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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">1128692</article-id>
<article-id pub-id-type="doi">10.3389/feart.2023.1128692</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>C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub> tricyclic terpanes abundance patterns: Origin and application to depositional environment identification</article-title>
<alt-title alt-title-type="left-running-head">Wang 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.2023.1128692">10.3389/feart.2023.1128692</ext-link>
</alt-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Wang</surname>
<given-names>Aiguo</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
<uri xlink:href="https://loop.frontiersin.org/people/2147129/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Li</surname>
<given-names>Chunyu</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Li</surname>
<given-names>Long</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Pu</surname>
<given-names>Renhai</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Yang</surname>
<given-names>Zeguang</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Zhu</surname>
<given-names>Nan</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Guo</surname>
<given-names>Kai</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
</contrib-group>
<aff id="aff1">
<sup>1</sup>
<institution>State Key Laboratory of Continental Dynamics</institution>, <institution>Department of Geology</institution>, <institution>Northwest University</institution>, <addr-line>Xi&#x2019;an</addr-line>, <country>China</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Department of Earth and Atmospheric Sciences</institution>, <institution>University of Alberta</institution>, <addr-line>Edmonton</addr-line>, <addr-line>AB</addr-line>, <country>Canada</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/2076639/overview">Jiyuan Yin</ext-link>, Chinese Academy of Geological Sciences (CAGS), 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/2149869/overview">Feng Guo</ext-link>, Xi&#x2019;an Shiyou University, China</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/2151194/overview">Jiawang Ge</ext-link>, Southwest Petroleum University, China</p>
</fn>
<corresp id="c001">&#x2a;Correspondence: Aiguo Wang, <email>wag@nwu.edu.cn</email>
</corresp>
<fn fn-type="other">
<p>This article was submitted to Petrology, a section of the journal Frontiers in Earth Science</p>
</fn>
</author-notes>
<pub-date pub-type="epub">
<day>19</day>
<month>01</month>
<year>2023</year>
</pub-date>
<pub-date pub-type="collection">
<year>2023</year>
</pub-date>
<volume>11</volume>
<elocation-id>1128692</elocation-id>
<history>
<date date-type="received">
<day>21</day>
<month>12</month>
<year>2022</year>
</date>
<date date-type="accepted">
<day>09</day>
<month>01</month>
<year>2023</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2023 Wang, Li, Li, Pu, Yang, Zhu and Guo.</copyright-statement>
<copyright-year>2023</copyright-year>
<copyright-holder>Wang, Li, Li, Pu, Yang, Zhu and Guo</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>Reconstruction of paleo-depositional environments in a sedimentary basin is often obstructed by the absence of typical environmental indicators in sedimentary rocks. Here, we propose a biomarker method using C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub> tricyclic terpanes (TTs) as a tracer, which is simple in analysis but robust to provide reliable and detailed environmental information. Based on the analysis of 271 C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data from 32 basins in 18 countries, we observed a relationship between C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns and depositional environments. This relationship was attributed to the control of depositional environments on the input proportions of plankton and terrigenous plants, which act as two end-member precursors for the TTs in a depositional system. The various mixing proportions between these two end-members result in different C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns