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<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>
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<article-meta>
<article-id pub-id-type="publisher-id">1609741</article-id>
<article-id pub-id-type="doi">10.3389/feart.2025.1609741</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>Syn-to post-orogenic mineralization in the Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposit, North Qaidam: insights from H&#x2013;O&#x2013;S isotopes and U&#x2013;Pb geochronology</article-title>
<alt-title alt-title-type="left-running-head">Yu 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.2025.1609741">10.3389/feart.2025.1609741</ext-link>
</alt-title>
</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname>Yu</surname>
<given-names>Junzhen</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
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<contrib contrib-type="author">
<name>
<surname>Li</surname>
<given-names>Dexian</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
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</contrib>
<contrib contrib-type="author">
<name>
<surname>Zheng</surname>
<given-names>Youye</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
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<contrib contrib-type="author">
<name>
<surname>Ma</surname>
<given-names>Bo</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
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<contrib contrib-type="author">
<name>
<surname>Wang</surname>
<given-names>Jian</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
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<contrib contrib-type="author">
<name>
<surname>Shi</surname>
<given-names>Guomei</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
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<contrib contrib-type="author">
<name>
<surname>Xu</surname>
<given-names>Rongke</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
</xref>
<role content-type="https://credit.niso.org/contributor-roles/conceptualization/"/>
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</contrib>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Khan</surname>
<given-names>Junaid</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
<uri xlink:href="https://loop.frontiersin.org/people/2921908/overview"/>
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<contrib contrib-type="author">
<name>
<surname>Tahir</surname>
<given-names>Asma</given-names>
</name>
<xref ref-type="aff" rid="aff4">
<sup>4</sup>
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<aff id="aff1">
<sup>1</sup>
<institution>State Key Laboratory of Ni and Co Associated Minerals Resources Development and Comprehensive Utilization</institution>, <addr-line>Jinchang</addr-line>, <addr-line>Gansu</addr-line>, <country>China</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Jinchuan Nickel and Cobalt Research and Engineering Institute</institution>, <addr-line>Jinchang</addr-line>, <addr-line>Gansu</addr-line>, <country>China</country>
</aff>
<aff id="aff3">
<sup>3</sup>
<institution>School of Earth Resources</institution>, <institution>China University of Geosciences</institution>, <addr-line>Wuhan</addr-line>, <country>China</country>
</aff>
<aff id="aff4">
<sup>4</sup>
<institution>Geological Survey Institute</institution>, <institution>China University of Geosciences</institution>, <addr-line>Wuhan</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/1191197/overview">Huan Li</ext-link>, Central South University, China</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/2618257/overview">Mohamed Faisal</ext-link>, Suez Canal University, Egypt</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/3071940/overview">Shan Liu</ext-link>, University of South China, China</p>
</fn>
<corresp id="c001">&#x2a;Correspondence: Junaid Khan, <email>junaidkhan5615@yahoo.com</email>
</corresp>
</author-notes>
<pub-date pub-type="epub">
<day>21</day>
<month>07</month>
<year>2025</year>
</pub-date>
<pub-date pub-type="collection">
<year>2025</year>
</pub-date>
<volume>13</volume>
<elocation-id>1609741</elocation-id>
<history>
<date date-type="received">
<day>10</day>
<month>04</month>
<year>2025</year>
</date>
<date date-type="accepted">
<day>27</day>
<month>05</month>
<year>2025</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2025 Yu, Li, Zheng, Ma, Wang, Shi, Xu, Khan and Tahir.</copyright-statement>
<copyright-year>2025</copyright-year>
<copyright-holder>Yu, Li, Zheng, Ma, Wang, Shi, Xu, Khan and Tahir</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 Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposits, hosted within meta-basaltic rocks of the Tanjianshan Group in the North Qaidam Orogenic Belt, northwest China, present significant insights into syn-to post-orogenic mineralization processes. Preliminary fluid inclusion studies suggest distinct fluid origins for Ag&#x2013;Pb and Au mineralization at Shuangkoushan; however, due to the lack of geochronological and isotopic data, as well as comprehensive textural analysis, this hypothesis remains unverified. This research aims to identify the orogenic phase associated with the Shuangkoushan Au and Ag-Pb ore deposits and to constrain the potential sources of the fluid and ore-forming materials through detailed microscopic investigations, zircon U-Pb dating, and H&#x2013;O&#x2013;S isotopic analyses. The syn-orogenic meta-basaltic rocks, intruded by gabbros, host numerous orogenic Au deposits and are structurally controlled by a NW&#x2013;SE-trending ductile shear zone. The contact morphology indicates proximal emplacement of both igneous units, with the influence of the ductile shear zone evident in each assemblage. Geochronological analysis using zircon U&#x2013;Pb dating of the gabbroic pluton yields a Concordia age of <sup>206</sup>Pb/<sup>238</sup>U &#x3d; 448.5 &#xb1; 2.5 Ma, which likely predates the formation of the ductile shear zone/quartz veins and provides critical temporal constraints on the Au mineralization sequence. The Au mineralization stage characterized by fluid isotopic compositions (&#x3b4;D<sub>V-</sub>SMOW &#x3d; &#x2212;72.9&#x2030; to &#x2212;81.5&#x2030;; &#x3b4;18OH2O-SMOW &#x3d; 3.45&#x2030;&#x2013;4.95&#x2030;; &#x3b4;18OV-SMOW &#x3d; 10.4&#x2030;&#x2013;13.9&#x2030;) and pyrite sulfur isotopes (&#x3b4;34S &#x3d; &#x2b;4.8&#x2030; to &#x2b;10&#x2030;), indicating predominantly metamorphic fluids mixed with substantial meteoric water and a basalt-derived metal source. The Ag-Pb ore body formed in association with post-orogenic deep magmatism in late Devonian, rather than the adjacent Neoproterozoic granitic gneisses (206 Pb/238U &#x3d; 835 &#xb1; 6.3 Ma, 924 &#xb1; 6.3 Ma). The Ag-Pb mineralization stage shows H-O (&#x3b4;DV-SMOW -108.2&#x2030; to &#x2212;113.8&#x2030;, &#x3b4;18OH2O-SMOW 6.45&#x2030;&#x2013;6.55&#x2030;, &#x3b4;18OV<sub>-SMOW</sub> 14.1&#x2030;&#x2013;14.3&#x2030;) and S-isotopic (&#x3b4;<sup>34</sup>S &#x2b; 0.2&#x2030; to &#x2b;3.3&#x2030;) compositions, suggesting that Ag-Pb mineralizing fluids were primarily sourced from primitive magmatic water with a minor meteoric water component, and Ag-Pb ore-forming materials were primarily sourced from deep magmatic source. Field geological features, isotopic data, and orogenic deposits comparisons, indicate that the Shuangkoushan Au-Ag-Pb deposit formed through Syn-to Post-orogenic mineralization stages.</p>
</abstract>
<kwd-group>
<kwd>Tanjianshan metabasalt</kwd>
<kwd>Shuangkoushan Au-Ag-Pb deposits</kwd>
<kwd>syn-post orogeny</kwd>
<kwd>H-O-S isotopes</kwd>
<kwd>North Qaidam orogeny</kwd>
</kwd-group>
<custom-meta-wrap>
<custom-meta>
<meta-name>section-at-acceptance</meta-name>
<meta-value>Economic Geology</meta-value>
</custom-meta>
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</article-meta>
</front>
<body>
<sec id="s1">
<title>1 Introduction</title>
