent with the sulfur isotopic compositions of Permian marine sulfates, indicating that thermochemical sulfate reduction was the main source of the reduced sulfur in the hydrothermal fluids. <italic>In situ</italic> Pb isotopic composition analysis revealed <sup>208</sup>Pb/<sup>204</sup>Pb, <sup>207</sup>Pb/<sup>204</sup>Pb, and <sup>206</sup>Pb/<sup>204</sup>Pb values for galena in the range of 38.5&#x2013;38.651, 15.666&#x2013;15.733, and 18.539&#x2013;19.124, respectively. The <italic>in situ</italic> Pb isotopic ratios of most galenas plot on the field of the basement metamorphic rocks of the Kunyang Group. These <italic>in situ</italic> Pb isotopic signatures reveal that the metallogenic metals are mainly derived from crustal basement. The findings of this study suggest that the Fuli Pb-Zn deposit is a MVT Pb-Zn deposit controlled by the interlayer compressional structure with characteristics of carbonate-hosted, epigenetic, simple mineral symbiosis, high Pb-Zn grade, and abundant Cd, Ga, and Ge along with other dispersed elements.</p>
</abstract>
<kwd-group>
<kwd>LA-MC-ICPMS</kwd>
<kwd>
<italic>in situ</italic> S-Pb isotopic</kwd>
<kwd>genesis mechanism</kwd>
<kwd>isotope geochemistry</kwd>
<kwd>sichuan-yunnan-guizhou Pb-Zn metallogenic province</kwd>
</kwd-group>
</article-meta>
</front>
<body>
<sec id="s1">
<title>1 Introduction</title>
<p>In the southwestern block of the Yangtze craton, South China, the Sichuan-Yunnan-Guizhou (SYG) metallogenic province hosts world-class carbonate-hosted Pb-Zn deposits, which are mostly associated with low-temperature fluids (&#x3c;300&#xb0;C) (<xref ref-type="bibr" rid="B15">Huang et al., 2011</xref>; <xref ref-type="bibr" rid="B12">Hu et al., 2017</xref>; <xref ref-type="bibr" rid="B52">Zhou et al., 2018b</xref>). The Pb-Zn deposits in this area mainly occur in a range of carbonate rocks from the Neoproterozoic Sinian Dengying Formation to the Late Paleozoic Permian Yangxin Formation. These deposits are characterized by high Pb and Zn grades along with enrichment in Cd, Ge, Ga, etc. Mineralization, which is generally structurally controlled by faults and folds, is interpreted as epigenetic and controlled by the fault&#x2013;fold structural system (<xref ref-type="bibr" rid="B50">Zhou et al., 2015</xref>; <xref ref-type="bibr" rid="B51">2018a</xref>; <xref ref-type="bibr" rid="B17">Jin et al., 2016</xref>; <xref ref-type="bibr" rid="B23">Li, 2016</xref>; <xref ref-type="bibr" rid="B8">Cui et al., 2018</xref>).</p>
<p>The Fuli Pb-Zn deposit is located in the southeast of the SYG Pb-Zn metallogenic province (<xref ref-type="fig" rid="F1">Figure 1</xref>). The orebody is stratiform and occurs in the Interlayered Fracture zone of Middle Permian Yangxin Formation Dolomite. There are few studies and reports available on this deposit. Sphalerite is the primary mineral of the Pb-Zn deposit, and it contains numerous trace elements, including Au, Ag, Cu, As, and Sb, as well as scattered elements such as Ge, Cd, Se, Te, and Tl, providing rich geochemical information (<xref ref-type="bibr" rid="B10">Fleet et al., 1993</xref>; <xref ref-type="bibr" rid="B36">Tu et al., 2003</xref>; <xref ref-type="bibr" rid="B39">Xu et al., 2014</xref>; <xref ref-type="bibr" rid="B37">Wei et al., 2019</xref>; <xref ref-type="bibr" rid="B38">2021</xref>, 221). Isotope analyses are an effective way to trace the sources of ore-forming materials and is widely used to study the genesis of ore deposits; however, the origins revealed by single isotopes are often contradictory, and the mutual restriction of multi-isotope systems has become a development trend (<xref ref-type="bibr" rid="B16">Huang et al., 2004</xref>; <xref ref-type="bibr" rid="B57">Zhou et al., 2013d</xref>). Studying the trace elements and S and Pb isotopic compositions of sphalerite can not only reveal the sources of ore-forming materials, but also indicate the compositions of fluids and the geneses of ore deposits (<xref ref-type="bibr" rid="B2">Barker et al., 2009</xref>; <xref ref-type="bibr" rid="B43">Ye et al., 2011</xref>; <xref ref-type="bibr" rid="B17">Jin et al., 2016</xref>; <xref ref-type="bibr" rid="B9">Deng et al., 2017</xref>). LA-ICP-MS <italic>in situ</italic> analysis has advantages over traditional trace element analysis because it overcomes the problem of sample bias and dilution caused by sample selection. Moreover, LA-ICP-MS can efficiently determine the spatial distributions of trace elements in samples.</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>
<bold>(A)</bold> A map showing the location of the SYG metallogenic province. <bold>(B)</bold> Geological framework of Southwestern China. <bold>(C)</bold> Geological map showing the distribution of the Pb-Zn deposits and Emeishan Flood basalt of the SYG metallogenic province, and the location of the Fuli deposit in the region.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g001.tif"/>
</fig>
<p>In this paper, LA-MC-ICP MS is used to determine the compositions of trace elements <italic>in situ</italic> along with the enrichment regularity of scattered elements and the S and Pb isotopes in the Fuli Pb-Zn deposit. The compositions and distributions of trace elements and scattered elements in sphalerite and the source of the ore-forming materials are discussed. The findings improve our understanding of the mineralization of ore deposits in the study region and provide a new theoretical basis for determining the genesis of Pb-Zn deposits.</p>
</sec>
<sec id="s2">
<title>2 Geological setting</title>
<sec id="s2-1">
<title>2.1 Tectonic features of the fuli district</title>
<p>The Fuli Pb-Zn deposit is located 32&#xa0;km southeast of Fuyuan County, Yunnan Province. It is controlled by the Qujing fault and a secondary splay of the Mile-Shizong fault (<xref ref-type="fig" rid="F1">Figure 1</xref>). In the study region, the Kunyang Group is exposed as the basement; however, sediments from the Sinian to Silurian are missing above the Kunyang Group. This area exhibits three distinct types of structural belts: NS trending, NE trending, and NW trendingFollowing the Jinning, Caledonian, and Hercynian movements, the structures in this region are primarily north-south in orientation, followed by structures of a northeastern orientation. The NW-trending structures developed rapidly during the Yanshan-Himalayan tectonic movement and gradually formed the present-day north-south oriented structures, follow by the NE-trending structure and NW-trending structure. The structures that are oriented north-south and north-east play an essential role in determining the formation of Pb-Zn deposits, as well as their distribution and enrichment, in this region.</p>
<p>This region&#x2019;s geology is primarily determined by the Maitreya-Shizong fault. Several gentle anticlines, synclines, and reverse fault structures with a severe dip are dispersed across the mining area. Together, the Erle and Xinjuntai anticlines make up the principal fold structure in this region. The distribution of regional strata, secondary structures, and mineralization is governed by both faults and anticlines.</p>
<p>Among the approximate NS trending, NE trending and approximate EW trending structures developed in the mining area, the near NS trending faults have a large scale, which is a multi-stage active regional fault and an important ore fluid transporting structure, while the EW trending faults are small in scale and mostly secondary structures, mainly post-metallogenic structures. The NE trending faults are mainly ore-controlling structures, and a series of extensional fissures and interlayer fracture zones are produced in the strata of the middle Yangxin formation (P<sub>2</sub>y<sup>2</sup>), which provides a favorable structural trap for the emplacement of the Fuli Pb-Zn orebody. The orebodies mainly occur in these fissures and interlayer fracture zones (<xref ref-type="bibr" rid="B32">Ren et al., 2019</xref>).</p>
</sec>
<sec id="s2-2">
<title>2.2 Deposit geology</title>