associated with different depositional environments, e.g., C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3e;C<sub>23</sub>TT in river-lake transitional, C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT in marine or saline lacustrine environments, C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3e;C<sub>23</sub>TT in freshwater lacustrine and C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3c;C<sub>23</sub>TT in marine-continental transitional environments. In addition, the C<sub>23</sub>/C<sub>21</sub>TT ratio increases with elevated salinity of depositional water, and the C<sub>21</sub>/C<sub>20</sub>TT ratio increases with increasing water depths. Based on these observations, a discrimination diagram using C<sub>23</sub>/C<sub>21</sub>TT vs. C<sub>21</sub>/C<sub>20</sub>TT was developed for environmental identification. The validity of this C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method is well demonstrated by the rock samples with typical environmental indicators. This method is applicable in a broad spectrum of rocks and in maturities up to 2.4%Ro. Its strength was shown by a case study of a complex depositional system in the East China Sea Basin, which has been strongly affected by eustasy.</p>
</abstract>
<kwd-group>
<kwd>tricyclic terpanes</kwd>
<kwd>depositional environment</kwd>
<kwd>biomarker</kwd>
<kwd>East China Sea Basin</kwd>
<kwd>environmental identification</kwd>
</kwd-group>
</article-meta>
</front>
<body>
<sec id="s1">
<title>1 Introduction</title>
<p>Reconstruction of paleo-depositional environment is critical in oil-gas exploration, paleoclimatic and paleoenvironmental studies. Conventional methods for environmental reconstruction mostly rely on sedimentary, petrological and/or mineralogical characterizations (e.g., <xref ref-type="bibr" rid="B37">Oskay et al., 2019</xref>; <xref ref-type="bibr" rid="B41">Pichat et al., 2021</xref>), paleontological record (e.g., <xref ref-type="bibr" rid="B22">Heard et al., 2020</xref>), and/or geochemical tracing (e.g., <xref ref-type="bibr" rid="B21">Govind et al., 2021</xref>). For example, lithology, sedimentary/biogenic structures, rock fabrics and texture in sedimentary rocks have been used to reconstruct sedimentary microfacies, which is further used to infer depositional environments (e.g., <xref ref-type="bibr" rid="B16">El-Sabbagh et al., 2017</xref>; <xref ref-type="bibr" rid="B36">Mtelela et al., 2017</xref>; <xref ref-type="bibr" rid="B6">Barrera et al., 2020</xref>). However, these sedimentological, mineralogical and petrological characterizations are sometimes limited by the availability of outcrops and drilling cores, or the lack of typical depositional indicators. Paleontological methods are highly efficient in revealing paleo-depositional environment. Fossils, bioglyphs and their assemblages have been used to classify biofacies (e.g., <xref ref-type="bibr" rid="B26">Laprida et al., 2007</xref>; <xref ref-type="bibr" rid="B16">El-Sabbagh et al., 2017</xref>; <xref ref-type="bibr" rid="B35">Mahfouz et al., 2021</xref>). However, well-preserved characteristic fossils are not always available in sedimentary rocks because most of organisms in sediments have been degraded during burial and diagenesis. Geochemical data are sensitive to a variety of depositional conditions, such as redox condition (e.g., V/Cr, Ni/Co, U/Th) and salinity (e.g., Sr/Ba, B/Ga, Rb/K). However, these geochemical parameters are not diagnostic to a specific depositional environment, and thus cannot be used solely for depositional environment identification. Recently, biomarkers produced from the degradation of organisms living in different environments has attracted increasing attention in depositional environment studies (e.g., <xref ref-type="bibr" rid="B2">Aderoju and Bend, 2018</xref>; <xref ref-type="bibr" rid="B55">Wendorff-Belon et al., 2021</xref>; <xref ref-type="bibr" rid="B32">Liu et al., 2022</xref>). Here, we demonstrate a new biomarker method using C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub> tricyclic terpanes (TTs) as a robust tool for the identification of depositional environment.</p>