<p>Orogenic events are critical in forming significant mineral deposits, particularly gold (Au), as these geological processes create conditions conducive to fluid mobilization and metal concentration (<xref ref-type="bibr" rid="B50">Kim and Choi, 2009</xref>; <xref ref-type="bibr" rid="B52">Langille et al., 2012</xref>). Syn-orogenic mineralization refers to ore-forming processes that occur concurrently with tectonic deformation, commonly resulting in the concentration of Au in structurally controlled settings such as faults, shear zones, and fold hinges, but also in disseminated forms within altered host rocks developed during the same tectonic regime (<xref ref-type="bibr" rid="B65">Oberth&#xfc;r and Weiser, 2008</xref>; <xref ref-type="bibr" rid="B72">Sanusi and Amigun, 2020</xref>; <xref ref-type="bibr" rid="B17">Cheval-Garab&#xe9;dian et al., 2021</xref>). Conversely, post-orogenic mineralization refers to processes that occur after the main compressive tectonic events, often under different temperature and pressure conditions. These settings commonly facilitate the formation of a variety of metal and element deposits&#x2014;often through hydrothermal processes&#x2014;such as Ag, Pb, and other base or precious metals (<xref ref-type="bibr" rid="B4">Becker et al., 2009</xref>; <xref ref-type="bibr" rid="B103">Yoo and White, 2013</xref>; <xref ref-type="bibr" rid="B83">Sun C. et al., 2022</xref>).</p>
<p>Mineral assemblages associated with syn-orogenic Au deposits are often characterized by Au-bearing quartz veins formed under metamorphic conditions, whereas post-orogenic Ag-Pb deposits exhibit varying mineralogy, frequently influenced by interactions with meteoric water (<xref ref-type="bibr" rid="B36">Groves et al., 2003</xref>; <xref ref-type="bibr" rid="B4">Becker et al., 2009</xref>; <xref ref-type="bibr" rid="B103">Yoo and White, 2013</xref>). The role of magmatic fluids in driving this evolution is also significant, as they are often enriched in volatile components that can leach metals from surrounding rocks and facilitate deposition in suitable geological settings (<xref ref-type="bibr" rid="B52">Langille et al., 2012</xref>; <xref ref-type="bibr" rid="B46">Kalinin et al., 2019</xref>). Moreover, the changing conditions associated with tectonic uplift can lead to episodic mineralization events that are distinct but interconnected through their geological history (<xref ref-type="bibr" rid="B50">Kim and Choi, 2009</xref>; <xref ref-type="bibr" rid="B4">Becker et al., 2009</xref>).</p>
<p>The influence of magmatic and metamorphic processes, as well as the interaction with surface waters, is postulated to affect the isotopic signatures of the minerals formed during these later stages (<xref ref-type="bibr" rid="B45">Jing and Pring, 2019</xref>). This duality in mineralization reflects different fluid sources and geochemical environments, suggesting that advanced analytical techniques are necessary to fully capture these transitions and their geochemical implications (<xref ref-type="bibr" rid="B45">Jing and Pring, 2019</xref>).</p>
<p>Stable isotope geochemistry is a fundamental analytical tool for constraining the source characteristics, transport mechanisms, and physicochemical conditions of ore-forming fluids, thereby elucidating both the metallogenic processes and evolution of ore-forming fluids (<xref ref-type="bibr" rid="B73">Seo et al., 2006</xref>; <xref ref-type="bibr" rid="B103">Yoo and White, 2013</xref>; <xref ref-type="bibr" rid="B75">Shi et al., 2024</xref>; <xref ref-type="bibr" rid="B25">Faisal et al., 2025</xref>). Specifically, the examination of hydrogen and oxygen isotopes in quartz veins provides significant insights into the sources of mineral-forming fluids. Similarly, sulfur isotopes (&#x3b4;<sup>34</sup>S) help identify the source of sulfur in the ore-forming fluids, which indirectly constrains the origin of the fluids and biogeochemical processes that control Au incorporation (<xref ref-type="bibr" rid="B47">Kerrich, 1986</xref>; <xref ref-type="bibr" rid="B121">Zoheir et al., 2019</xref>; <xref ref-type="bibr" rid="B86">Tian et al., 2024</xref>). Additionally, zircon U-Pb dating serves as a robust method for determining the timing of geological events (<xref ref-type="bibr" rid="B43">Ito, 2024</xref>). This approach helps delineate the temporal relationships between mineral deposits and their host wall rocks, elucidating the complex interactions that occur during tectonic and magmatic processes.</p>
<p>Numerous studies (e.g., <xref ref-type="bibr" rid="B104">Yu et al., 1998</xref>) have documented the Shuangkoushan deposit hosted in meta-basaltic rocks of the Tanjianshan group of North Qaidam, which is a significant area for understanding mineralization processes related to geological evolution. The presence of Au-Bi-Te-S deposits and associated mineral assemblages in the region suggests a complex hydrothermal system, indicating that fluid pathways and interaction with host rocks significantly influence the ore body&#x2019;s distribution and composition (<xref ref-type="bibr" rid="B65">Oberth&#xfc;r and Weiser, 2008</xref>; <xref ref-type="bibr" rid="B98">Xu et al., 2019</xref>). The Shuangkoushan area is a large-scale Ag&#x2013;Pb producing area that requires further in-depth investigation (<xref ref-type="bibr" rid="B57">Liu and Deying, 2019</xref>). Preliminary fluid inclusion studies in ore-bearing quartz veins by <xref ref-type="bibr" rid="B63">Meng (2017)</xref> and <xref ref-type="bibr" rid="B105">Yu et al. (2020)</xref> suggest that Ag&#x2013;Pb mineralization is associated with magmatic&#x2013;hydrothermal activity, while Au mineralization is driven by metamorphic fluids. Yet, due to the lack of geochronological and isotopic data, as well as a comprehensive textural analysis of the ore minerals, this hypothesis remains unjustified. This research aims to constrain the syn-to post-orogenic mineralization processes of the Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposits (North Qaidam) by investigating the sources of ore-forming fluids and materials, utilizing zircon U&#x2013;Pb geochronology, H&#x2013;O&#x2013;S isotopic analysis, and textural studies.</p>
</sec>
<sec id="s2">
<title>2 Geological setting</title>
<sec id="s2-1">
<title>2.1 Regional geology</title>
<p>The North Qaidam Orogenic Belt (NQOB) is a high-pressure/ultrahigh-pressure (HP/UHP) metamorphic belt located at the northeastern margin of the Qinghai-Tibetan Plateau (<xref ref-type="fig" rid="F1">Figure 1a</xref>). It represents a Paleozoic continental collision zone between the Qaidam Block to the south and the Qilian Block to the north (<xref ref-type="bibr" rid="B81">Song et al., 2005</xref>; <xref ref-type="bibr" rid="B111">Zhang et al., 2008</xref>; <xref ref-type="bibr" rid="B13">Chen et al., 2022b</xref>; <xref ref-type="bibr" rid="B56">Lin et al., 2025</xref>). The NQOB, encompassing the Yeluotuoquan, Qianmeiling, Hongliugou, Tanjianshan, and Yuka areas, are a critical region for orogenic mineral deposits&#x2014;particularly Au and base metals. These deposits are primarily hosted within specific lithological units, including carbonaceous phyllite and carbonate rocks of the Wandonggou Group and mafic volcanic rocks (metabasalt) of the Tanjianshan Group (<xref ref-type="bibr" rid="B104">Yu et al., 1998</xref>; <xref ref-type="bibr" rid="B107">Zhang et al., 2010</xref>; <xref ref-type="bibr" rid="B28">Fan, 2016</xref>). These deposits are controlled by a NW&#x2013;SE-trending ductile shear zone, similar to other regional deposits such as the Qinglonggou and Jinlonggou deposits (<xref ref-type="bibr" rid="B59">Liu et al., 2005</xref>). Geological structures and magmatic activities have played a crucial role in the formation of polymetallic ore deposits in northwest China (<xref ref-type="bibr" rid="B78">Shi et al., 2004</xref>; <xref ref-type="bibr" rid="B77">Shi et al., 2006</xref>; <xref ref-type="bibr" rid="B95">Wu et al., 2001</xref>; <xref ref-type="bibr" rid="B94">2007</xref>). The exposed stratigraphy comprises a Cambrian&#x2013;Ordovician greenschist facies, metamorphosed sequence of arc-related volcanic and sedimentary rocks of Tanjianshan Group, Maojiushan sandstone and tuff, Yukahe schist and gneiss (<xref ref-type="bibr" rid="B116">Zhao et al., 2003</xref>; <xref ref-type="bibr" rid="B15">Chen et al., 2018a</xref>).</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>