<p>The study area suffered transgression cycles in the early and middle Permian, forming extremely thick carbonate strata. The exposed strata in the mining area are distributed along a N-S trend direction (<xref ref-type="fig" rid="F2">Figure 2A</xref>). From oldest to youngest, the host strata are as follows: interbeds of limestone and dolomite of the Middle Permian Yangxin Formation (P<sub>2</sub>y), Upper Permian Emeishan basalt (P<sub>2</sub>&#x3b2;), Upper Permian calcareous and argillaceous shale of the Xuanwei Formation (P<sub>3</sub>x), yellow brown mudstone and Lower Triassic shale of the Feixianguan Formation (T<sub>1</sub>f), and argillaceous dolomite and limestone of the Yongningzhen Formation (T<sub>1</sub>y). Mudstone and dolomite of Middle Triassic Guanling Formation (T<sub>2</sub>g<sup>1</sup>). The Yangxin Formation of the Middle Permian is the main deposit-bearing stratum. At present, two orebodies have been found in the Fuli Pb-Zn deposit: they mainly occur in dolomitic limestone, the orebodies are controlled by strata, and the metal content of zinc is the highest, with lead contents subordinate to zinc. It is approximately 320&#xa0;m long, 210&#xa0;m wide, and 1.2&#xa0;m thick, with a SE dip of 15&#xb0;. The orebody has the characteristics of being of greater thickness in the middle and thin at both ends. Shallow parts of the orebody are thin and the metal content are low, becoming thicker with higher Zn-Pb grades at depth (<xref ref-type="fig" rid="F2">Figure 2B</xref>).</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>
<bold>(A)</bold> Geological map of the Fuli Pb&#x2212;Zn deposit showing the structure and the A-B cross-section. <bold>(B)</bold> A-B Cross-section of the Fuli deposit through the Fuli deposit showing the ore body, structure and strata.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g002.tif"/>
</fig>
<p>Through examination of geological characteristics and the microscopic observation of mineral associations, the genesis of the Fuli lead-zinc deposit can be separated into three phases: the early-mineralization stage, the syn-mineralization stage, and the post-mineralization stage (<xref ref-type="fig" rid="F3">Figures 3</xref>, <xref ref-type="fig" rid="F4">4</xref>):<list list-type="simple">
<list-item>
<p>1) Early-mineralization period: The main feature of the ore is characterized by two distinct types of hydrothermal dolomitization in the early-mineralization period: Dol-1 and Dol-2. The Dol-1 dolomite appears as grey-black, fine-grained xenomorphic granules and often cemented by ore-forming grey dolomite (<xref ref-type="fig" rid="F3">Figure 3D</xref>). The Dol-2 dolomite has a euhedral white core and a dark grey-grey edge with coarse particles. Sphalerite and galena are found as bulk or disseminated replacements in the dolomite (<xref ref-type="fig" rid="F3">Figures 3C, F</xref>).</p>
</list-item>
<list-item>
<p>2) Syn-mineralization period: The occurrence of minerals formed in the syn-mineralization period is consistent with that of the strata and developed in the interlayer fracture zone. The main minerals are sphalerite in massive, vein or disseminated forms, and galena as cubic crystal. In general, the sulfides have a granular texture (<xref ref-type="fig" rid="F5">Figure 5A, B, E</xref>), metasomatic texture (<xref ref-type="fig" rid="F5">Figures 5C, D, F</xref>), and some have formed massive structures, disseminated structures (<xref ref-type="fig" rid="F3">Figure 3A</xref>), breccia structures (<xref ref-type="fig" rid="F3">Figure 3B</xref>), and vein structures (<xref ref-type="fig" rid="F3">Figure 3E</xref>). At this stage, the sphalerite is predominantly reddish-brown to brown-black, and its crystals are predominantly euhedral and anhedral.</p>
</list-item>
<list-item>
<p>3) Post-mineralization period: The euhedral calcite (Cal-5) is a gangue mineral generated in the post-mineralization stage. It is in the shape of a coarse vein and envelops sphalerite and galena in the syn-mineralization stage. (<xref ref-type="fig" rid="F3">Figures 3B,E</xref>).</p>
</list-item>
</list>
</p>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>Photographs of field and specimens from the Fuli Pb-Zn deposit. <bold>(A, B)</bold> Bulk Sp and/or Gn are cemented by Dol/Cal veins. <bold>(C)</bold> Massive black sphalerite. <bold>(D)</bold> Massive red sphalerite. <bold>(E)</bold> Black sphalerite veins filled in dolomite fissures. <bold>(F)</bold> Black sphalerite breccia in hydrothermal dolomite vein.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g003.tif"/>
</fig>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>Paragenesis sequence of minerals in the Fuli Pb-Zn deposit.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g004.tif"/>
</fig>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>Sulfide mineral textures and structures from the Fuli Pb-Zn deposit. <bold>(A)</bold> Dolomite coexists with sphalerite. <bold>(B)</bold> Sphalerite with a granular structure. <bold>(C, D)</bold> Galena metasomatic pyrite and/or tetrahedrite. <bold>(E)</bold> Pyrite and chalcopyrite observed as bulk or disseminated in the dolomite <bold>(F)</bold> Metasomatic relict pyrite and xeno-morphic sphalerite in anhedral sphalerite fracture.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g005.tif"/>
</fig>
</sec>
</sec>
<sec sec-type="methods" id="s3">
<title>3 Methods</title>
<sec id="s3-1">
<title>3.1 LA-ICP-MS elemental measurement</title>
<p>LA-ICP-MS was used to analyze the trace elements in minerals at Wuhan Sample Solution Analytical Technology Co., Ltd. (Wuhan, China). The operating conditions and data reduction for the laser system and the ICP-MS instrument were the same as described in (<xref ref-type="bibr" rid="B58">Zong et al., 2017</xref>). A GeolasPro laser ablation system was used to perform the sampling, which comprises a COMPexPro 102 ArF excimer laser (wavelength of 193&#xa0;nm, maximum energy of 200&#xa0;mJ) and a MicroLas optical system. For the acquisition of ion signal intensities, an Agilent 7700e ICP-MS instrument was utilized. In this experiment, helium was used as a carrier gas. The make-up gas was argon, which was mixed with the carrier gas <italic>via</italic> a T-connector prior to entering the ICP system. A &#x201c;wire&#x201d; signal-smoothing device was included in the laser ablation system (<xref ref-type="bibr" rid="B14">Hu et al., 2015</xref>). A spot size of 44 microns, a fluence of 5&#xa0;J/cm<sup>2</sup> and a frequency of 5&#xa0;Hz were used for experimental conditons. The trace element compositions of sulfides were calibrated against various reference materials (NIST 610 and NIST 612) without using an internal standard (<xref ref-type="bibr" rid="B27">Liu et al., 2008</xref>). To verify the accuracy of the calibration method, a sulfide reference material (MASS-1, USGS) was used as the unknown sample. The background acquisition for each analysis was approximately 20&#x2013;30&#xa0;s, followed by the acquisition of data from the sample for 50&#xa0;s. A software program ICP-MS-DataCal v12.2 based on Excel was used to perform off-line selection and integration of the background and analyzed signals, as well as time-drift correction and quantitative calibration for the analysis of trace elements (<xref ref-type="bibr" rid="B27">Liu et al., 2008</xref>).</p>
</sec>
<sec id="s3-2">
<title>3.2 <italic>In situ</italic> sulfur isotope analysis</title>
<p>
<italic>In situ</italic> sulfur isotope analyses of sphalerite were conducted using a Neptune Plus MC-ICP-MS instrument (Thermo Fisher Scientific, Bremen, Germany) and a Geolas HD excimer ArF laser ablation system (Coherent, G&#xf6;ttingen, Germany) at Wuhan Sample Solution Analytical Technology Co., Ltd. (Hubei, China). The laser ablation system utilized helium as the carrier gas for the ablation cell, which was then mixed with argon (the makeup gas) once it had left the ablation cell. During the ablation process, the single-spot mode was employed. To counteract the downhole fractionation effect, a large spot size of 44&#xa0;&#x3bc;m and a slow pulse frequency of 2&#xa0;Hz were used, as reported by (<xref ref-type="bibr" rid="B11">Fu et al., 2016</xref>).100 laser pulses were utilized in one analysis. Signal-smoothing devices were used downstream from the sample cell to effectively eliminate short-term variations in the signal, particularly for slow pulse frequencies (<xref ref-type="bibr" rid="B14">Hu et al., 2015</xref>). The laser fluence was maintained at a constant level of 5&#xa0;J/cm<sup>2</sup>. Nine Faraday cups with 10<sup>11</sup>&#x3a9; resistors were mounted on the Neptune Plus instrument. The <sup>32</sup>S, <sup>33</sup>S, and <sup>34</sup>S isotopes were collected in Faraday cups in static mode. For improved signal intensity, the Neptune Plus instrument utilizes the newly developed X skimmer cone and Jet sample cone. To reduce polyatomic interference, nitrogen was added to the central gas flow at a rate of 4&#xa0;mL/min. Measurements were conducted at medium resolution with a revolving power of greater than 5,000, as defined by peak edge widths between 5% and 95% of peak height.</p>