<p>TTs with carbon numbers range from C<sub>19</sub> to C<sub>29</sub> are ubiquitous in crude oils and extracts of sedimentary rocks (<xref ref-type="bibr" rid="B12">De Grande et al., 1993</xref>). Higher carbon TTs are also present but are often masked by hopanes in the <italic>m/z</italic> 191 mass chromatogram (<xref ref-type="bibr" rid="B44">Samuel et al., 2010</xref>) (<xref ref-type="fig" rid="F1">Figure 1</xref>). TTs have been widely applied to oil-source correlation due to their high thermal stability and resistance to biodegradation (<xref ref-type="bibr" rid="B17">Farrimond et al., 1999</xref>; <xref ref-type="bibr" rid="B56">Xiao et al., 2019a</xref>). Although the exact precursors of TTs have not been identified yet (<xref ref-type="bibr" rid="B14">Dutta et al., 2006</xref>; <xref ref-type="bibr" rid="B40">Philp et al., 2021</xref>), previous studies have noticed a close relationship between TTs and depositional environments. TTs always show a predominance of C<sub>23</sub>TT in marine facies and a predominance of C<sub>21</sub>TT in freshwater lacustrine facies, and more abundant lower than higher carbon numbers of TTs in shallow-water environments (e.g., <xref ref-type="bibr" rid="B70">Zumberge, 1987</xref>; <xref ref-type="bibr" rid="B50">Tao et al., 2015</xref>; <xref ref-type="bibr" rid="B5">Atoyebi et al., 2017</xref>; <xref ref-type="bibr" rid="B57">Xiao et al., 2019b</xref>).</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>Mass chromatogram (<italic>m/z</italic> 191) showing the distribution of tricyclic terpanes (TTs) and hopanes (Hs) in the rock extract from C1 well in the East China Sea Basin.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g001.tif"/>
</fig>
<p>However, the exact correspondences between TTs and various depositional environments have not been clearly defined, limiting their applications to environmental identification. Here, we carried out a thorough examination of new and published C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data from a range of known depositional environments worldwide and discovered good correspondences between C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns and typical depositional environments. Based on the analysis on the origin of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns, a discriminating diagram of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TTs was developed for environmental identification and was then demonstrated for its validity and applicability, and was finally applied to a complex depositional system in the East China Sea Basin to show its strength.</p>
</sec>
<sec sec-type="materials|methods" id="s2">
<title>2 Materials and methods</title>
<p>A total of 232 C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data from a range of depositional environments in 30 basins across 18 countries were compiled from the literature (<xref ref-type="table" rid="T1">Table 1</xref>; <xref ref-type="sec" rid="s12">Supplementary Table S1</xref>). The data were obtained from gas chromatography-mass spectrometry (GC-MS) analysis of crude oils and source-rock extracts, with rock ages mainly ranging from the Devonian to Neogene (<xref ref-type="sec" rid="s12">Supplementary Table S1</xref>).</p>
<table-wrap id="T1" position="float">
<label>TABLE 1</label>
<caption>
<p>The ratios of C<sub>21</sub>/C<sub>20</sub>TT and C<sub>23</sub>/C<sub>21</sub>TT from a range of depositional environments.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th rowspan="1" align="center">Depositional environment</th>
<th rowspan="1" align="center">C<sub>21</sub>/C<sub>20</sub>TT</th>
<th rowspan="1" align="center">C<sub>23</sub>/C<sub>21</sub>TT</th>
<th rowspan="1" align="center">Sample type</th>
<th rowspan="1" align="center">Source-rock/reservoir age</th>
<th rowspan="1" align="center">Basin</th>
<th rowspan="1" align="center">Country</th>
<th rowspan="1" align="center">Data source</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td rowspan="1" align="center">&#x2003;Marine facies</td>
<td rowspan="1" align="center">0.98&#x2013;2.83</td>