<bold>(a)</bold> Geological map showing distribution of Au deposits in China (modified after <xref ref-type="bibr" rid="B21">Deng and Wang, 2016</xref>); <bold>(b)</bold> The distribution of Au deposits in the NQOB (modified after <xref ref-type="bibr" rid="B59">Liu et al., 2005</xref>); <bold>(c)</bold> Geological map of NQOB terrane showing sampling locations from Tanjianshan group hosted Shuangkoushan ore-deposits (modified after <xref ref-type="bibr" rid="B24">Du, 2017</xref>).</p>
</caption>
<graphic xlink:href="feart-13-1609741-g001.tif"/>
</fig>
<p>The gabbros intrude into the Tanjianshan Group, which consists of low-grade metamorphic volcanic-sedimentary rocks, including metabasalts, metabasaltic andesites, dacites, sericite schists, carbonaceous schists, marbles, metasandstones, and conglomerates (<xref ref-type="bibr" rid="B42">Huichu et al., 2003</xref>; <xref ref-type="bibr" rid="B53">Lei et al., 2022</xref>). The Tanjianshan Group contains the Shuangkoushan Au&#x2013;Ag&#x2013;Pb ore deposits, adjacent to a Pb&#x2013;Zn magmatic-hydrothermal deposit and numerous orogenic Au deposits from other complexes in the region (Xietieshan and Luliangshan complexes, respectively; <xref ref-type="bibr" rid="B21">Deng and Wang, 2016</xref>; <xref ref-type="bibr" rid="B84">Sun et al., 2017</xref>; <xref ref-type="bibr" rid="B8">Cai et al., 2018</xref>). The exposed deformation features in the Shuangkoushan area include a NW-trending ductile shear zone, a brittle&#x2013;ductile shear zone, and a NE-trending brittle fracture system. The formation and localization of the deposit were primarily controlled by these structural features.</p>
</sec>
<sec id="s2-2">
<title>2.2 Local geology</title>
<p>The exposed lithologies in the Shuangkoushan area include tonalite, granodiorite, gabbro, mica quartz schist, quartzite, meta-sandstone with associated conglomerates, and Quaternary alluvium (<xref ref-type="fig" rid="F2">Figure 2a</xref>). Additionally, mafic and ultramafic pyroclastic rocks were emplaced along thrust faults, with protolith ages ranging from 450 to 530 Ma (<xref ref-type="bibr" rid="B85">Sun et al., 2019</xref>; <xref ref-type="bibr" rid="B7">Cai et al., 2021</xref>; <xref ref-type="bibr" rid="B53">Lei et al., 2022</xref>; <xref ref-type="bibr" rid="B123">Jiang et al., 2024</xref>; <xref ref-type="bibr" rid="B125">Chen et al., 2025</xref>). Preliminary drilling has indicated that the Shuangkoushan ore deposit consists of distinct Au and Ag&#x2013;Pb mineralization bodies, with total reserves exceeding 5 t of Au and 39 t of Ag, along with a significant amount of Pb (<xref ref-type="bibr" rid="B63">Meng, 2017</xref>). In the study area, both mineralized bodies are hosted within metabasaltic rocks of the Tanjianshan Group deposits, located at the western margin between the Xietieshan and Luliangshan complexes (<xref ref-type="fig" rid="F1">Figures 1b,c</xref>). These metabasalts have undergone significant mylonitization and fragmentation (<xref ref-type="bibr" rid="B14">Chen et al., 2018b</xref>).</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>
<bold>(a)</bold> Modified Geological map of the Shuangkoushan Au-Ag-Pb deposits area (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). <bold>(b)</bold> Geological cross-section (A, B) of the Shuangkoushan Au-Ag-Pb deposit area, showing subsurface lithology.</p>
</caption>
<graphic xlink:href="feart-13-1609741-g002.tif"/>
</fig>
<p>The Au ore body is primarily hosted in a NW&#x2013;SE trending brittle-ductile shear zone, dipping 50&#xb0;&#x2013;75&#xb0; to the NW. A total of 10 ore bodies have been identified through exploration, including following main ore bodies number: 10, 9, 4, and 5 with an average grade of 2.24 g/t (<xref ref-type="fig" rid="F2">Figure 2b</xref>). Orebody No. 9 is approximately 172 m long and 3.7 m wide, with an average Au grade of 6.3 g/t. Orebody No. 10 consists of three orebody layers, extending a total of 2 km in length and 60 m in width, with a grade ranging from 1 to 3.8 g/t. Orebody No. 4 is about 700 m long and 2 m wide, with a grade of 1.02&#x2013;3.6 g/t (<xref ref-type="bibr" rid="B24">Du, 2017</xref>). These ores are primarily classified as structurally altered rock and quartz-vein types (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). A critical aspect of recent research is the recognition of multistage pyrite formation&#x2014;classified as Py1, Py2, Py3, and Py4&#x2014;which plays a key role in constraining the mineralization sequence and fluid evolution. Each generation of pyrite exhibits distinct textural, compositional, and isotopic signatures that correlate with different mineralization stages. Arsenian pyrite (Py1) is the predominant ore mineral in the hypogene ores of area, occurring as subhedral or euhedral fine-grained infillings in quartz fractures (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). The gangue minerals mainly include quartz, sericite, and chlorite (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). Au occurs primarily as invisible Au in Py1, with grain sizes ranging from 10 &#x3bc;m to 70 &#x3bc;m. The Au size range can be observed in the photograph from the preliminary research work of this area by <xref ref-type="bibr" rid="B14">Chen et al. (2018b)</xref>. Sulfide minerals appear as disseminations or infilling veinlets within brittle fracture zones and brittle&#x2013;ductile shear fracture zones, displaying various metamorphic relationships and textures within the alteration zones (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). Py2 is porous and coexists with other sulfide minerals (Py1, Py3, etc.). Py2 metasomatized by Py3. Py3 is anhedral and forms in later stages, Py3 further metasomatized by chalcopyrite. The Au grade is positively correlated with pyrite content. Hydrothermal alteration in the Au mineralization stage is characterized by sericitization, silicification, and sulfidation, with no clear zonation.</p>
<p>The Ag&#x2013;Pb orebodies contain reserves exceeding 39 t of Ag, with an average grade of 343.52 g/t, along with a significant amount of Pb, averaging 11.10% (<xref ref-type="bibr" rid="B63">Meng, 2017</xref>). These orebodies are controlled by NE-trending extensional faults and occur as infilling hydrothermal veinlets that cut through the earlier Au ore bodies (<xref ref-type="fig" rid="F2">Figure 2a</xref>). The ore bodies form lens-shaped deposits at the surface and extend to depths greater than 330 m.</p>
<p>The predominant hypogene ore minerals include galena, stromeyerite (AgCuS), and pyrargyrite (Ag<sub>3</sub>SbS<sub>3</sub>), with minor amounts of chalcopyrite and sphalerite. Galena occurs as fine subhedral or euhedral grains filling fractures in pyrite (Py4) (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). Stromeyerite and pyrargyrite display solid-solution separation textures, typically enclosed by galena (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). The gangue minerals consist of quartz, calcite, sericite, and carbonaceous materials (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). Sulfide minerals occur as thin infilling veinlets within the brittle fracture zone (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). Hydrothermal alteration associated with Ag&#x2013;Pb mineralization is characterized by silicification, sulfidation, and carbonatization.</p>
</sec>
</sec>
<sec id="s3">
<title>3 Analytical methods</title>
<sec id="s3-1">
<title>3.1 Sample collection</title>