<p>An instrument mass fractionation correction was conducted using standard sample bracketing (SSB). To eliminate the matrix effect, the natural pyrite, pyrrhotite, pentlandite samples, the natural chalcopyrite samples, and the natural Ag<sub>2</sub>S samples, were corrected using a pyrite standard (PPP-1), a pressed pellet chalcopyrite standard (GBW07268), and a synthetic Ag<sub>2</sub>S pressed pellet standard (IAEA-S-1), respectively. The reference values of &#x3b4;<sup>34</sup>Sv-CDT in these standards were reported by <xref ref-type="bibr" rid="B11">Fu et al. (2016)</xref>. In addition, the in-house references of a pyrrhotite (SP-Po-01, &#x3b4;<sup>34</sup>Sv-CDT &#x3d; 1.4 &#xb1; 0.4), chalcopyrite (SP-CP-01, &#x3b4;<sup>34</sup>Sv-CDT &#x3d; 5.45 &#xb1; 0.3), and two synthetic Ag2S standards (IAEA-S-2, &#x3b4;<sup>34</sup>Sv-CDT &#x3d; 22.58 &#xb1; 0.39 and IAEA-S-3, &#x3b4;<sup>34</sup>Sv-CDT &#x3d; &#x2212;32.18 &#xb1; 0.45) were analyzing repeatedly as unknown samples to verify the accuracy of the calibration method. A detailed description of the <italic>in situ</italic> analysis of the S isotopic ratios can be found in <xref ref-type="bibr" rid="B11">Fu et al. (2016)</xref>. All data reduction for the MC-ICP-MS analysis of S isotopic ratios was conducted using Iso-Compass software (<xref ref-type="bibr" rid="B47">Zhang et al., 2020</xref>).</p>
</sec>
<sec id="s3-3">
<title>3.3 <italic>In situ</italic> lead isotope analysis</title>
<p>
<italic>In situ</italic> lead isotope analyses of galena were conducted using a Neptune Plus MC-ICP-MS instrument (Thermo Fisher Scientific, Bremen, Germany) and a Geolas HD excimer ArF laser ablation system (Coherent, G&#xf6;ttingen, Germany) at Wuhan Sample Solution Analytical Technology Co., Ltd. (Hubei, China). The laser ablation system utilized helium as the carrier gas for the ablation cell, which was then mixed with argon (the makeup gas) once it had left the ablation cell. Depending on the intensity of the Pb signal, the spot diameter ranged from 44&#xa0;&#x3bc;m to 90&#xa0;&#x3bc;m. Pulses were delivered at a frequency of 8&#xa0;Hz, while laser fluence was maintained at 10&#xa0;J/cm<sup>2</sup>. To eliminate short-term variations in the signal and to remove mercury from the background aerosol particles and sample aerosol particles, a new signal-smoothing and mercury-removing device was applied downstream from the sample cell (<xref ref-type="bibr" rid="B14">Hu et al., 2015</xref>). Nine Faraday cups with 10<sup>11</sup>&#x3a9; resistors were mounted on the Neptune Plus instrument. The <sup>208</sup>Pb, <sup>207</sup>Pb, <sup>206</sup>Pb, <sup>204</sup>Pb, <sup>205</sup>TL, <sup>203</sup>TL, and <sup>202</sup>Hg isotopes were collected in the Faraday cups in static mode. Using a Tl solution that was nebulized simultaneously with the sample using an Aridus II desolving nebulizer, the mass discrimination actor for Pb was calculated. The mass fractionation of Pb isotopes was adjusted based on the exponential rule and the ratio of <sup>205</sup>TL/<sup>203</sup>TL. The optimized <sup>205</sup>TL/<sup>203</sup>TL values obtained from the calibration of 2&#xa0;Pb isotope standards MASS-1 (USGS) and Sph-HYLM (an in-house sphalerite standard), were substituted for the natural Tl isotopic composition when correcting for mass fractionation. The <sup>202</sup>Hg signal was used to correct the remaining <sup>204</sup>Hg interference on <sup>204</sup>Pb using the natural <sup>202</sup>Hg/<sup>204</sup>Hg ratio (0.2301). A normalization of <sup>205</sup>TL/<sup>203</sup>TL was performed to correct the mass fractionation of <sup>204</sup>Hg/<sup>202</sup>Hg. <sup>204</sup>Hg/<sup>202</sup>Hg and <sup>205</sup>TL/<sup>203</sup>TL are assumed to have the same mass fractionation factors in this case. The precision and accuracy of the measurements were monitored using Sph-HYLM over the course of the analysis after 10 samples had been analyzed. For <sup>208</sup>Pb/<sup>204</sup>Pb, <sup>207</sup>Pb/<sup>204</sup>Pb, and <sup>206</sup>Pb/<sup>204</sup>Pb, the achieved accuracy was judged to be equivalent to or more than 0.2&#x2030; compared to the solution value measured by MC-ICP-MS. The typical precision was 0.4&#x2030; (2&#x3c3;). <italic>In situ</italic> analysis of Pb isotopic ratios is described in more detail in (<xref ref-type="bibr" rid="B46">Zhang et al., 2016</xref>). All data reduction for the MC-ICP-MS analysis of Pb isotope ratios was conducted using Iso-Compass software (<xref ref-type="bibr" rid="B47">Zhang et al., 2020</xref>).</p>
</sec>
</sec>
<sec sec-type="results" id="s4">
<title>4 Results</title>
<sec id="s4-1">
<title>4.1 Trace elements of sphalerite</title>
<p>
<xref ref-type="table" rid="T1">Table 1</xref> summarizes the LA-ICP-MS trace element concentrations in sphalerites from the Fuli Pb-Zn deposit. <xref ref-type="fig" rid="F6">Figure 6</xref> shows a box-and-whisker graphic depicting the absolute concentration ranges for chosen elements.</p>
<table-wrap id="T1" position="float">
<label>TABLE 1</label>
<caption>
<p>Summary of LA-ICP-MS sphalerites trace element concentration (ppm) in the Fuli Pb-Zn deposit.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="left">Color</th>
<th align="center">Sample no.</th>
<th align="center">Cr</th>
<th align="center">Mn</th>
<th align="center">Fe</th>
<th align="center">Co</th>
<th align="center">Ni</th>
<th align="center">Cu</th>
<th align="center">Ga</th>
<th align="center">Ge</th>
<th align="center">As</th>
<th align="center">Se</th>
<th align="center">Ag</th>
<th align="center">Cd</th>
<th align="center">In</th>
<th align="center">Sb</th>
<th align="center">Tl</th>
<th align="center">Pb</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td rowspan="17" align="left">Black</td>
<td align="center">FL1-1-1</td>
<td align="center">0.89</td>
<td align="center">0.71</td>
<td align="center">1,224</td>
<td align="center">12.9</td>
<td align="center">2.3</td>
<td align="center">939</td>
<td align="center">5.1</td>
<td align="center">130.5</td>
<td align="center">14.5</td>
<td align="center">7.7</td>
<td align="center">13.1</td>
<td align="center">10,001</td>
<td align="center">0.26</td>
<td align="center">471</td>
<td align="center">0.22</td>
<td align="center">873</td>
</tr>
<tr>
<td align="center">FL1-1-2</td>
<td align="center">67.20</td>
<td align="center">0.64</td>
<td align="center">1,473</td>
<td align="center">13.6</td>
<td align="center">8.2</td>
<td align="center">1,238</td>
<td align="center">8.6</td>
<td align="center">563.5</td>
<td align="center">58.2</td>
<td align="center">6.9</td>
<td align="center">7.5</td>
<td align="center">7,250</td>
<td align="center">0.43</td>
<td align="center">394</td>
<td align="center">0.67</td>
<td align="center">1,574</td>
</tr>
<tr>
<td align="center">FL1-1-3</td>
<td align="center">0.27</td>
<td align="center">1.49</td>
<td align="center">1,360</td>
<td align="center">13.2</td>
<td align="center">6.6</td>
<td align="center">1,377</td>
<td align="center">6.8</td>
<td align="center">277.2</td>
<td align="center">117.0</td>
<td align="center">11.0</td>
<td align="center">3.0</td>
<td align="center">8,628</td>
<td align="center">0.41</td>
<td align="center">347</td>
<td align="center">0.32</td>
<td align="center">243</td>
</tr>
<tr>
<td align="center">FL1-1-4</td>
<td align="center">15.16</td>
<td align="center">1.73</td>
<td align="center">1,504</td>
<td align="center">3.2</td>
<td align="center">11.8</td>
<td align="center">2,114</td>
<td align="center">553.3</td>
<td align="center">539.8</td>
<td align="center">86.1</td>
<td align="center">7.2</td>
<td align="center">18.7</td>
<td align="center">13,354</td>
<td align="center">3.33</td>
<td align="center">1,469</td>
<td align="center">1.14</td>
<td align="center">1,347</td>
</tr>
<tr>
<td align="center">FL1-1-5</td>
<td align="center">1.09</td>
<td align="center">0.53</td>
<td align="center">1,455</td>
<td align="center">9.8</td>
<td align="center">0.6</td>
<td align="center">814</td>
<td align="center">2.2</td>
<td align="center">351.0</td>
<td align="center">25.6</td>
<td align="center">1.1</td>
<td align="center">1.9</td>
<td align="center">4,614</td>
<td align="center">0.05</td>
<td align="center">93</td>
<td align="center">0.03</td>
<td align="center">41</td>
</tr>
<tr>
<td align="center">FL1-1-6</td>
<td align="center">7.62</td>
<td align="center">0.76</td>
<td align="center">1708</td>
<td align="center">9.2</td>
<td align="center">0.3</td>
<td align="center">146</td>
<td align="center">2.5</td>
<td align="center">20.6</td>
<td align="center">20.0</td>
<td align="center">0.0</td>
<td align="center">1.2</td>
<td align="center">7,786</td>
<td align="center">1.02</td>
<td align="center">55</td>
<td align="center">0.11</td>
<td align="center">2,911</td>
</tr>