<td rowspan="1" align="center">1.20&#x2013;3.57</td>
<td rowspan="1" align="center">89 oils</td>
<td rowspan="1" align="center">Silurian, Devonian, Carboniferous, Permian, Triassic, Jurassic, Cretaceous, Paleogene, Neogene</td>
<td rowspan="1" align="center">Cuanza, Benguala, Neuquan, North Sea, W. Canadian, Magdalans, Gulf of Suez, Oriente, Overthrust, North Slope, Nemaha, Great, Williston, Anadarko, GOM, Barinas, Los Angeles, Ventura, Santa Maria</td>
<td rowspan="1" align="center">Angola, Argentina, Britain, Canada, Colombia, Egypt, Netherlands, Norway, Peru, United States, Venezuela</td>
<td rowspan="1" align="center">
<xref ref-type="bibr" rid="B70">Zumberge (1987)</xref>
</td>
</tr>
<tr>
<td rowspan="1" align="center">&#x2003;Saline lacustrine facies</td>
<td rowspan="1" align="center">1.00&#x2013;2.08</td>
<td rowspan="1" align="center">1.15&#x2013;1.52</td>
<td rowspan="1" align="center">5 oils, 9 source rocks</td>
<td rowspan="1" align="center">Permian, Paleogene</td>
<td rowspan="1" align="center">Bohai Bay, Junggar</td>
<td rowspan="1" align="center">China</td>
<td rowspan="1" align="center">This study; <xref ref-type="bibr" rid="B62">Yu et al. (2017)</xref>
</td>
</tr>
<tr>
<td rowspan="1" align="center">&#x2003;Brackish-freshwater lacustrine facies</td>
<td rowspan="1" align="center">1.11&#x2013;3.03</td>
<td rowspan="1" align="center">0.36&#x2013;1.23</td>
<td rowspan="1" align="center">34 oils, 25 source rocks</td>
<td rowspan="1" align="center">Triassic, Cretaceous, Paleogene</td>
<td rowspan="1" align="center">Bohai Bay, Ordos, Sudan</td>
<td rowspan="1" align="center">China, Sudan, South Sudan</td>
<td rowspan="1" align="center">This study; <xref ref-type="bibr" rid="B33">Lv and Thesis, (2019)</xref>; <xref ref-type="bibr" rid="B56">Xiao et al. (2019a)</xref>
</td>
</tr>
<tr>
<td rowspan="1" align="center">&#x2003;Marine-continental transitional facies</td>
<td rowspan="1" align="center">0.24&#x2013;1.03</td>
<td rowspan="1" align="center">0.96&#x2013;3.01</td>
<td rowspan="1" align="center">24 oils, 6 source rocks</td>
<td rowspan="1" align="center">Cambrian, Triassic, Jurassic, Cretaceous, Paleogene, Neogene</td>
<td rowspan="1" align="center">Vulcan, Lianos, Java Sea, Niger Delta, Indus, North slope, Williston, GOM, Paradox, Maracabio, Junggar</td>
<td rowspan="1" align="center">Australia, China, Colombia, Indonesia, Nigeria, Pakistan, Thailand, United States, Venezuela</td>
<td rowspan="1" align="center">
<xref ref-type="bibr" rid="B70">Zumberge (1987)</xref>; <xref ref-type="bibr" rid="B20">Gao et al. (2017)</xref>
</td>
</tr>
<tr>
<td rowspan="1" align="center">&#x2003;River-lake transitional facies</td>
<td rowspan="1" align="center">0.52&#x2013;1.04</td>
<td rowspan="1" align="center">0.51&#x2013;1.03</td>
<td rowspan="1" align="center">13 oils, 43 source rocks</td>
<td rowspan="1" align="center">Permian, Jurassic</td>
<td rowspan="1" align="center">Qaidam, Junggar</td>
<td rowspan="1" align="center">China</td>
<td rowspan="1" align="center">This study; <xref ref-type="bibr" rid="B54">Wang et al. (2020)</xref>; <xref ref-type="bibr" rid="B8">Cao et al. (2008)</xref>
</td>
</tr>
<tr>
<td rowspan="1" align="center">&#x2003;Terrigenous source</td>
<td rowspan="1" align="center">0.50&#x2013;0.91</td>
<td rowspan="1" align="center">0.25&#x2013;0.53</td>
<td rowspan="1" align="center">25 source rocks</td>
<td rowspan="1" align="center">Triassic</td>
<td rowspan="1" align="center">Junggar</td>
<td rowspan="1" align="center">China</td>
<td rowspan="1" align="center">
<xref ref-type="bibr" rid="B20">Gao et al. (2017)</xref>
</td>
</tr>
</tbody>
</table>
</table-wrap>