<p>The sample collection site is Shuangkoushan, located in the North Qaidam region of western China. During the field survey, two fresh rock samples were collected: one from the gabbro unit (95&#xb0;3&#x2032;0&#x2033;E, 37&#xb0;45&#x2032;36&#x2033;N) and another from the granitic gneiss unit (95&#xb0;4&#x2032;26.4&#x2033;E, 37&#xb0;46&#x2032;12&#x2033;N), both adjacent to the Shuangkoushan ore deposits for age dating (<xref ref-type="fig" rid="F1">Figure 1c</xref>). An H&#x2013;O isotope study was conducted on eight quartz samples collected near 95&#xb0;4&#x2032;12&#x2033;E, 37&#xb0;45&#x2032;36&#x2033;N from the Au and Ag&#x2013;Pb ore bodies. Additionally, ten galena&#x2013;chalcopyrite-bearing samples from the Ag&#x2013;Pb ore body, collected from drill holes ZK01 (95&#xb0;4&#x2032;12&#x2033;E, 37&#xb0;45&#x2032;36&#x2033;N) and ZK02 (95&#xb0;4&#x2032;33.6&#x2033;E, 37&#xb0;43&#x2032;48&#x2033;N) (<xref ref-type="fig" rid="F2">Figure 2a</xref>), and twenty-two pyrite-bearing samples from the Au ore body in the vicinity of 95&#xb0;43&#x2032;12&#x2033;E, 37&#xb0;46&#x2032;12&#x2033;N were subjected to <italic>in situ</italic> sulfur isotope analysis (<xref ref-type="fig" rid="F1">Figure 1c</xref>). Approximately six fresh rock samples were also collected from Tanjianshan metabasalts&#x2014;hosting Au&#x2013;Ag&#x2013;Pb deposits&#x2014;near 95&#xb0;4&#x2032;12&#x2033;E, 37&#xb0;45&#x2032;50.4&#x2033;N for textural studies. Each sample, weighing approximately 1 kg, was placed in a labeled bag with a unique identification number and subsequently dispatched to the laboratory.</p>
</sec>
<sec id="s3-2">
<title>3.2 Textural analysis</title>
<p>Sulfide-bearing rock samples were cut, polished to a mirror finish, and carbon-coated to ensure conductivity. A Scanning Electron Microscope (SEM) equipped with a Backscattered Electron (BSE) detector was used at the State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan). The SEM was operated at an accelerating voltage of 10&#x2013;20 kV, with a moderate beam current and a working distance of 10&#x2013;15 mm. BSE images were formed by detecting electrons backscattered from the sample surface, providing compositional contrast based on atomic number differences. This is crucial for distinguishing between different sulfide phases (<xref ref-type="bibr" rid="B64">Novikov, 2014</xref>). High-resolution grayscale images were obtained, clearly revealing the textural relationships among various sulfide phases. For further details on the procedure, refer to <xref ref-type="bibr" rid="B9">&#x10c;alkovsk&#xfd; et al. (2023)</xref>.</p>
</sec>
<sec id="s3-3">
<title>3.3 Geochronology</title>
<p>Crushing and zircon selection for the Gabbro (SK01) and Granitic Gneiss (GS01) samples were conducted at the Langfang Institute of Geological and Mineral Research Laboratory. Initially, samples were broken into small fragments, washed, dried, and then pulverized to 200 mesh. Zircons were separated using conventional heavy liquid and magnetic separation techniques, mounted in epoxy resin, and polished to expose grain centers.</p>
<p>Zircons were selected for isotopic analysis based on cathodoluminescence (CL) imaging, performed at the Wuhan Sample Solution Analytical Technology Co., Ltd., using an Analytical Scanning Electron Microscope (JSM-IT100) equipped with a GATAN MINICL system. Imaging was conducted with a 10.0&#x2013;13.0 kV electric field and an 80&#x2013;85 &#xb5;A tungsten filament.</p>
<p>A total of thirty-five zircon grains underwent U&#x2013;Pb dating and trace element analysis simultaneously using LA-ICP-MS at Wuhan Sample Solution Analytical Technology Co., Ltd. The laser ablation system consisted of a GeolasPro system, including a COMPexPro 102 ArF excimer laser (193 nm wavelength, 200 mJ maximum energy) and a MicroLas optical system. Ion signal intensities were measured using an Agilent 7700e ICP-MS. Helium was used as a carrier gas, while argon served as the make-up gas, mixed with helium via a T-connector before entering the ICP. A &#x201c;wire&#x201d; signal smoothing device was employed (<xref ref-type="bibr" rid="B40">Hu et al., 2015</xref>). Zircon 91,500 and glass NIST610 were used as external standards for U&#x2013;Pb dating and trace element calibration, respectively. Each analysis included background acquisition for &#x223c;20&#x2013;30 s, followed by 50 s of data acquisition. Data processing, including background selection, integration, time-drift correction, and quantitative calibration, was performed using Excel-based ICPMSDataCal software (<xref ref-type="bibr" rid="B58">Liu et al., 2008</xref>). Concordia diagrams and weighted mean age calculations were generated using Isoplot/Ex_ver3. The laser ablation system and ICP-MS operating conditions, as well as data reduction methods, followed <xref ref-type="bibr" rid="B122">Zong et al. (2017)</xref>.</p>
</sec>
<sec id="s3-4">
<title>3.4 Oxygen-hydrogen isotope geochemistry</title>
<p>Four quartz samples were collected from the Au ore body and four from the Ag&#x2013;Pb ore body. Testing was conducted at the Analytical Testing Research Center of the Beijing Institute of Geology. The samples were first crushed, and a preliminary selection to 40&#x2013;60 mesh was conducted under a stereo microscope to ensure that the quartz mineral purity exceeded 99&#x2030;. Isotopic analysis was performed using the DZ/T 0184.19-1997 water hydrogen isotope zinc reduction method. This involved drying the samples at a low temperature to remove adsorbed water and then heating to above 600&#xb0;C to extract water from the fluid inclusions. The extracted water was then reacted with zinc to produce hydrogen, which was analyzed using mass spectrometry.</p>
<p>Oxygen isotopes were measured using the bromine pentafluoride (BrF<sub>5</sub>) method following the DZ/T 0184.13-1997 standard for silicate and oxide minerals. In this method, BrF<sub>5</sub> reacts with quartz at 500&#xb0;C&#x2013;680&#xb0;C under vacuum, releasing oxygen, which is then analyzed via mass spectrometry. The analytical precision was &#xb1;1&#x2030; for hydrogen isotopes and &#xb1;0.2&#x2030; for oxygen isotopes.</p>
<p>The homogenization temperature of the fluid inclusions in quartz and the mineral&#x2013;water oxygen isotopic fractionation equation was used to calculate the &#x3b4;<sup>18</sup>O_H<sub>2</sub>O value of the fluid. The average temperature of the fluid was taken as the representative value, and the equation used for oxygen isotope equilibrium between quartz and water was: <inline-formula id="inf1">
<mml:math id="m1">
<mml:mrow>
<mml:msup>
<mml:mn>10</mml:mn>
<mml:mn>3</mml:mn>
</mml:msup>
<mml:mo>&#x2061;</mml:mo>
<mml:mi>ln</mml:mi>
<mml:mo>&#x2061;</mml:mo>
<mml:msub>
<mml:mi mathvariant="italic">&#x3b1;</mml:mi>
<mml:mrow>
<mml:mtext>quartz</mml:mtext>
<mml:mo>&#x2212;</mml:mo>
<mml:msub>
<mml:mi mathvariant="normal">H</mml:mi>
<mml:mn>2</mml:mn>
</mml:msub>
<mml:mi mathvariant="normal">O</mml:mi>
</mml:mrow>
</mml:msub>
<mml:mo>&#x3d;</mml:mo>
<mml:mfrac>
<mml:mrow>
<mml:mn>3.42</mml:mn>
<mml:mo>&#xd7;</mml:mo>
<mml:msup>
<mml:mn>10</mml:mn>
<mml:mn>6</mml:mn>
</mml:msup>
</mml:mrow>
<mml:msup>
<mml:mi>T</mml:mi>
<mml:mn>2</mml:mn>
</mml:msup>
</mml:mfrac>
<mml:mo>&#x2212;</mml:mo>
<mml:mn>3.40</mml:mn>
</mml:mrow>
</mml:math>
</inline-formula> (<xref ref-type="bibr" rid="B18">Clayton et al., 1972</xref>).</p>
</sec>
<sec id="s3-5">
<title>3.5 Sulfur isotope geochemistry</title>
<p>
<italic>In-situ</italic> sulfur isotope analyses of the Au ore body and the Ag&#x2013;Pb ore body were conducted on drill core samples. Au-bearing pyrite, primarily from the Au mineralization stage, was identified based on deformation intensity, metamorphic characteristics, and cross-cutting relationships observed from deep to shallow levels. Galena and chalcopyrite samples were also primarily collected from the Ag&#x2013;Pb mineralization stage.</p>
<p>Polished thin sections were prepared, and suitable samples were selected through inspection under a reflected-light microscope. Sulfur isotope analysis was performed using laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) at the State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan). For clean ablation of pure sulfide phases backscattered electron (BSE) imaging also used to identifies zoning, inclusions, grain boundaries, and distinguishes sulfides from gangue minerals.</p>