<tr>
<td align="center">FL1-1-7</td>
<td align="center">0.82</td>
<td align="center">1.05</td>
<td align="center">2,431</td>
<td align="center">7.8</td>
<td align="center">1.0</td>
<td align="center">272</td>
<td align="center">13.2</td>
<td align="center">117.9</td>
<td align="center">20.4</td>
<td align="center">0.0</td>
<td align="center">0.4</td>
<td align="center">3,742</td>
<td align="center">0.03</td>
<td align="center">16</td>
<td align="center">0.02</td>
<td align="center">20</td>
</tr>
<tr>
<td align="center">FL2-1-1</td>
<td align="center">3.34</td>
<td align="center">0.83</td>
<td align="center">1840</td>
<td align="center">11.6</td>
<td align="center">2.7</td>
<td align="center">1,210</td>
<td align="center">647.2</td>
<td align="center">160.1</td>
<td align="center">25.7</td>
<td align="center">13.3</td>
<td align="center">4.1</td>
<td align="center">7,835</td>
<td align="center">1.52</td>
<td align="center">214</td>
<td align="center">0.10</td>
<td align="center">49</td>
</tr>
<tr>
<td align="center">FL2-1-2</td>
<td align="center">1.63</td>
<td align="center">0.80</td>
<td align="center">1,363</td>
<td align="center">9.2</td>
<td align="center">0.7</td>
<td align="center">1,396</td>
<td align="center">36.9</td>
<td align="center">463.4</td>
<td align="center">96.9</td>
<td align="center">0.0</td>
<td align="center">6.2</td>
<td align="center">5,247</td>
<td align="center">0.39</td>
<td align="center">400</td>
<td align="center">0.05</td>
<td align="center">135</td>
</tr>
<tr>
<td align="center">FL2-1-3</td>
<td align="center">0.72</td>
<td align="center">0.78</td>
<td align="center">1781</td>
<td align="center">9.0</td>
<td align="center">0.8</td>
<td align="center">309</td>
<td align="center">10.9</td>
<td align="center">76.8</td>
<td align="center">32.6</td>
<td align="center">11.8</td>
<td align="center">3.8</td>
<td align="center">6,791</td>
<td align="center">0.10</td>
<td align="center">125</td>
<td align="center">0.01</td>
<td align="center">51</td>
</tr>
<tr>
<td align="center">FL2-1-4</td>
<td align="center">1.18</td>
<td align="center">0.00</td>
<td align="center">2082</td>
<td align="center">10.4</td>
<td align="center">0.7</td>
<td align="center">3,391</td>
<td align="center">673.9</td>
<td align="center">262.1</td>
<td align="center">254.8</td>
<td align="center">0.0</td>
<td align="center">69.8</td>
<td align="center">9,386</td>
<td align="center">0.32</td>
<td align="center">2019</td>
<td align="center">0.31</td>
<td align="center">557</td>
</tr>
<tr>
<td align="center">FL2-1-5</td>
<td align="center">1.24</td>
<td align="center">0.46</td>
<td align="center">1,194</td>
<td align="center">10.0</td>
<td align="center">0.6</td>
<td align="center">292</td>
<td align="center">69.1</td>
<td align="center">60.1</td>
<td align="center">14.4</td>
<td align="center">0.0</td>
<td align="center">2.4</td>
<td align="center">5,783</td>
<td align="center">0.21</td>
<td align="center">99</td>
<td align="center">0.05</td>
<td align="center">27</td>
</tr>
<tr>
<td align="center">FL2-1-6</td>
<td align="center">9.15</td>
<td align="center">0.00</td>
<td align="center">2,344</td>
<td align="center">11.0</td>
<td align="center">0.9</td>
<td align="center">825</td>
<td align="center">309.3</td>
<td align="center">80.2</td>
<td align="center">55.0</td>
<td align="center">0.0</td>
<td align="center">14.5</td>
<td align="center">17,475</td>
<td align="center">2.00</td>
<td align="center">296</td>
<td align="center">0.15</td>
<td align="center">53</td>
</tr>
<tr>
<td align="center">FL2-1-7</td>
<td align="center">2.04</td>
<td align="center">0.85</td>
<td align="center">2,279</td>
<td align="center">11.3</td>
<td align="center">0.8</td>
<td align="center">614</td>
<td align="center">73.7</td>
<td align="center">50.3</td>
<td align="center">66.1</td>
<td align="center">2.9</td>
<td align="center">34.0</td>
<td align="center">8,384</td>
<td align="center">0.07</td>
<td align="center">389</td>
<td align="center">0.12</td>
<td align="center">131</td>
</tr>
<tr>
<td align="center">FL2-1-8</td>
<td align="center">1.80</td>
<td align="center">1.68</td>
<td align="center">2,540</td>
<td align="center">11.1</td>
<td align="center">1.2</td>
<td align="center">1,401</td>
<td align="center">415.9</td>
<td align="center">89.4</td>
<td align="center">94.4</td>
<td align="center">13.8</td>
<td align="center">27.4</td>
<td align="center">16,174</td>
<td align="center">0.24</td>
<td align="center">798</td>
<td align="center">0.12</td>
<td align="center">353</td>
</tr>
<tr>
<td align="center">FL2-1-9</td>
<td align="center">1.85</td>
<td align="center">0.77</td>
<td align="center">1888</td>
<td align="center">10.7</td>
<td align="center">0.9</td>
<td align="center">683</td>
<td align="center">29.1</td>
<td align="center">140.6</td>
<td align="center">72.5</td>
<td align="center">15.5</td>
<td align="center">15.0</td>
<td align="center">6,955</td>
<td align="center">0.01</td>
<td align="center">322</td>
<td align="center">0.06</td>
<td align="center">139</td>
</tr>
<tr>
<td align="center">FL2-1-10</td>
<td align="center">1.38</td>
<td align="center">0.00</td>
<td align="center">2066</td>
<td align="center">9.8</td>
<td align="center">0.9</td>
<td align="center">634</td>
<td align="center">8.7</td>
<td align="center">182.6</td>
<td align="center">59.6</td>
<td align="center">0.0</td>
<td align="center">7.4</td>
<td align="center">8,182</td>
<td align="center">0.00</td>
<td align="center">199</td>
<td align="center">0.02</td>
<td align="center">121</td>
</tr>
<tr>
<td rowspan="14" align="left">Red</td>
<td align="center">FL1-3-1</td>
<td align="center">1.67</td>
<td align="center">0.98</td>
<td align="center">2031</td>
<td align="center">9.8</td>
<td align="center">0.9</td>
<td align="center">808</td>
<td align="center">6.6</td>
<td align="center">219.7</td>
<td align="center">76.1</td>
<td align="center">8.7</td>
<td align="center">7.8</td>
<td align="center">11,015</td>
<td align="center">0.01</td>
<td align="center">312</td>
<td align="center">0.01</td>
<td align="center">88</td>
</tr>
<tr>
<td align="center">FL1-3-2</td>
<td align="center">0.91</td>
<td align="center">0.74</td>
<td align="center">1,675</td>
<td align="center">9.7</td>
<td align="center">0.6</td>
<td align="center">946</td>
<td align="center">84.9</td>
<td align="center">230.1</td>
<td align="center">72.0</td>
<td align="center">0.0</td>
<td align="center">7.0</td>
<td align="center">8,004</td>
<td align="center">0.33</td>
<td align="center">379</td>
<td align="center">0.03</td>
<td align="center">167</td>
</tr>
<tr>
<td align="center">FL1-3-3</td>
<td align="center">0.76</td>
<td align="center">0.56</td>
<td align="center">1,436</td>
<td align="center">8.9</td>
<td align="center">0.7</td>
<td align="center">17</td>
<td align="center">3.3</td>
<td align="center">3.8</td>
<td align="center">0.6</td>
<td align="center">15.1</td>
<td align="center">0.4</td>
<td align="center">6,126</td>
<td align="center">0.01</td>
<td align="center">2</td>
<td align="center">0.00</td>
<td align="center">1</td>
</tr>
<tr>
<td align="center">FL1-3-4</td>
<td align="center">0.00</td>
<td align="center">0.00</td>
<td align="center">1,693</td>
<td align="center">9.9</td>
<td align="center">0.6</td>
<td align="center">103</td>
<td align="center">4.1</td>
<td align="center">18.5</td>
<td align="center">9.4</td>
<td align="center">0.0</td>
<td align="center">2.3</td>
<td align="center">5,532</td>
<td align="center">0.00</td>
<td align="center">51</td>
<td align="center">0.02</td>
<td align="center">12</td>
</tr>
<tr>
<td align="center">FL1-3-5</td>
<td align="center">1.87</td>
<td align="center">1.28</td>
<td align="center">2,706</td>
<td align="center">8.7</td>
<td align="center">1.1</td>
<td align="center">32</td>
<td align="center">0.7</td>
<td align="center">0.6</td>
<td align="center">14.3</td>
<td align="center">12.5</td>
<td align="center">0.6</td>
<td align="center">17,485</td>
<td align="center">0.64</td>
<td align="center">8</td>
<td align="center">0.14</td>
<td align="center">5</td>
</tr>
<tr>
<td align="center">FL1-3-6</td>
<td align="center">3.99</td>
<td align="center">0.96</td>
<td align="center">2,896</td>
<td align="center">8.9</td>
<td align="center">1.3</td>
<td align="center">79</td>
<td align="center">0.0</td>
<td align="center">0.2</td>
<td align="center">0.0</td>
<td align="center">0.0</td>
<td align="center">1.9</td>
<td align="center">19,370</td>
<td align="center">0.02</td>
<td align="center">3</td>
<td align="center">0.00</td>
<td align="center">13</td>
</tr>
<tr>
<td align="center">FL16-1-1</td>
<td align="center">1.10</td>
<td align="center">0.86</td>