<p>Additionally, new C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data were acquired from four source-rock samples and 35 oil samples from three basins (the Ordos, Bohai Bay and Qaidam basins) in China (<xref ref-type="table" rid="T1">Table 1</xref> and <xref ref-type="sec" rid="s12">Supplementary Table S1</xref>). The soluble organic matter was extracted from the source rocks following the description by <xref ref-type="bibr" rid="B40">Philp et al. (2021)</xref>. The biomarkers including C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TTs in the rock extracts and oils were analyzed by GC-MS as described by <xref ref-type="bibr" rid="B52">Wang et al. (2019)</xref>. Subsequently, the source rocks for the oils were determined by the previous oil-source correlations in these basins (e.g., <xref ref-type="bibr" rid="B49">Sun, 2006</xref>; <xref ref-type="bibr" rid="B8">Cao et al., 2008</xref>; <xref ref-type="bibr" rid="B64">Zhang et al., 2009</xref>). As the depositional environments of source rocks in these three basins have been well constrained by previous studies (e.g., <xref ref-type="bibr" rid="B68">Zhu and Jin, 2003</xref>; <xref ref-type="bibr" rid="B49">Sun, 2006</xref>; <xref ref-type="bibr" rid="B8">Cao et al., 2008</xref>; <xref ref-type="bibr" rid="B64">Zhang et al., 2009</xref>; <xref ref-type="bibr" rid="B19">Gao et al., 2014</xref>), the correspondence between C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data and depositional environments were easily determined.</p>
<p>In order to verify the validity of our biomarker method and its applicability to thermal maturity, 13 core samples from 8 wells were collected from the Ordovician and Permian in the Ordos Basin (<xref ref-type="table" rid="T2">Table 2</xref>). These samples contain typical depositional environment indicators or were deposited in the well-defined depositional environments. All these samples are now at highly mature stages (<xref ref-type="table" rid="T2">Table 2</xref>). C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TTs in these rock extracts were also analyzed by GC-MS as described by <xref ref-type="bibr" rid="B52">Wang et al. (2019)</xref>. Two samples (i.e., L65, 4296.3&#xa0;m and L41-1, 4120&#xa0;m) were selected to measure vitrinite reflectance (Ro%) following the description by <xref ref-type="bibr" rid="B24">Kalinowski and Gurba (2020)</xref>. Two thin sections (i.e., L65, 4296.3&#xa0;m and L66, 4040.45&#xa0;m) were prepared for the observation of petrography and fossil.</p>
<table-wrap id="T2" position="float">
<label>TABLE 2</label>
<caption>
<p>The ratios of C<sub>21</sub>/C<sub>20</sub>TT, C<sub>23</sub>/C<sub>21</sub>TT and vitrinite reflectance (Ro) from the known depositional environments in the Ordos Basin.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="center">Well</th>
<th align="center">Depth(m)</th>
<th align="center">Sample lithology</th>
<th align="center">Environmental indicators</th>
<th align="center">Period</th>
<th align="center">Formation</th>
<th align="center">C<sub>21</sub>/C<sub>20</sub>TT</th>
<th align="center">C<sub>23</sub>/C<sub>21</sub>TT</th>
<th align="center">Ro (%)</th>
<th align="center">Depositional environment&#x2a;</th>
<th align="center">Depositional environment&#x23;</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="center">&#x2003;L66</td>
<td align="center">4040.5</td>
<td align="center">Gravel limestone</td>
<td align="center">Fuzulinid fossil, Storm deposit</td>
<td rowspan="5" align="center">Early Permian</td>
<td rowspan="5" align="center">Taiyuan</td>
<td align="center">0.88</td>
<td align="center">1.24</td>
<td align="center">2.0</td>
<td align="center">Sub-tidal</td>
<td align="center">Marine-continental transitional facies</td>
</tr>
<tr>
<td align="center">&#x2003;CH3</td>
<td align="center">3802.8</td>
<td rowspan="2" align="center">Siderite bearing mudstone</td>
<td rowspan="2" align="center">Nodular siderite, Pyrite absent</td>
<td align="center">0.87</td>
<td align="center">0.76</td>
<td align="center">2.0</td>
<td rowspan="2" align="center">Delta</td>
<td rowspan="2" align="center">River-lake&#xa0;transitional&#xa0;facies</td>
</tr>
<tr>
<td align="center">&#x2003;L65</td>
<td align="center">4296.3</td>
<td align="center">0.83</td>
<td align="center">0.52</td>
<td align="center">
<bold>2.3</bold>
</td>
</tr>
<tr>
<td align="center">&#x2003;L47-1</td>
<td align="center">4120.0</td>
<td align="center">Carbonaceous mudstone</td>
<td align="center">Cordaites fossil</td>
<td align="center">0.76</td>
<td align="center">0.73</td>
<td align="center">