<p>Sulfide samples were analyzed using a laser spot diameter of 30 &#x3bc;m, a repetition rate of 4 Hz, and a laser energy density of approximately 2.5 J/cm<sup>2</sup>. To address instrumental drift and mass bias, a standard-sample bracketing (SSB) approach was applied, while the use of a femtosecond laser ablation system mitigated matrix effects during sulfur isotope analysis of sulfides, as demonstrated in prior studies (e.g., <xref ref-type="bibr" rid="B106">Zhang et al., 2013</xref>; <xref ref-type="bibr" rid="B29">Fu et al., 2017</xref>). Data processing for the LA-MC-ICP-MS analysis was performed using Iso-Compass software, following established protocols (<xref ref-type="bibr" rid="B113">Zhang et al., 2020</xref>). The analytical precision was &#xb1;0.2&#x2030;. For further details on the procedure, refer to <xref ref-type="bibr" rid="B92">Wang et al. (2024)</xref>.</p>
</sec>
</sec>
<sec id="s4">
<title>4 Analytical results</title>
<sec id="s4-1">
<title>4.1 Zircon U&#x2013;Pb dating</title>
<p>The detailed analytical results for the zircon U&#x2013;Pb ages of gabbro (GS01) and granitic gneiss (SKS01) are presented in <xref ref-type="sec" rid="s13">Supplementary Tables S1, S2</xref>, with Concordia diagrams and cathodoluminescence (CL) images shown in <xref ref-type="fig" rid="F3">Figures 3</xref>, <xref ref-type="fig" rid="F4">4</xref>.</p>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>Showing zircon U&#x2013;Pb Concordia diagrams: <bold>(a)</bold>Gabbro sample (GS01); <bold>(b)</bold>Granitic gneiss sample (SKS01).</p>
</caption>
<graphic xlink:href="feart-13-1609741-g003.tif"/>
</fig>
<p>The zircons from GS01 are predominantly rounded or short columnar crystals with length-to-width ratios of 2:1 and exhibit no evidence of metamorphism or post-formation alteration (<xref ref-type="fig" rid="F4">Figure 4a</xref>). In contrast, the zircons from SKS01 are generally long, prismatic, or euhedral, with length-to-width ratios of 2:1 or 3:1 (<xref ref-type="fig" rid="F4">Figure 4b</xref>). The Th/U ratios of these zircons range from 0.23 to 1.14 and 0.03 to 0.4, respectively, consistent with those classified as magmatic origin (<xref ref-type="bibr" rid="B5">Belousova et al., 2002</xref>; <xref ref-type="bibr" rid="B26">Faisal et al., 2020</xref>; <xref ref-type="bibr" rid="B68">Phyo et al., 2025a</xref>; <xref ref-type="bibr" rid="B69">Phyo et al., 2025b</xref>).</p>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>Representative Cathodoluminescence (CL) Images of Zircons. <bold>(a)</bold> Gabbro sample (GS01); <bold>(b)</bold> Granitic gneiss sample (SKS01).</p>
</caption>
<graphic xlink:href="feart-13-1609741-g004.tif"/>
</fig>
<p>A total of seventeen spots on seventeen zircon grains from GS01 were analyzed, yielding a weighted mean <sup>206</sup>Pb/<sup>238</sup>U age of 448.5 &#xb1; 2.5 Ma (MSWD &#x3d; 0.17; <xref ref-type="fig" rid="F3">Figure 3a</xref>), representing the crystallization age of the Shuangkoushan gabbro intrusion.</p>
<p>For SKS01, eighteen zircon grains were analyzed, forming two distinct age groups. The first group, consisting of 11 measurements, yielded a weighted mean <sup>206</sup>Pb/<sup>238</sup>U age of 839.8 &#xb1; 5 Ma (MSWD &#x3d; 0.69; Th/U average 0.16). The second group, comprising seven measurements, yielded a weighted mean <sup>206</sup>Pb/<sup>238</sup>U age of 924 &#xb1; 6.3 Ma (MSWD &#x3d; 0.35; Th/U average 0.17), representing the crystallization age of the granitic gneiss (<xref ref-type="fig" rid="F3">Figure 3b</xref>).</p>
</sec>
<sec id="s4-2">
<title>4.2 Hydrogen- oxygen isotopic analysis</title>
<p>The results of the H&#x2013;O isotopic analysis of quartz veins from the two metallogenic stages are presented in <xref ref-type="sec" rid="s13">Supplementary Table S3</xref>. In the Ag-Pb mineralization stage, &#x3b4;D<sub>V&#x2212;</sub>SMOW values range from &#x2212;108.2&#x2030; to &#x2212;113.8&#x2030;, with an average of &#x2212;110.6&#x2030;. The &#x3b4;18OH2O-SMOW values range from 6.45&#x2030; to 6.55&#x2030;, with an average of 6.48&#x2030;. The &#x3b4;18OV-SMOW values range from 14.1&#x2030; to 14.3&#x2030;, with an average of 14.17&#x2030;. In contrast, during the Au mineralization stage, &#x3b4;DV&#x2212;SMOW values range from &#x2212;72.9&#x2030; to &#x2212;81.5&#x2030;, with an average of &#x2212;76.2&#x2030;. The &#x3b4;18OH2O-SMOW values range from 3.45&#x2030; to 4.95&#x2030;, with an average of 3.97&#x2030;. The &#x3b4;18OV<sub>-SMOW</sub> values range from 10.4&#x2030; to 13.9&#x2030;, with an average of 11.9&#x2030;.</p>
</sec>
<sec id="s4-3">
<title>4.3 Sulfur isotopic analysis</title>
<p>The results of the <italic>in situ</italic> sulfur isotope analysis are presented in <xref ref-type="sec" rid="s13">Supplementary Table S4</xref>. The tests were conducted on pyrite, galena, and chalcopyrite from drillhole samples representing different ore-bearing types at varying depths. The isotopic composition of pyrite from the Au mineralization stage shows significant variation, with &#x3b4;<sup>34</sup>S values ranging from &#x2b;4.8&#x2030; to &#x2b;10&#x2030;, averaging &#x2b;7.05&#x2030;. Within this dataset: Py1 ranges from &#x2b;8.1&#x2030; to &#x2b;10&#x2030; (average: &#x2b;9.3&#x2030;), Py2 ranges from &#x2b;5.9&#x2030; to &#x2b;7&#x2030; (average: &#x2b;6.4&#x2030;), and Py3 ranges from &#x2b;4.8&#x2030; to &#x2b;5.6&#x2030; (average: &#x2b;5.4&#x2030;).</p>
<p>In contrast, the sulfur isotopic composition exhibits less variation in the Ag&#x2013;Pb mineralization stage. The &#x3b4;<sup>34</sup>S values for galena range from &#x2b;0.2&#x2030; to &#x2b;2.3&#x2030; (average: &#x2b;1.4&#x2030;), while those for chalcopyrite range from &#x2b;1.0&#x2030; to &#x2b;3.3&#x2030; (average: &#x2b;1.9&#x2030;).</p>
</sec>
<sec id="s4-4">
<title>4.4 Ore paragenesis</title>
<p>In the Shuangkoushan area, two main mineralization stages and five sub-stages have been identified based on cross-cutting relationships among ore-bearing veinlets, observed mineral textures, and assemblages. These stages (<xref ref-type="fig" rid="F5">Figure 5</xref>) include syn-orogenic Au stage (pre-ore, quartz&#x2013;pyrite, and polymetallic sulfide stage), and post-orogenic Ag&#x2013;Pb stage (Ag&#x2013;Pb stage and carbonate stage). Additionally, four types of pyrite were recognized based on textures and paragenetic relationships. During the pre-ore stage (I), the host rocks were subjected to intense tectonic reworking and alteration due to orogenic processes, including strong metamorphism and deformation (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>). Au-bearing pyrite (Py1) began to pre-enrich the rocks, occurring mainly as fine subhedral grains&#x2014;either sparsely disseminated or in bamboo-shaped veinlets&#x2014;within altered mylonites along the shear zone. Some Py1 is intergrown with Py2 in quartz&#x2013;pyrite veins (stage II), accompanied by gangue minerals such as serpentine, chlorite, epidote, and quartz (<xref ref-type="fig" rid="F6">Figures 6a,b</xref>). Py1 frequently displays evidence of dissolution, metamorphism, and secondary overgrowth from subsequent hydrothermal events. Both Py1 and associated quartz were later crushed, transformed, and metamorphosed by fault activity and hydrothermal overprinting, experiencing both brittle and ductile deformations. Sericite alteration was widespread during this stage. Due to intense structural reworking and alteration, the original composition of the host rocks cannot be accurately determined.</p>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>Paragenetic sequence of the Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposit.</p>
</caption>
<graphic xlink:href="feart-13-1609741-g005.tif"/>
</fig>
<fig id="F6" position="float">
<label>FIGURE 6</label>
<caption>
<p>Backscattered electron (BSE) images illustrating sulfide textures and relationships. <bold>(a&#x2013;b)</bold>Py1 metasomatized by Py2; <bold>(c)</bold>Py2 metasomatized by Py3, and Py3 further metasomatized by chalcopyrite; <bold>(d&#x2013;f)</bold>Galena and stromeyerite, along with quartz, filling zonations and fractures in Py4. Py, Pyrite; Sym, Stromeyerite; Ccp, Chalcopyrite; Qz, Quartz; Gn, Galena.</p>
</caption>
<graphic xlink:href="feart-13-1609741-g006.tif"/>
</fig>