<td align="center">2,412</td>
<td align="center">10.4</td>
<td align="center">1.1</td>
<td align="center">96</td>
<td align="center">48.0</td>
<td align="center">3.8</td>
<td align="center">3.1</td>
<td align="center">30.4</td>
<td align="center">1.5</td>
<td align="center">15,919</td>
<td align="center">0.01</td>
<td align="center">42</td>
<td align="center">0.00</td>
<td align="center">15</td>
</tr>
<tr>
<td align="center">FL16-1-2</td>
<td align="center">1.50</td>
<td align="center">1.39</td>
<td align="center">2,117</td>
<td align="center">10.5</td>
<td align="center">1.0</td>
<td align="center">141</td>
<td align="center">92.5</td>
<td align="center">9.1</td>
<td align="center">4.1</td>
<td align="center">10.1</td>
<td align="center">1.3</td>
<td align="center">25,238</td>
<td align="center">0.01</td>
<td align="center">49</td>
<td align="center">0.00</td>
<td align="center">26</td>
</tr>
<tr>
<td align="center">FL16-1-3</td>
<td align="center">1.78</td>
<td align="center">0.00</td>
<td align="center">1,166</td>
<td align="center">13.3</td>
<td align="center">0.4</td>
<td align="center">114</td>
<td align="center">40.6</td>
<td align="center">18.8</td>
<td align="center">22.8</td>
<td align="center">0.0</td>
<td align="center">0.8</td>
<td align="center">5,633</td>
<td align="center">0.60</td>
<td align="center">3</td>
<td align="center">0.04</td>
<td align="center">4</td>
</tr>
<tr>
<td align="center">FL16-1-4</td>
<td align="center">1.15</td>
<td align="center">1.08</td>
<td align="center">1,662</td>
<td align="center">11.9</td>
<td align="center">0.8</td>
<td align="center">2</td>
<td align="center">0.1</td>
<td align="center">0.4</td>
<td align="center">0.5</td>
<td align="center">0.0</td>
<td align="center">0.1</td>
<td align="center">16,152</td>
<td align="center">0.00</td>
<td align="center">1</td>
<td align="center">0.00</td>
<td align="center">1</td>
</tr>
<tr>
<td align="center">FL16-1-5</td>
<td align="center">0.61</td>
<td align="center">2.95</td>
<td align="center">1984</td>
<td align="center">12.6</td>
<td align="center">2.4</td>
<td align="center">975</td>
<td align="center">8.2</td>
<td align="center">3.4</td>
<td align="center">3.9</td>
<td align="center">10.5</td>
<td align="center">0.7</td>
<td align="center">10,701</td>
<td align="center">0.13</td>
<td align="center">179</td>
<td align="center">0.13</td>
<td align="center">44</td>
</tr>
<tr>
<td align="center">FL16-1-6</td>
<td align="center">3.58</td>
<td align="center">1.99</td>
<td align="center">1767</td>
<td align="center">13.3</td>
<td align="center">2.7</td>
<td align="center">647</td>
<td align="center">2.6</td>
<td align="center">4.3</td>
<td align="center">13.6</td>
<td align="center">10.6</td>
<td align="center">1.3</td>
<td align="center">7,617</td>
<td align="center">0.15</td>
<td align="center">79</td>
<td align="center">0.12</td>
<td align="center">28</td>
</tr>
<tr>
<td align="center">FL16-1-7</td>
<td align="center">0.43</td>
<td align="center">3.79</td>
<td align="center">1,553</td>
<td align="center">12.4</td>
<td align="center">3.5</td>
<td align="center">852</td>
<td align="center">3.3</td>
<td align="center">39.4</td>
<td align="center">1.0</td>
<td align="center">13.6</td>
<td align="center">0.8</td>
<td align="center">8,619</td>
<td align="center">0.98</td>
<td align="center">95</td>
<td align="center">0.22</td>
<td align="center">109</td>
</tr>
<tr>
<td align="center">FL16-1-8</td>
<td align="center">1.34</td>
<td align="center">2.36</td>
<td align="center">1,278</td>
<td align="center">0.8</td>
<td align="center">1.8</td>
<td align="center">2,176</td>
<td align="center">582.3</td>
<td align="center">24.1</td>
<td align="center">6.2</td>
<td align="center">20.8</td>
<td align="center">1.7</td>
<td align="center">16,796</td>
<td align="center">0.85</td>
<td align="center">173</td>
<td align="center">0.40</td>
<td align="center">180</td>
</tr>
<tr>
<td colspan="18" align="left">Measured concentrations (ppm)</td>
</tr>
</tbody>
</table>
</table-wrap>
<fig id="F6" position="float">
<label>FIGURE 6</label>
<caption>
<p>Box diagrams illustrating the concentration of trace elements in sphalerites from the Fuli Pb-Zn deposit.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g006.tif"/>
</fig>
</sec>
<sec id="s4-2">
<title>4.2 Enrichment of Cu, Cd, Ge, and Ga</title>
<p>The contents of Cu, Cd, Ge, and Ga in sphalerite in the Fuli deposit are relatively high (<xref ref-type="fig" rid="F6">Figure 6</xref>). The Cu content in the sphalerite samples ranges from 2.1 ppm to 3,390&#xa0;ppm. The black sphalerite displays a higher Cu content (146 ppm&#x2013;3390 ppm, with a mean value of 1,038&#xa0;ppm) in comparison to the red sphalerite (2.1 ppm&#x2013;2176 ppm, with a mean value of 499&#xa0;ppm). The Cd content ranges greatly from 3,742&#xa0;ppm to 25,238&#xa0;ppm. The Cd content of black sphalerite (3,742 ppm&#x2013;17475 ppm, mean value: 8,681&#xa0;ppm) is lower than that of red sphalerite (5,532 ppm&#x2013;25238 ppm, mean value: 12,443&#xa0;ppm). The Ge content ranges from 0.22 ppm to 563&#xa0;ppm. The black sphalerite exhibits a Ge content range of 20.6 ppm&#x2013;563&#xa0;ppm (with a mean value of 210&#xa0;ppm), while the Ge content of red sphalerite ranges from 0.21 ppm to 230&#xa0;ppm (mean value: 41&#xa0;ppm). The Ga content ranges from 0.05 ppm to 674&#xa0;ppm. The Ga contents of black sphalerite (2.2 ppm&#x2013;674&#xa0;ppm) and red sphalerite (0.05 ppm&#x2013;582&#xa0;ppm) are not significantly different.</p>
</sec>
<sec id="s4-3">
<title>4.3 Depletion of Fe, Ag, Sb, and Mn</title>
<p>The contents of Fe, Ag, Sb, and Mn in the sphalerite of the Fuli deposit are relatively low (<xref ref-type="fig" rid="F6">Figure 6</xref>). The Fe content ranges from 1,166&#xa0;ppm to 2,896&#xa0;ppm. The Fe contents of black sphalerite (1,194&#xa0;ppm&#x2013;2,540&#xa0;ppm, mean value: 1796&#xa0;ppm) and red sphalerite (1,166&#xa0;ppm&#x2013;2,896&#xa0;ppm, mean value: 1884&#xa0;ppm) are not significantly different. The Ag content ranges from 0.12 ppm to 70&#xa0;ppm. The Ag content of black sphalerite (0.39&#xa0;ppm&#x2013;70&#xa0;ppm, mean value: 13.6&#xa0;ppm) is higher than that of red sphalerite (0.12&#xa0;ppm&#x2013;7.7 ppm, mean value: 2.02&#xa0;ppm). The Sb content ranges from 1.21 ppm to 2019&#xa0;ppm. The Sb content of black sphalerite ranges from 15.5 ppm to 2019&#xa0;ppm (mean value: 453&#xa0;ppm), while the Sb content of red sphalerite is relatively low (1.21&#xa0;ppm&#x2013;379&#xa0;ppm, mean value: 98&#xa0;ppm). The Mn content ranges from 0 to 3.79&#xa0;ppm. The Mn contents of black sphalerite (0&#x2013;1.73&#xa0;ppm) and red sphalerite (0&#x2013;3.79&#xa0;ppm) are not significantly different. In summary, the contents of Cu, Ag, As, Ge, Pb, and Sb decreased from black sphalerite to red sphalerite.</p>
</sec>
<sec id="s4-4">
<title>4.4 &#x3b4;<sup>34</sup>S values</title>
<p>The in situ-measured &#x3b4;<sup>34</sup>S values of the black and red sphalerites are listed in <xref ref-type="table" rid="T2">Table 2</xref>. The &#x3b4;<sup>34</sup>S values of the sphalerites determined <italic>in situ</italic> by LA-ICP-MS range from &#x2b;15.57&#x2030; to &#x2b;16.91&#x2030;. Significant differences are not observed in the &#x3b4;<sup>34</sup>S values of the black and red sphalerites (15.88&#x2030;&#x2013;16.91&#x2030; and 15.57&#x2030;&#x2013;16.79&#x2030;, respectively), indicating similar sources.</p>
<table-wrap id="T2" position="float">
<label>TABLE 2</label>
<caption>
<p>Summary of <italic>in situ</italic> S isotopic compositions in the Fuli Pb-Zn deposit.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="center">Mineral</th>
<th align="center">Color</th>
<th align="center">Sample no.</th>
<th align="center">&#x3b4;<sup>34</sup>S<sub>v</sub>-CDT (&#x2030;)</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td rowspan="16" align="center">Sphalerite</td>
<td rowspan="8" align="center">Black</td>
<td align="center">FL2-2</td>
<td align="center">16.690</td>
</tr>
<tr>
<td align="center">FL6-1</td>
<td align="center">16.500</td>
</tr>
<tr>
<td align="center">FL7-1</td>
<td align="center">16.170</td>
</tr>
<tr>
<td align="center">FL9-1</td>
<td align="center">16.910</td>
</tr>
<tr>
<td align="center">FL10-1</td>
<td align="center">16.250</td>
</tr>
<tr>
<td align="center">FL11-1</td>
<td align="center">16.580</td>
</tr>
<tr>
<td align="center">FL18-1</td>
<td align="center">15.920</td>
</tr>
<tr>
<td align="center">FL18-2</td>
<td align="center">15.880</td>
</tr>
<tr>
<td rowspan="8" align="center">Red</td>
<td align="center">FL1-3-01</td>
<td align="center">16.790</td>
</tr>
<tr>
<td align="center">FL1-3-02</td>
<td align="center">16.340</td>