<bold>2.4</bold>
</td>
<td align="center">Swamp</td>
<td align="center">River-lake&#xa0;transitional&#xa0;facies</td>
</tr>
<tr>
<td align="center">&#x2003;HT7</td>
<td align="center">4435.0</td>
<td align="center">Pyrite bearing mudstone</td>
<td align="center">Pyrite crystal</td>
<td align="center">0.97</td>
<td align="center">1.21</td>
<td align="center">2.2</td>
<td align="center">Lagoon; Tidal flat</td>
<td align="center">Marine-continental transitional facies</td>
</tr>
<tr>
<td rowspan="3" align="center">&#x2003;XY1</td>
<td align="center">3067.2</td>
<td rowspan="4" align="center">Dark mudstone</td>
<td rowspan="4" align="center">Thin coal interlayer</td>
<td rowspan="4" align="center">Early Permian</td>
<td rowspan="4" align="center">Shanxi</td>
<td align="center">1.33</td>
<td align="center">1.10</td>
<td rowspan="4" align="center">1.4</td>
<td rowspan="4" align="center">Continental facies</td>
<td rowspan="4" align="center">Brackish-freshwater lacustrine facies</td>
</tr>
<tr>
<td align="center">3132.0</td>
<td align="center">1.28</td>
<td align="center">0.95</td>
</tr>
<tr>
<td align="center">3132.4</td>
<td align="center">1.27</td>
<td align="center">0.76</td>
</tr>
<tr>
<td align="center">&#x2003;XY2</td>
<td align="center">2796.7</td>
<td align="center">1.15</td>
<td align="center">0.84</td>
</tr>
<tr>
<td rowspan="4" align="center">&#x2003;MT3</td>
<td align="center">2976.6</td>
<td align="center">Calcareous mudstone</td>
<td align="center">mudstone interlayer in carbonate rocks</td>
<td rowspan="4" align="center">Middle Ordovician</td>
<td rowspan="2" align="center">Majiagou (4th Member)</td>
<td align="center">1.45</td>
<td align="center">2.04</td>
<td rowspan="4" align="center">1.6</td>
<td rowspan="2" align="center">Marine facies</td>
<td rowspan="2" align="center">Marine facies</td>
</tr>
<tr>
<td align="center">2976.8</td>
<td align="center">Massive limestone</td>
<td align="center">Carbonate rocks</td>
<td align="center">1.2</td>
<td align="center">1.47</td>
</tr>
<tr>
<td align="center">3177.7</td>
<td rowspan="2" align="center">Gypsum bearing mudstone</td>
<td rowspan="2" align="center">Depositional gypsum</td>
<td rowspan="2" align="center">Majiagou (3rd Member)</td>
<td align="center">1.54</td>
<td align="center">2.42</td>
<td rowspan="2" align="center">Marine facies</td>
<td rowspan="2" align="center">Marine facies</td>
</tr>
<tr>
<td align="left">3180.0</td>
<td align="left">1.53</td>
<td align="left">2.16</td>
</tr>
</tbody>
</table>
<table-wrap-foot>
<fn>
<p>(&#x2a;) denotes the depositional environments identified by fossil, characteristic mineral or previous studies; (&#x23;) denotes the depositional environments identified by the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT, method; <bold>2.3</bold> and <bold>2.4</bold> Ro% were measured in this study; the Ro values for the Permian were estimated according to <xref ref-type="bibr" rid="B48">Sun (2017)</xref>; the Ro values for the Ordovician were cited from <xref ref-type="bibr" rid="B25">Kong et al. (2019)</xref> which was converted from asphalt reflectivity.</p>
</fn>
</table-wrap-foot>
</table-wrap>
<p>Forty-four sets of geochemical data (including total organic carbon (TOC), Rock-Eval pyrolysis, chloroform asphalt &#x2018;A&#x2019;, Ro and biomarkers of rock extracts) obtained from 14 wells in the Pingbei area in the East China Sea Basin (<xref ref-type="table" rid="T3">Table 3</xref>), were collected from the SINOPEC Shanghai Offshore Oil &#x26; Gas Company for a case study.</p>
<table-wrap id="T3" position="float">
<label>TABLE 3</label>
<caption>
<p>Geochemical data of sedimentary rock in the Pingbei area, East China Sea Basin.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th align="center">Well</th>
<th align="center">Depth (m)</th>
<th align="center">Sample lithology</th>
<th align="center">Formation</th>
<th align="center">TOC (%)</th>
<th align="center">&#x201c;A&#x201d; (%)</th>
<th align="center">S<sub>1</sub>&#x2b;S<sub>2</sub> (mg/g)</th>
<th align="center">Tmax (&#xb0;C)</th>
<th align="center">Ro (%)</th>
<th align="center">C<sub>21</sub>/C<sub>20</sub>TT</th>