<p>The quartz&#x2013;pyrite stage (II) represents the main phase of Au mineralization and corresponds to a transition from ductile to brittle deformation structures. Au-bearing pyrite (Py2) is typically subhedral and fine-grained, occurring in disseminated, veinlet-disseminated, and veinlet-type ores hosted in quartz fractures. Py2 often replaces or overgrows Py1 (<xref ref-type="fig" rid="F6">Figure 6b</xref>). Gangue minerals include quartz and sericite. The dominant alteration style during this stage was quartz&#x2013;pyrite alteration, with minor sericitization (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>).</p>
<p>By the polymetallic sulfide stage (III), Au mineralization had significantly weakened. The primary minerals were quartz and sericite, with sparse ore minerals including pyrite (Py3) and chalcopyrite. Py2 was overgrown by Py3 (<xref ref-type="fig" rid="F6">Figure 6c</xref>), which was in turn replaced by chalcopyrite. Silicification dominated the alteration assemblage, accompanied by minor pyrite alteration.</p>
<p>The Ag&#x2013;Pb polymetallic sulfide stage (IV) marks the main phase of Ag&#x2013;Pb mineralization. The ore bodies occur as veins or lenses that cut across the earlier Au-bearing zones (<xref ref-type="fig" rid="F6">Figures 6a&#x2013;c</xref>). It can observe in the field photograph from the preliminary research work of this area by <xref ref-type="bibr" rid="B14">Chen et al. (2018b)</xref>. Many Au-bearing breccias were overprinted by Ag&#x2013;Pb-bearing hydrothermal deposits. Pyrite (Py4) is mostly euhedral and occasionally displays weak zoning (<xref ref-type="fig" rid="F6">Figures 6d, e</xref>).</p>
<p>In the carbonate stage (V), the mineral assemblage becomes simple in composition, dominated by quartz and calcite, with minor chalcopyrite and pyrite. These sulfides have been partially oxidized to malachite and limonite (<xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>).</p>
</sec>
</sec>
<sec sec-type="discussion" id="s5">
<title>5 Discussion</title>
<sec id="s5-1">
<title>5.1 Syn-orogenic Au to post-orogenic Ag-Pb mineralization</title>
<p>The metallogenic framework of northern Qaidam reflects its dynamic tectonic history. The formation ages of the ore deposits are consistent with the regional tectonic evolution, encompassing: oceanic subduction (520&#x2013;460 Ma), continental collision (460&#x2013;440 Ma), and Continental Exhumation with Orogenic Fluid Modification (430&#x2013;420 Ma) (<xref ref-type="bibr" rid="B12">Chen et al., 2010</xref>; <xref ref-type="bibr" rid="B79">Shuguang et al., 2009</xref>; <xref ref-type="bibr" rid="B114">Zhang et al., 2015</xref>; <xref ref-type="bibr" rid="B85">Sun et al., 2019</xref>). The northern Qaidam margin and East Kunlun Mountains host thirteen structurally controlled Au deposits, each of which formed during successive phases of orogenic activity. The primary episodes of Au mineralization occurred during the Silurian-Triassic periods, with ages ranging from &#x223c;425 Ma to &#x223c;218 Ma. These ages decrease progressively from north to south (<xref ref-type="bibr" rid="B108">Zhang et al., 2005</xref>).</p>
<p>Geochronological data provide critical constraints on the timing of syn-orogenic Au mineralization and its transition to post-orogenic Ag-Pb systems. In the Shuangkoushan area, the formation of the metallic ore body was associated with the metabasaltic rocks of the Tanjianshan Group, which host numerous orogenic Au deposits, all controlled by the NW&#x2013;SE-trending ductile shear zone of the North Qaidam Orogeny (<xref ref-type="bibr" rid="B110">Zhang et al., 2007</xref>). For instance, <xref ref-type="bibr" rid="B30">Fu et al. (2016)</xref> measured a sericite Ar&#x2013;Ar age of 399 &#xb1; 4 Ma for the Xitieshan ductile shear zone. <xref ref-type="bibr" rid="B99">Xu et al. (2003)</xref> obtained muscovite Ar&#x2013;Ar ages ranging between 402 Ma and 406 Ma for the Northern Qaidam ultra-high-pressure ductile shear zone (UP &#x3d; 443&#x2013;473 Ma and UHP &#x3d; 420&#x2013;426 Ma by <xref ref-type="bibr" rid="B79">Shuguang et al., 2009</xref>). <xref ref-type="bibr" rid="B109">Zhang et al. (2001)</xref> determined a muscovite Ar&#x2013;Ar age of 401 Ma for the NW&#x2013;SE-trending ductile shear zone in the Tanjianshan Group. Additionally, <xref ref-type="bibr" rid="B110">Zhang et al. (2007)</xref> reported a sericite Ar&#x2013;Ar age of 409.4 &#xb1; 2.3 Ma from the NW&#x2013;SE-trending ore-controlling shear zone of the Tanjianshan deposit, consistent with the earlier Ar&#x2013;Ar age of 409 &#xb1; 2.3 Ma for metamorphic sericite from the similarly oriented (NW&#x2013;SE) Au ore-controlling shear zone of the Qinglonggou deposit (<xref ref-type="bibr" rid="B108">Zhang et al., 2005</xref>). These ages fall within the period of ductile shear activity, indicating that ductile shear deformation and metamorphism played a major role in the formation of the Au deposits. The Shuangkoushan Au orebodies are also controlled by the NW&#x2013;SE trending ductile shear zone, suggesting that they may have formed during this time. Furthermore, orogenic Au deposits worldwide are typically interpreted to have formed within collision or accretion zones during peak or late-collision metamorphism (<xref ref-type="bibr" rid="B34">Goldfarb et al., 2001</xref>). In this study, we obtained an LA-ICP-MS zircon U&#x2013;Pb age of 448.5 &#xb1; 2.5 Ma for Shuangkoushan gabbro (<xref ref-type="fig" rid="F3">Figure 3a</xref>; <xref ref-type="sec" rid="s13">Supplementary Table S1</xref>), which is likely consistent with the formation age (443 &#xb1; 2.9 Ma; <xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>) of the Shuangkoushan ore-bearing metabasaltic continental back-arc basin related rocks (<xref ref-type="bibr" rid="B32">Gao et al., 2011</xref>; <xref ref-type="bibr" rid="B114">Zhang et al., 2015</xref>; <xref ref-type="bibr" rid="B85">Sun et al., 2019</xref>). The age of the ductile shear zone and Au-bearing quartz vein (402 &#xb1; 4.2 Ma; <xref ref-type="bibr" rid="B105">Yu et al., 2020</xref>) in the Shuangkoushan area is younger than that of the host rocks, and therefore likely represents the timing of Au mineralization to some extent.</p>
<p>For the Ag&#x2013;Pb mineralization stage, work by <xref ref-type="bibr" rid="B97">Xu (2012)</xref> on inclusions in galena and sphalerite yielded an Rb&#x2013;Sr mineralization age of 347.9 &#xb1; 3.5 Ma. The zircon U&#x2013;Pb age obtained for the granitic gneisses is 835 &#xb1; 6.3 Ma and 924 &#xb1; 6.3 Ma, indicating multistage crystallization (<xref ref-type="fig" rid="F3">Figure 3b</xref>; <xref ref-type="sec" rid="s13">Supplementary Table S2</xref>). These oldest ages represent the continental rifting stage of Rodinia, with corresponding ages (700&#x2013;850 Ma) discovered by <xref ref-type="bibr" rid="B119">Zhu et al. (2015)</xref> on the northern margin of the Qaidam Basin. These results suggest that the Ag-Pb ore-forming fluids and metals were not sourced from the adjacent Neoproterozoic granitic gneiss. The North Qaidam granites age is 386&#x2013;356 Ma postdate UHP metamorphism (438&#x2013;420 Ma) of the deeply subducted continental crust, confirming their post-collisional origin (<xref ref-type="bibr" rid="B83">Sun G. C. et al., 2022</xref>).</p>
</sec>
<sec id="s5-2">
<title>5.2 Source of ore-forming fluids</title>