</tr>
<tr>
<td align="center">FL16-1-01</td>
<td align="center">16.200</td>
</tr>
<tr>
<td align="center">FL16-1-02</td>
<td align="center">15.880</td>
</tr>
<tr>
<td align="center">FL16-2-01</td>
<td align="center">16.280</td>
</tr>
<tr>
<td align="center">FL16-2-02</td>
<td align="center">16.460</td>
</tr>
<tr>
<td align="center">FL16-2-03</td>
<td align="center">15.760</td>
</tr>
<tr>
<td align="center">FL16-2-04</td>
<td align="center">15.570</td>
</tr>
</tbody>
</table>
</table-wrap>
</sec>
<sec id="s4-5">
<title>4.5 Pb isotopic compositions</title>
<p>The <italic>in situ</italic> measured Pb isotopic values of galena are listed in <xref ref-type="table" rid="T3">Table 3</xref>. The Pb isotopic composition of galena in the Fuli deposit varies little (<sup>208</sup>Pb/<sup>204</sup>Pb &#x3d; 38.5&#x2013;38.651, <sup>207</sup>Pb/<sup>204</sup>Pb &#x3d; 15.666&#x2013;15.733, and <sup>206</sup>Pb/<sup>204</sup>Pb &#x3d; 18.539&#x2013;19.124). The narrow range of lead isotope values in galena and concentrated data imply similar source areas or high homogenization.</p>
<table-wrap id="T3" position="float">
<label>TABLE 3</label>
<caption>
<p>Summary of <italic>in situ</italic> Pb isotopic compositions in the Fuli Pb-Zn deposit.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="center">Mineral</th>
<th align="center">Sample no.</th>
<th align="center">
<sup>208</sup>Pb/<sup>204</sup>Pb</th>
<th align="center">
<sup>207</sup>Pb/<sup>204</sup>Pb</th>
<th align="center">
<sup>206</sup>Pb/<sup>204</sup>Pb</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td rowspan="17" align="center">Galena</td>
<td align="center">FL2-1-01</td>
<td align="center">38.563</td>
<td align="center">15.700</td>
<td align="center">18.563</td>
</tr>
<tr>
<td align="center">FL2-1-02</td>
<td align="center">38.500</td>
<td align="center">15.672</td>
<td align="center">18.539</td>
</tr>
<tr>
<td align="center">FL2-1-03</td>
<td align="center">38.542</td>
<td align="center">15.684</td>
<td align="center">18.634</td>
</tr>
<tr>
<td align="center">FL2-1-04</td>
<td align="center">38.534</td>
<td align="center">15.687</td>
<td align="center">18.650</td>
</tr>
<tr>
<td align="center">FL2-1-05</td>
<td align="center">38.534</td>
<td align="center">15.687</td>
<td align="center">18.623</td>
</tr>
<tr>
<td align="center">FL6-1-01</td>
<td align="center">38.651</td>
<td align="center">15.733</td>
<td align="center">18.637</td>
</tr>
<tr>
<td align="center">FL7-1-01</td>
<td align="center">38.552</td>
<td align="center">15.695</td>
<td align="center">18.563</td>
</tr>
<tr>
<td align="center">FL9-1-01</td>
<td align="center">38.606</td>
<td align="center">15.694</td>
<td align="center">18.589</td>
</tr>
<tr>
<td align="center">FL10-1-01</td>
<td align="center">38.543</td>
<td align="center">15.690</td>
<td align="center">18.558</td>
</tr>
<tr>
<td align="center">FL1-3-01</td>
<td align="center">38.525</td>
<td align="center">15.666</td>
<td align="center">18.602</td>
</tr>
<tr>
<td align="center">FL1-3-02</td>
<td align="center">38.576</td>
<td align="center">15.680</td>
<td align="center">18.544</td>
</tr>
<tr>
<td align="center">FL16-1-1</td>
<td align="center">38.545</td>
<td align="center">15.689</td>
<td align="center">18.558</td>
</tr>
<tr>
<td align="center">FL16-1-2</td>
<td align="center">38.568</td>
<td align="center">15.676</td>
<td align="center">18.555</td>
</tr>
<tr>
<td align="center">FL16-1-3</td>
<td align="center">38.610</td>
<td align="center">15.688</td>
<td align="center">18.561</td>
</tr>
<tr>
<td align="center">FL16-1-4</td>
<td align="center">38.606</td>
<td align="center">15.692</td>
<td align="center">18.565</td>
</tr>
<tr>
<td align="center">FL16-1-5</td>
<td align="center">38.609</td>
<td align="center">15.724</td>
<td align="center">19.124</td>
</tr>
<tr>
<td align="center">FL16-1-6</td>
<td align="center">38.601</td>
<td align="center">15.705</td>
<td align="center">18.759</td>
</tr>
</tbody>
</table>
</table-wrap>
</sec>
</sec>
<sec sec-type="discussion" id="s5">
<title>5 Discussion</title>
<sec id="s5-1">
<title>5.1 Mechanisms of trace element incorporation in sphalerite</title>
<p>Among the trace elements found in the Fuli Pb-Zn deposit sphalerite, Cu, Fe, and Cd have the highest contents. The range of Fe and Cd contents is narrow, and these elements appear as homogeneous patterns in the LA-ICP-MS time resolution profiles; these are parallel to those of Zn and S (<xref ref-type="fig" rid="F7">Figure 7</xref>), indicating that Fe and Cd occur in sphalerite <italic>via</italic> isomorphism. Since the ion radii of Fe<sup>2&#x2b;</sup>, Cd<sup>2&#x2b;</sup>, and Zn<sup>2&#x2b;</sup> are similar, these ions can replace each other in the sphalerite structure (<xref ref-type="bibr" rid="B26">Liu et al., 2015</xref>). In high-temperature environments, Fe has a strong ability to replace Zn <italic>via</italic> isomorphism. However, as the temperature decreases, Cd enters sphalerite and occupies the lattice position of the original Fe, resulting in a weak negative correlation between the contents of Cd and Fe in black sphalerite. However, red sphalerite is mostly formed in the middle and late stages of hydrothermal mineralization, when Cd and Fe mutually enter sphalerite; thus, a weak positive correlation is observed between the contents of Cd and Fe in red sphalerite (<xref ref-type="fig" rid="F8">Figure 8I</xref>).</p>
<fig id="F7" position="float">
<label>FIGURE 7</label>
<caption>
<p>Representative time-resolved LA-ICP-MS depth profiles for sphalerite.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g007.tif"/>
</fig>
<fig id="F8" position="float">
<label>FIGURE 8</label>
<caption>
<p>Binary plots illustrating the relationship of trace elements in sphalerite from the Fuli Pb-Zn deposit.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g008.tif"/>
</fig>
<p>Although the contents of Cu and Ge vary greatly in the red and black sphalerite, at most of the test points, the content of Cu exceeds 300ppm, and the content of Ge is more than 10&#xa0;ppm. Meanwhile, Cu and Ge appear in a nearly homogeneous patternin the LA-ICPMS time resolution profile (<xref ref-type="fig" rid="F7">Figure 7</xref>), and the range of Cu and Ge contents parallels that of Zn and S. This indicates that Cu and Ge may also exist as an isomorphic substitution in sphalerite. The tetrahedral covalent radii of Cu<sup>2&#x2b;</sup>, Zn<sup>2&#x2b;</sup>, and Ge<sup>2&#x2b;</sup> ions are 1.35, 1.31, and 1.22 respectively; thus, Cu<sup>2&#x2b;</sup> more easily enters the sphalerite lattice than Ge<sup>2&#x2b;</sup>. The average ion radius of the combination of the Cu<sup>2&#x2b;</sup> and Ge<sup>2&#x2b;</sup> is closer to the ion radius of Zn<sup>2&#x2b;</sup>, which is more conducive to the occurrence of isomorphic substitution and a possible mechanism is: nCu<sup>2&#x2b;</sup>&#x2b;Ge<sup>2&#x2b;</sup>&#x2194; (n&#x2b;1) Zn<sup>2&#x2b;</sup> (<xref ref-type="bibr" rid="B42">Ye L et al., 2016</xref>). This possible mechanism has also been confirmed in this study: 1) identification of arsenic tetrahedrite and a small amount of chalcopyrite in the deposit (<xref ref-type="fig" rid="F5">Figure 5C</xref>), indicating that the ore fluid was saturated in Cu at some stage; 2) a significant positive association exists between Cu and Ge in the Cu-Ge diagram (<xref ref-type="fig" rid="F8">Figure 8</xref>), indicating that Cu and Ge entered sphalerite synchronously. This coupled substitution may be an important reason for the enrichment of Ge in sphalerite in this deposit. The contents of Ag and As in sphalerite are relatively low and vary greatly. In some LA-ICPMS time resolution profiles, Pb appears as an unsmooth curve, while the range of Ag, As, and Sb contents are parallel to Pb (<xref ref-type="fig" rid="F7">Figure 7</xref>), indicating that Pb may exist in the form of fine-grained galena inclusions. However, Ag, As, and Sb may occur in galena micro-inclusions in the form of an isomorphic substitution.</p>