<p>Fluids transport thermal energy and ore-bearing minerals in various forms, such as hydrothermal fluids, CO<sub>2</sub>-rich fluids, geothermal fluids, etc., (<xref ref-type="bibr" rid="B22">Deng et al., 2000</xref>; <xref ref-type="bibr" rid="B49">Kesler, 2005</xref>; <xref ref-type="bibr" rid="B41">Huan-zhang, 2008</xref>). Previous studies (<xref ref-type="bibr" rid="B126">Chen et al., 2023</xref>) have suggested that multiple fluid sources contribute to the formation of ore deposits: Hydrous fluids liberated by metamorphic dehydration (<xref ref-type="bibr" rid="B102">Yardley and Cleverley, 2015</xref>), Magmatic&#x2013;hydrothermal fluids (<xref ref-type="bibr" rid="B51">Lang and Baker, 2001</xref>; <xref ref-type="bibr" rid="B87">Treloar et al., 2015</xref>), Deep metamorphic dehydration fluids or magmatic&#x2013;hydrothermal fluids convecting with meteoric water during uplift (<xref ref-type="bibr" rid="B44">Jenkin et al., 1994</xref>), CO<sub>2</sub>-rich fluids released when the mantle interacts with other hydrothermal fluids (<xref ref-type="bibr" rid="B66">Phillips and Evans, 2004</xref>). During the Au mineralization stage in the Shuangkoushan area, the values of &#x3b4;D<sub>V-SMOW</sub> and &#x3b4;<sup>18</sup>O<sub>H2O-SMOW</sub> (<xref ref-type="sec" rid="s13">Supplementary Table S3</xref>) are lower than typical values for orogenic Au deposits (&#x3b4;D<sub>V-SMOW</sub> &#x3d; &#x2212;20&#x2030; to &#x2212;80&#x2030;; &#x3b4;<sup>18</sup>O<sub>H2O-SMOW</sub> &#x3d; &#x2b;5&#x2030; to &#x2b;10&#x2030;; <xref ref-type="bibr" rid="B48">Kerrich et al., 2000</xref>; <xref ref-type="bibr" rid="B118">Zheng and Chen, 2000</xref>). In the &#x3b4;D<sub>V-SMOW</sub> vs. &#x3b4;<sup>18</sup>O<sub>H2O-SMOW</sub> plot (<xref ref-type="fig" rid="F5">Figure 5</xref>), the Au samples trend between metamorphic fluids and meteoric water, with values lower than those of typical orogenic Au deposits (<xref ref-type="bibr" rid="B35">Groves et al., 1998</xref>; <xref ref-type="bibr" rid="B36">2003</xref>; <xref ref-type="bibr" rid="B33">Goldfarb and Groves, 2015</xref>) and local deposits such as Hongliugou (<xref ref-type="sec" rid="s13">Supplementary Table S5</xref>). However, these values align with the variations observed in orogenic Au deposits in China (<xref ref-type="bibr" rid="B115">Zhang, 2011</xref>; <xref ref-type="bibr" rid="B27">Fan et al., 2012</xref>; <xref ref-type="bibr" rid="B88">Wang, 2012</xref>). This suggests that the Au mineralization fluids originated from metamorphic fluids mixed with a substantial meteoric water component. During the Ag&#x2013;Pb mineralization stage in Shuangkoushan, the samples in the plot trend toward magmatic water alongside meteoric water (<xref ref-type="fig" rid="F7">Figure 7</xref>; <xref ref-type="sec" rid="s13">Supplementary Table S3</xref>). This indicates that Ag&#x2013;Pb mineralization fluids were sourced primarily from primitive magmatic water with a minor meteoric water component.</p>
<fig id="F7" position="float">
<label>FIGURE 7</label>
<caption>
<p>Plot of &#x3b4;D versus &#x3b4;<sup>18</sup>O for the ore-forming fluids of the Shuangkoushan Au&#x2013;Ag&#x2013;Pb ore field (modified after <xref ref-type="bibr" rid="B74">Sheppard, 1977</xref>). Data regarding orogenic Au deposits and Carlin-type Au deposits in China are compiled from multiple sources (<xref ref-type="bibr" rid="B112">Zhang et al., 2000</xref>; <xref ref-type="bibr" rid="B76">Shi et al., 2010</xref>; <xref ref-type="bibr" rid="B12">Chen et al., 2010</xref>; <xref ref-type="bibr" rid="B117">Zhao, 2011</xref>; <xref ref-type="bibr" rid="B100">Xue, 2011</xref>; <xref ref-type="bibr" rid="B115">Zhang, 2011</xref>; <xref ref-type="bibr" rid="B55">Liang et al., 2011</xref>; <xref ref-type="bibr" rid="B60">Lu et al., 2011</xref>; <xref ref-type="bibr" rid="B27">Fan et al., 2012</xref>; <xref ref-type="bibr" rid="B88">Wang, 2012</xref>; <xref ref-type="bibr" rid="B96">Xia et al., 2013</xref>).</p>
</caption>
<graphic xlink:href="feart-13-1609741-g007.tif"/>
</fig>
</sec>
<sec id="s5-3">
<title>5.3 Potential source of Au-Ag-Pb</title>
<p>Previous studies have identified several sources of metals in ore deposits such as metamorphosed rocks (<xref ref-type="bibr" rid="B67">Phillips and Powell, 2010</xref>), intrusion-related primary magmatic sources (<xref ref-type="bibr" rid="B51">Lang and Baker, 2001</xref>; <xref ref-type="bibr" rid="B37">Hart et al., 2004</xref>), carbonaceous, pyrite-rich sedimentary rocks (<xref ref-type="bibr" rid="B20">Daliran, 2007</xref>; <xref ref-type="bibr" rid="B31">Gaboury, 2013</xref>), and metabasaltic rocks (<xref ref-type="bibr" rid="B3">Augustin et al., 2016</xref>). Among these, metabasaltic rocks have a greater potential to serve as a primary source of remobilized Au during the metamorphogenic formation of orogenic Au deposits such as, Wona-Kona Au deposit (<xref ref-type="bibr" rid="B6">Bierlein and Craw, 2009</xref>; <xref ref-type="bibr" rid="B2">Augustin and Gaboury, 2017</xref>). Evaluating the origins of metals and fluids particularly during the Au mineralization stage, requires identifying the source of sulfur (<xref ref-type="bibr" rid="B10">Chang et al., 2008</xref>).</p>
<p>The pyrite &#x3b4;<sup>34</sup>S values in this study ranging from &#x2b;4.8&#x2030; to &#x2b;10.0&#x2030; (<xref ref-type="sec" rid="s13">Supplementary Table S4</xref>), overlap with those of biogenic sulfide (&#x3b4;<sup>34</sup>S &#x3d; 2&#x2030;&#x2013;46&#x2030;; <xref ref-type="bibr" rid="B23">Detmers et al., 2001</xref>) and metamorphic rocks (&#x3b4;<sup>34</sup>S &#x3d; &#x2212;20&#x2030; to &#x2b;20&#x2030;) but are higher than those of magmatic rocks (&#x3b4;<sup>34</sup>S &#x3d; &#x2212;1.1&#x2030;&#x2013;3.5&#x2030;; <xref ref-type="bibr" rid="B61">McClenaghan, 2013</xref>). Previous research has indicated that there is no biological component in sulfides from volcanic rocks and that sulfur concentrations in minerals are largely preserved in ore deposits subjected to metamorphism up to the amphibolite facies. Beyond this stage, sulfur content increases with the degree of metamorphism, reaching up to 2000 &#x3bc;g/g in amphibolite facies fluids (<xref ref-type="bibr" rid="B70">Rauchenstein-Martinek et al., 2014</xref>; <xref ref-type="bibr" rid="B71">Rauchenstein-Martinek et al., 2016</xref>). As shown in <xref ref-type="sec" rid="s13">Supplementary Table S4</xref>, the &#x3b4;<sup>34</sup>S value for pyrite gradually decreases from deep to shallow samples (9.3 &#x2192; 6.9 &#x2192; 6.1 &#x2192; 5.4), correlating with a decrease in metamorphic intensity (<xref ref-type="fig" rid="F8">Figure 8</xref>). Additionally, most orogenic Au deposits in the western part of North Qaidam, including the Yuka, Yeluotuoquan, Qianmeiling, and Hongliugou deposits, exhibit a spatial, temporal, and genetic association with Tanjianshan meta-basaltic rocks. These rocks are favorable for Au mineralization and show positive anomalies in elements such as Ag, As, Au, B, Bi, Sb, Te, and W (<xref ref-type="bibr" rid="B35">Groves et al., 1998</xref>). The Tanjianshan meta-basaltic rocks contain higher concentrations of Au, Cr, and Ni (Au: 19.09 &#xd7; 10<sup>&#x2212;9</sup>; Cr: 167.40 &#xd7; 10<sup>&#x2212;6</sup>; Ni: 64.36 &#xd7; 10<sup>&#x2212;6</sup>) compared to local average values (Au: 1.35 &#xd7; 10<sup>&#x2212;9</sup>; Cr: 55.4 &#xd7; 10<sup>&#x2212;6</sup>; Ni: 9.94 &#xd7; 10<sup>&#x2212;6</sup>). These characteristics are similar to those of Au-bearing greenstone belts worldwide (<xref ref-type="bibr" rid="B38">Henley et al., 1976</xref>; <xref ref-type="bibr" rid="B62">McKeag et al., 1989</xref>). Together with the deposit geology and H&#x2013;O isotopic results (<xref ref-type="fig" rid="F9">Figure 9</xref>), these findings suggest that the Au ore-forming material was sourced from the Syn-orogenic meta-basaltic rocks of the Tanjianshan Group, which have relatively high background Au values.</p>
<fig id="F8" position="float">
<label>FIGURE 8</label>
<caption>
<p>Sulfur isotopic composition of pyrite from the Au mineralization stage, and chalcopyrite and galena from the Ag&#x2013;Pb mineralization stage of the Shuangkoushan Au-Ag-Pb deposits.</p>
</caption>
<graphic xlink:href="feart-13-1609741-g008.tif"/>
</fig>
<fig id="F9" position="float">
<label>FIGURE 9</label>
<caption>
<p>Summary bar diagram showing &#x3b4;<sup>18</sup>O<sub>quartz (&#x2030;) V&#x2013;SMOW</sub> values for the Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposit (after <xref ref-type="bibr" rid="B1">Anderson et al., 2004</xref>).</p>
</caption>
<graphic xlink:href="feart-13-1609741-g009.tif"/>
</fig>
<p>During the Ag&#x2013;Pb mineralization stage in study area, &#x3b4;<sup>34</sup>S values for galena range from 0.2&#x2030; to 2.3&#x2030; (<xref ref-type="sec" rid="s13">Supplementary Table S4</xref>), while those for chalcopyrite range from 1.0&#x2030; to 3.3&#x2030;. These values fall within the typical range of magmatic sulfur (0&#x2030; &#xb1; 3&#x2030;; <xref ref-type="bibr" rid="B11">Chaussidon and Lorand, 1990</xref>) and are consistent with those observed in the large-scale Xitieshan Pb&#x2013;zinc deposits (galena &#x3b4;<sup>34</sup>S &#x3d; 2.0&#x2030;&#x2013;2.2&#x2030;; <xref ref-type="bibr" rid="B89">Wang et al., 2009</xref>; <xref ref-type="bibr" rid="B120">Zhu et al., 2010</xref>; <xref ref-type="fig" rid="F10">Figure 10</xref>). This suggests that the Ag&#x2013;Pb ore-forming material was primarily sourced from post-orogenic deep magma or Devonian granite.</p>