<p>Previous work suggests that the varying sphalerite colors are related to the following factors. 1) With increases in the Fe content in sphalerite increases, its color changes from colorless to yellow, brown, or even black (<xref ref-type="bibr" rid="B5">Chen, 1979</xref>). 2) It can be caused by various impurity elements in natural sphalerite, including those related to the addition of Cu, Tl, and Cd (<xref ref-type="bibr" rid="B35">Toulmin et al., 1991</xref>). 3) Sphalerite may have other colors only when the Fe content is lower than 1%; whilst, yellow sphalerite may be related to the incorporation of Cu and Ga <italic>via</italic> isomorphism, and red sphalerite may be caused by the addition of elements such as Cu, Ga, and Hg (<xref ref-type="bibr" rid="B21">Li and Peng, 1990</xref>). In a systematic study of the nearby Fule deposit, the color of Fule sphalerite is related to various elements such as Ni, Cu, Tl, Ga, Hg, Fe, and Cr; Ni and Cu result in purple sphalerite, Cu results in red sphalerite, and Ga results in yellow sphalerite (<xref ref-type="bibr" rid="B34">Si, 2005</xref>). Our findings indicate that the contents of Fe in black and red sphalerite are similar (average Fe contents of 1795.993&#xa0;ppm&#xa0;ppm and 1884.106ppm, respectively), implying that Fe may not affect the sphalerite color. Rather, the color may result from a combination of various factors. The variation in sulfur isotopes between the black and red sphalerites in this study is small, which does not affectthe sphalerite color. Generally, the microscopic color of sphalerite is uneven, and the overall color results from a combination of purple, red, yellow, and colorless varieties; thus, the change rule for trace elements in sphalerite of different colors is not significant (<xref ref-type="bibr" rid="B34">Si, 2005</xref>). The contents of Cu, Ag, As, Ge, Pb, and Sb decrease gradually from black sphalerite to red sphalerite, implying that these elements are more enriched in dark sphalerite.</p>
</sec>
<sec id="s5-2">
<title>5.2 Sources of reduced sulfur</title>
<p>There are three potential sources of sulfur sources in hydrothermal deposits. 1) Mantle-derived sulfur. Many materials are derived from the mantle, and it is not possible to directly determine the composition of mantle-derived S isotopes. The S isotope composition of chondrite is generally thought to be close to that of the mantle, and its &#x3b4;<sup>34</sup>S value is close to 0 (approximately 0&#x2030; &#xb1; 3&#x2030;) (<xref ref-type="bibr" rid="B4">Chaussidon et al., 1989</xref>). 2) Seawater sulfur, which has a &#x3b4;<sup>34</sup>S value of approximately &#x2b;20&#x2030;, although a significant amount of variation exists. It is widely recognized that the &#x3b4;34S value of marine evaporites reflects the sulphur isotope composition of seawater sulphate. 3) Reduced (deposited) sulfur, characterized by its highly negative values of &#x3b4;<sup>34</sup>S.</p>
<p>In the Fuli Pb-Zn deposit, the mineral assemblage is relatively simple; with the exception of sulfides such as sphalerite, galena, and a small amount of pyrite, no sulfate minerals are found. Therefore, the mean &#x3b4;<sup>34</sup>S value of sulfide approximately represents the &#x3b4;<sup>34</sup>S<sub>&#x2211;S</sub> value of the hydrothermal fluid (<xref ref-type="bibr" rid="B30">Ohmoto, 1972</xref>; <xref ref-type="bibr" rid="B28">Ohmoto and HGMB, 1997</xref>). The range of &#x3b4;<sup>34</sup>S values for the black and red sphalerite in the deposit is narrow (15.57&#x2030;&#x2013;16.91&#x2030;, average &#x3d; 16.261&#x2030;). These values are much higher than those of magmatic sulfates (<xref ref-type="fig" rid="F9">Figure 9</xref>), ruling out the possibility that magmatism provided massive reduced sulfur. Evaporated gypsum strata are developed in many sedimentary strata where the deposit is located. These strata are rich in seawater sulfate minerals such as gypsum and barite, and their &#x3b4;<sup>34</sup>S values range from 22&#x2030; to 28&#x2030; (<xref ref-type="bibr" rid="B16">Huang et al., 2004</xref>; <xref ref-type="bibr" rid="B55">Zhou et al., 2013b</xref>; <xref ref-type="bibr" rid="B17">Jin et al., 2016</xref>), higher than those of Permian seawater sulfates (11&#x2030;&#x2013;15&#x2030;) (<xref ref-type="bibr" rid="B6">Claypool et al., 1980</xref>), which are in good agreement with the &#x3b4;<sup>34</sup>S values observed in this study (<xref ref-type="fig" rid="F9">Figure 9</xref>). The thermochemical reduction of sulfate minerals can lead to a &#x394;sulfate-sulfide value (<xref ref-type="bibr" rid="B33">Seal, 2006</xref>; <xref ref-type="bibr" rid="B57">Zhou et al., 2013d</xref>) as high as 15&#x2030;. Thus, it can be concluded that the main sulfur source for Fuli Pb-Zn deposits is the seawater sulfate rock in sedimentary strata.</p>
<fig id="F9" position="float">
<label>FIGURE 9</label>
<caption>
<p>A comparison of sulfur isotopic compositions between the Pb-Zn deposits located in different strata ages of the SYG metallogenic province, seawater and mantle-derived sulfur (modified after <xref ref-type="bibr" rid="B6">Claypool et al., 1980</xref>). The data sourced from (<xref ref-type="bibr" rid="B4">Chaussidon et al., 1989</xref>; <xref ref-type="bibr" rid="B16">Huang et al., 2004</xref>; <xref ref-type="bibr" rid="B54">Zhou et al., 2010</xref>; <xref ref-type="bibr" rid="B55">2013b</xref>; <xref ref-type="bibr" rid="B56">2013c</xref>; <xref ref-type="bibr" rid="B53">2013a</xref>; <xref ref-type="bibr" rid="B44">Yuan et al., 2014</xref>; <xref ref-type="bibr" rid="B38">Wei et al., 2021</xref>).</p>
</caption>
<graphic xlink:href="feart-11-1104631-g009.tif"/>
</fig>
<p>Sulfate reduction mainly occurs through two mechanisms: thermochemical sulfate reduction (TSR) and bacterial sulfate reduction (<xref ref-type="bibr" rid="B29">Ohmoto, 2018</xref>). Based on microthermometry, the homogenization temperatures of fluid inclusions in Fuli sphalerite is approximately 110&#xb0;C&#x2013;200&#xb0;C (unpublished data) higher than that of bacterial reduction (<xref ref-type="bibr" rid="B18">J&#xf8;rgensen et al., 1992</xref>). In addition, bacterial sulfate reduction will result in S isotope fractionation of 40% or more (relative to sulfate) (<xref ref-type="bibr" rid="B29">Ohmoto, 2018</xref>), which is inconsistent with the similar &#x3b4;<sup>34</sup>S values of sulfates and sulfides in the deposit. At the same time, the sulfur isotopes in Fuli sphalerite range from 15.57&#x2030; to 16.91&#x2030;, close to the &#x3b4;<sup>34</sup>S values of marine sulfate and regional underlying strata in the same period; thus, TSR may be the main mechanism of sulfur reduction in this deposit. A large amount of reducing sulfur can be produced through TSR within a short period of time (<xref ref-type="bibr" rid="B30">Ohmoto, 1972</xref>). There is no evident sulfur isotope fractionation (<xref ref-type="bibr" rid="B29">Ohmoto, 2018</xref>) between reduced sulfur and sulfate. The sulfur isotope fractionation coefficient between SO<sub>4</sub> and H<sub>2</sub>S during TSR is considered to be 1.030 (<xref ref-type="bibr" rid="B31">Ottaway et al., 1994</xref>). The production efficiency of TSR is highest in the temperature range of 110&#xb0;C&#x2013;200&#xb0;C (<xref ref-type="bibr" rid="B29">Ohmoto, 2018</xref>), commensurate with the temperature of fluid inclusion homogenization in Fuli sphalerite (<xref ref-type="bibr" rid="B25">Liang et al., 2022</xref>). Therefore, S<sup>2&#x2212;</sup> in the ore-forming fluid of the Fuli Pb-Zn deposit is most likely the product of marine sulfate mineral TSR.</p>
</sec>
<sec id="s5-3">
<title>5.3 Sources of metallic elements</title>
<p>The range of the <italic>in situ</italic> Pb isotopic compositions of galena in the Fuli Pb-Zn deposit is restricted (<xref ref-type="table" rid="T3">Table 3</xref>), implying a single source of ore-forming metals in the deposit or a mixed source with a high degree of homogenization (<xref ref-type="bibr" rid="B16">Huang et al., 2004</xref>; <xref ref-type="bibr" rid="B52">Zhou et al., 2018b</xref>). In the <sup>207</sup>Pb/<sup>204</sup>Pb-<sup>206</sup>Pb/<sup>204</sup>Pb diagram (<xref ref-type="fig" rid="F10">Figure 10</xref>), the galena in the Fuli Pb-Zn deposit has a uniform Pb isotope composition, and all the data plot near the Pb average evolution line of the upper crust. This further indicates a crustal source of the ore-forming materials. Plotting the lead isotopic composition of the regional crystalline basement (Kunyang Group), Emeishan basalt, Devonian-Permian carbonate sedimentary strata, and the Huize Pb-Zn deposit onto the <sup>207</sup>Pb/<sup>204</sup>Pb-<sup>206</sup>Pb/<sup>204</sup>Pb diagram (<xref ref-type="fig" rid="F10">Figure 10</xref>) indicates that the Pb isotopes of the deposit are mainly concentrated in the Pb isotopic range of the Kunyang Group; it&#x27;s isotopic range is different from that of the Emeishan basalts. The Pb isotope data of sphalerite in the Fuli deposit displays a positive correlation tendency, implying that the sulfide Pb in the Fuli deposit may have a mixed source (<xref ref-type="fig" rid="F11">Figure 11</xref>) (<xref ref-type="bibr" rid="B3">Canals and Cardellach, 1997</xref>). <xref ref-type="bibr" rid="B34">Si RJ (2005)</xref> and <xref ref-type="bibr" rid="B51">Zhou et al. (2018a)</xref> also found that the Pb isotopes of adjacent deposits in this area have the characteristics of multiple sources. Combined with the regional geological and geochemical characteristics of the deposit, the metal elements of the Fuli Pb-Zn deposit may have multiple sources but originate principally from the Kunyang Group.</p>
<fig id="F10" position="float">
<label>FIGURE 10</label>
<caption>
<p>The comparison plot of <sup>207</sup>Pb/<sup>204</sup>Pb vs. <sup>206</sup>Pb/<sup>204</sup>Pb that display the field of late Permian Emeishan basalts, Cambrian-middle Permian sedimentary rocks and Proterozoic metamorphic rocks, and the Pb evolution curves of U, O, M and L (after <xref ref-type="bibr" rid="B59">Zartman and Doe, 1981</xref>); Upper Crust (U), Orogen Belt (O), Mantle (M) and Lower Crust (L). The data sourced from (<xref ref-type="bibr" rid="B16">Huang et al., 2004</xref>; <xref ref-type="bibr" rid="B22">Li et al., 2007</xref>; <xref ref-type="bibr" rid="B40">Yan et al., 2007</xref>; <xref ref-type="bibr" rid="B55">Zhou et al., 2013b</xref>; <xref ref-type="bibr" rid="B49">2014</xref>; <xref ref-type="bibr" rid="B1">Bao et al., 2017</xref>).</p>
</caption>
<graphic xlink:href="feart-11-1104631-g010.tif"/>
</fig>
<fig id="F11" position="float">
<label>FIGURE 11</label>
<caption>
<p>Plots of <sup>208</sup>Pb/<sup>204</sup>Pb vs. <sup>206</sup>Pb/<sup>204</sup>Pb <bold>(A)</bold> and <sup>207</sup>Pb/<sup>204</sup>Pb vs. <sup>206</sup>Pb/<sup>204</sup>Pb <bold>(B)</bold> of galena.</p>
</caption>
<graphic xlink:href="feart-11-1104631-g011.tif"/>
</fig>
</sec>
<sec id="s5-4">
<title>5.4 Ore genesis</title>
<p>The trace element composition of sphalerite can provide valuable information about the conditions under which they formed. For example, variations in the concentration of certain trace elements can be used to infer the temperature, pressure, fO2, and pH during mineral formation (<xref ref-type="bibr" rid="B7">Cook et al., 2009</xref>; <xref ref-type="bibr" rid="B43">Ye et al., 2011</xref>; <xref ref-type="bibr" rid="B24">Li et al., 2020</xref>). Additionally, the presence of certain trace elements in sphalerite can be used to track the source of the mineralizing fluids, and to determine whether they were derived from deep-seated magmatic sources or from shallower, sedimentary sources. Thus, the trace element composition of sphalerite can provide important clues about the origin and evolution of ore deposits.</p>
<p>The compositional characterization of trace elements in sphalerite has been widely applied as an effective tool for distinguishing various deposit types. Among the numerous trace elements present in sphalerite, Fe, Mn, Cd, Co, Ge, Ga have been particularly useful in identifying the origin and formation conditions of ore deposits. Specifically, sphalerite found in magmatic-related deposits is typically characterized by high concentrations of Fe, Mn, and Co, but lower levels of Ge and Cd. In contrast, sphalerite from Mississippi Valley Type (MVT) deposits typically displays low levels of Fe, Mn, and Co, but elevated concentrations of Ge, Cd, and Ga (<xref ref-type="bibr" rid="B7">Cook et al., 2009</xref>; <xref ref-type="bibr" rid="B42">Ye L et al., 2016</xref>; <xref ref-type="bibr" rid="B37">Wei et al., 2019</xref>; <xref ref-type="bibr" rid="B13">Hu et al., 2020</xref>; <xref ref-type="bibr" rid="B24">Li et al., 2020</xref>).</p>
<p>The Fuli Pb-Zn deposit has a simple mineral composition and a low degree of wall rock alteration. The mineralization is primarily Zn, and the ore-forming temperature is inferred to be low (110&#xb0;C&#x2013;200&#xb0;C). The Pb-Zn orebody predominantly hosted in the dolomite of the Middle Permian Yangxin formation and is governed by fault structures. The Pb-Zn mineralization fills the fault fracture zone in a bedlike manner, and epigenetic mineralization is noticeable. These geological characteristics are similar to those of a classic MVT deposit (<xref ref-type="bibr" rid="B19">Leach et al., 2001</xref>; <xref ref-type="bibr" rid="B20">2010</xref>), and the metallogenic characteristics are similar to those of other Pb-Zn deposits in the SYG area (<xref ref-type="bibr" rid="B45">Zhang, 2008</xref>). In the Cd&#x2013;Mn&#x2013;1000Ge (<xref ref-type="fig" rid="F12">Figure 12</xref>), as well as in the Ge&#x2013;Mn (<xref ref-type="fig" rid="F13">Figure 13A</xref>), Fe&#x2013;Mn (<xref ref-type="fig" rid="F13">Figure 13B</xref>), and Mn&#x2013;Cd/Fe (<xref ref-type="fig" rid="F13">Figure 13C</xref>) discrimination plots, the Fuli sphalerite is located in the field that is indicative of MVT deposits. Compared with the typical MVT deposit, the content of Cu in this deposit is higher, and the chalcopyrite and tetrahedrite are distributed in a droplet-like manner within the sphalerite. Based on the field geologic characteristics, sphalerite trace elements, and S and Pb isotope geochemistry, the Fuli Pb-Zn deposit should belong a MVT type Pb-Zn deposit.</p>
<fig id="F12" position="float">
<label>FIGURE 12</label>
<caption>
<p>Ternary Cd&#x2013;Mn&#x2013;1000Ge plot of sphalerite from the Fuli deposit modified after (<xref ref-type="bibr" rid="B48">Zhou et al., 2022</xref>).</p>
</caption>
<graphic xlink:href="feart-11-1104631-g012.tif"/>
</fig>
<fig id="F13" position="float">
<label>FIGURE 13</label>
<caption>
<p>Binary plots of <bold>(A)</bold> Mn and Ge; <bold>(B)</bold> Mn and Fe; <bold>(C)</bold> Cd/Fe and Mn. These data are collected from (<xref ref-type="bibr" rid="B7">Cook et al., 2009</xref>; <xref ref-type="bibr" rid="B42">Ye L et al., 2016</xref>; <xref ref-type="bibr" rid="B24">Li et al., 2020</xref>; <xref ref-type="bibr" rid="B38">Wei et al., 2021</xref>; <xref ref-type="bibr" rid="B41">Yang et al., 2022</xref>).</p>
</caption>
<graphic xlink:href="feart-11-1104631-g013.tif"/>
</fig>
</sec>
</sec>
<sec sec-type="conclusion" id="s6">
<title>6 Conclusion</title>
<p>The main conclusions drawn from this study are summarized as follows:<list list-type="simple">
<list-item>
<p>1) Fe, Cd, Cu, and Ge in sphalerite may occur in the form of isomorphic substitutions, Pb may exist in the form of galena micro-inclusions, and Ag, As, and Sb may occur in galena micro-inclusions.</p>
</list-item>
<list-item>
<p>2) The contents of Cu, Ag, As, Ge, Pb, and Sb decrease gradually from black sphalerite to red sphalerite, and the color of sphalerite may change with the contents of Ni, Cu, Ga, and other elements.</p>
</list-item>
<list-item>
<p>3) Ore-forming fluids, sulfur was primarily derived from seawater sulfate rocks as a product of TSR, while ore-forming metals mainly come from basement rocks.</p>
</list-item>
<list-item>
<p>4) The Fuli Pb-Zn deposit occurs in the dolomite of the Middle Permian Yangxin formation and is controlled by the interlayer compressional structure. The characteristics of epigenetic ore are clear, the mineral composition is simple (mainly sphalerite, galena, and pyrite), and the Pb-Zn grade is high. The Fuli Pb-Zn deposit is enriched in Cd, Ga, Ge, and other dispersed elements. Based on the field geologic characteristics, sphalerite trace elements, and S and Pb isotope geochemistry, the Fuli Pb-Zn deposit should be classified as an MVT type Pb-Zn deposit.</p>
</list-item>
</list>
</p>
</sec>
</body>
<back>
<sec sec-type="data-availability" id="s7">
<title>Data availability statement</title>
<p>The original contributions presented in the study are included in the article/supplementary material, further inquiries can be directed to the corresponding author.</p>
</sec>
<sec id="s8">
<title>Author contributions</title>
<p>XL: Conceptualization, data curation, formal analysis, investigation, methodology, visualization, writing: Original draft, writing: Review and editing. BL: Conceptualization, funding acquisition, project administration, resources, writing: Review and editing. XZ: Visualization, data curation, investigation. HQ: Resources, investigation. GL: Resources, investigation. CZ: Resources, investigation. All authors contributed to manuscript revision, read, and approved the submitted version.</p>
</sec>
<sec sec-type="COI-statement" id="s9">
<title>Conflict of interest</title>
<p>Authors HQ and GL were employed by Fuli Lead Zinc Mine Co., Ltd. Author CZ was employed by Yunnan Tin Industry Group (Holding) Company Limted R &#x26; D Center.</p>
<p>The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.</p>
</sec>
<sec sec-type="disclaimer" id="s10">
<title>Publisher&#x2019;s note</title>
<p>All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.</p>
</sec>
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