<fig id="F10" position="float">
<label>FIGURE 10</label>
<caption>
<p>Range of sulfur isotope compositions in the Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposit compared with those in other deposits and geological settings (after <xref ref-type="bibr" rid="B39">Hoefs, 1975</xref>). Data for the Xitieshan Pb&#x2013;Zn deposit is from <xref ref-type="bibr" rid="B120">Zhu et al. (2010)</xref>.</p>
</caption>
<graphic xlink:href="feart-13-1609741-g010.tif"/>
</fig>
</sec>
<sec id="s5-4">
<title>5.4 Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposit formation</title>
<p>The Qaidam Orogenic Belt is part of the northern margin of the North China Craton and has played a significant role in the formation of the Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposit. The belt is characterized by a series of metamorphic and magmatic rocks, which have been shaped by the tectonic evolution of the region (<xref ref-type="bibr" rid="B101">Yang and Santosh, 2020</xref>; <xref ref-type="bibr" rid="B54">Li and Yan, 2023</xref>). The geological features, isotopic data, and comparison with orogenic deposits in the Shuangkoushan area (<xref ref-type="sec" rid="s13">Supplementary Table S5</xref>) all indicate that the Au-Ag&#x2013;Pb deposit formed through two distinct mineralization stages, which separately produced Au and Ag&#x2013;Pb ore bodies at different times and during different phases (syn- and post-) of the North Qaidam orogeny. The syn-post tectonic framework of the Qaidam Orogenic Belt is a result of multiple tectonic phases, including Cambrian&#x2212;Ordovician magmatic arc formation, Silurian&#x2212;Devonian orogeny, Permian&#x2212;Triassic magmatic arc, and Cenozoic collisional magmatism by UHPM exhumation and collapse (<xref ref-type="bibr" rid="B90">Wang et al., 2014</xref>; <xref ref-type="bibr" rid="B127">Chen et al., 2022a</xref>; <xref ref-type="bibr" rid="B91">Wang et al., 2023</xref>; <xref ref-type="bibr" rid="B93">Wu et al., 2024</xref>; <xref ref-type="bibr" rid="B124">Jiang et al., 2025</xref>).</p>
<p>The Shuangkoushan Au-ore body is a metamorphic-hydrothermal type deposit genetically associated with syn-orogenic metamorphism and deformation. In contrast, the Ag&#x2013;Pb ore body is an intrusion-related magmatic-hydrothermal type deposit. It was genetically associated to magmatic activity along extensional faults during the post-collision orogeny. These deposits formed through ore-bearing hydrothermal infill, as ore-bearing magma crystallized and differentiated from deep to shallow depths during the regional post-collision extension period, superseding the earlier Au ore body. The Ag&#x2013;Pb ore-forming fluids originated from deep magma or Devonian granite.</p>
<p>Based on the results of this study and the regional tectonic background of the area, a conceptual model suggests that the Shuangkoushan deposits underwent a two-stage mineralization process (<xref ref-type="fig" rid="F11">Figure 11</xref>). Stage I: Subduction related Ordovician basaltic rocks with high background Au values underwent metamorphism and deformation during the syn-orogenic process. As a result, fluids were released through dehydration, extracting Au elements. The Au-bearing fluids ascended along faults. In the ductile to brittle&#x2013;ductile transition zone, Au precipitated from the fluids and became enriched (<xref ref-type="fig" rid="F11">Figure 11</xref>). Stage II: After regional metamorphism and deformation reached their peak, stress began to relax, leading to detachment along the fault zone. Deep crustal material underwent decompression and partial melting, generating an Ag&#x2013;Pb-bearing magmatic melt that ascended along fault structures. Crystallization and differentiation occurred near the surface, filling tensile fractures that cut across the earlier Au ore body (<xref ref-type="fig" rid="F11">Figure 11</xref>).</p>
<fig id="F11" position="float">
<label>FIGURE 11</label>
<caption>
<p>Conceptual model of the Shuangkoushan Au&#x2013;Ag&#x2013;galena deposit (after <xref ref-type="bibr" rid="B16">Chen, 2013</xref>).</p>
</caption>
<graphic xlink:href="feart-13-1609741-g011.tif"/>
</fig>
</sec>
</sec>
<sec sec-type="conclusion" id="s6">
<title>6 Conclusion</title>
<p>The Tanjianshan meta-basaltic rocks host the Shuangkoushan Au&#x2013;Ag&#x2013;Pb deposits, located adjacent to gabbro intrusions (448 Ma) and granitic gneisses (835 and 924 Ma) within the North Qaidam Orogenic Belt. In the Shuangkoushan ore bodies, multistage pyrite formation&#x2014;classified as Py1, Py2, Py3, and Py4&#x2014;plays a key role in constraining both syn-orogenic Au mineralization (pre-ore (P1), quartz&#x2013;pyrite (P2), and polymetallic sulfide (P3) stages) and post-orogenic Ag&#x2013;Pb mineralization (Ag&#x2013;Pb sulfide (P4) and carbonate stages). The oxygen, hydrogen, and sulfur isotopic compositions of the Shuangkoushan ore bodies support the following conclusions:<list list-type="simple">
<list-item>
<p>(1) At the stage of Au mineralization, the mineralizing fluids were derived from metamorphic fluids mixed with a substantial meteoric water component, with the ore-forming material sourced from the syn-orogenic basaltic rocks.</p>
</list-item>
<list-item>
<p>(2) At the stage of Ag&#x2013;Pb mineralization, the mineralizing fluids originated from primitive magmatic fluids, supplemented by a minor component of meteoric water, with the ore-forming material sourced from post-orogenic deep-seated magma or Devonian granite.</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 sec-type="author-contributions" id="s8">
<title>Author contributions</title>
<p>JY: Investigation, Writing &#x2013; original draft. DL: Conceptualization, Methodology, Writing &#x2013; original draft. YZ: Funding acquisition, Writing &#x2013; original draft. BM: Conceptualization, Investigation, Methodology, Writing &#x2013; original draft. JW: Data curation, Project administration, Software, Writing &#x2013; original draft. GS: Investigation, Methodology, Writing &#x2013; original draft. RX: Conceptualization, Data curation, Writing &#x2013; original draft. JK: Conceptualization, Supervision, Writing &#x2013; review and editing. AT: Writing &#x2013; review and editing.</p>
</sec>
<sec sec-type="funding-information" id="s9">
<title>Funding</title>
<p>The author(s) declare that financial support was received for the research and/or publication of this article. This research was financially supported by the Project of the State Key Laboratory of Ni &#x26; Co Associated Mineral Resources Develo and Comprehensive Utilization (No. JKDGNZ26Z202406), the National Natural Science Foundation of China (Grant Nos. 41230311 and 41572069), and the China Geological Survey Project (Grant No. 12120113032800).</p>
</sec>
<ack>
<p>We gratefully acknowledge all project members and the State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan), for their support.</p>
</ack>
<sec sec-type="COI-statement" id="s10">
<title>Conflict of interest</title>
<p>The 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="ai-statement" id="s11">
<title>Generative AI statement</title>
<p>The author(s) declare that no Generative AI was used in the creation of this manuscript.</p>
</sec>
<sec sec-type="disclaimer" id="s12">
<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>
<sec sec-type="supplementary-material" id="s13">
<title>Supplementary material</title>
<p>The Supplementary Material for this article can be found online at: <ext-link ext-link-type="uri" xlink:href="https://www.frontiersin.org/articles/10.3389/feart.2025.1609741/full#supplementary-material">https://www.frontiersin.org/articles/10.3389/feart.2025.1609741/full&#x23;supplementary-material</ext-link>
</p>
<supplementary-material xlink:href="Table1.xlsx" id="SM1" mimetype="application/xlsx" xmlns:xlink="http://www.w3.org/1999/xlink"/>
</sec>
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