<th align="center">C<sub>23</sub>/C<sub>21</sub>TT</th>
<th align="center">Pr/Ph</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="center">A1</td>
<td align="center">4167.00</td>
<td align="center">Coal (cuttings)</td>
<td align="center">P4</td>
<td align="center">4.78</td>
<td align="center">3.77</td>
<td align="center">30.43</td>
<td align="center">437</td>
<td align="center">/</td>
<td align="center">0.98</td>
<td align="center">1.52</td>
<td align="center">3.89</td>
</tr>
<tr>
<td align="center">A1</td>
<td align="center">4367.00</td>
<td align="center">Carbonaceous mudstone (cuttings)</td>
<td align="center">P3</td>
<td align="center">16.40</td>
<td align="center">1.40</td>
<td align="center">71.89</td>
<td align="center">439</td>
<td align="center">/</td>
<td align="center">0.82</td>
<td align="center">1.34</td>
<td align="center">3.80</td>
</tr>
<tr>
<td align="center">A1</td>
<td align="center">4427.50</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P2</td>
<td align="center">1.14</td>
<td align="center">0.17</td>
<td align="center">5.69</td>
<td align="center">441</td>
<td align="center">/</td>
<td align="center">0.75</td>
<td align="center">0.93</td>
<td align="center">2.36</td>
</tr>
<tr>
<td align="center">A1</td>
<td align="center">4432.00</td>
<td align="center">Carbonaceous mudstone (sidewall core)</td>
<td align="center">P2</td>
<td align="center">19.60</td>
<td align="center">3.72</td>
<td align="center">88.89</td>
<td align="center">451</td>
<td align="center">/</td>
<td align="center">0.72</td>
<td align="center">0.77</td>
<td align="center">3.14</td>
</tr>
<tr>
<td align="center">A2</td>
<td align="center">4345.99</td>
<td align="center">Mudstone (core)</td>
<td align="center">P4</td>
<td align="center">0.62</td>
<td align="center">0.03</td>
<td align="center">0.73</td>
<td align="center">444</td>
<td align="center">0.78</td>
<td align="center">0.26</td>
<td align="center">0.97</td>
<td align="center">5.78</td>
</tr>
<tr>
<td align="center">A2</td>
<td align="center">4350.84</td>
<td align="center">Mudstone (core)</td>
<td align="center">P4</td>
<td align="center">0.29</td>
<td align="center">0.01</td>
<td align="center">0.21</td>
<td align="center">445</td>
<td align="center">0.78</td>
<td align="center">0.14</td>
<td align="center">1.10</td>
<td align="center">3.64</td>
</tr>
<tr>
<td align="center">A2</td>
<td align="center">4351.24</td>
<td align="center">Mudstone (core)</td>
<td align="center">P4</td>
<td align="center">0.23</td>
<td align="center">0.01</td>
<td align="center">0.20</td>
<td align="center">443</td>
<td align="center">0.78</td>
<td align="center">0.13</td>
<td align="center">1.31</td>
<td align="center">3.14</td>
</tr>
<tr>
<td align="center">A2</td>
<td align="center">4351.64</td>
<td align="center">Mudstone (core)</td>
<td align="center">P4</td>
<td align="center">0.38</td>
<td align="center">0.01</td>
<td align="center">0.33</td>
<td align="center">449</td>
<td align="center">0.78</td>
<td align="center">0.19</td>
<td align="center">1.14</td>
<td align="center">2.79</td>
</tr>
<tr>
<td align="center">A3</td>
<td align="center">3569.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P3</td>
<td align="center">0.88</td>
<td align="center">0.05</td>
<td align="center">3.43</td>
<td align="center">440</td>
<td align="center">/</td>
<td align="center">0.94</td>
<td align="center">0.73</td>
<td align="center">1.46</td>
</tr>
<tr>
<td align="center">A3</td>
<td align="center">4043.50</td>
<td align="center">Carbonaceous mudstone (core)</td>
<td align="center">P1</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">0.57</td>
<td align="center">0.71</td>
<td align="center">6.19</td>
</tr>
<tr>
<td align="center">A3</td>
<td align="center">3962.50</td>
<td align="center">Mudstone (core)</td>
<td align="center">P1</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">0.80</td>
<td align="center">0.66</td>
<td align="center">4.86</td>
</tr>
<tr>
<td align="center">A4</td>
<td align="center">3320.50</td>
<td align="center">Mudstone (core)</td>
<td align="center">P2</td>
<td align="center">2.18</td>
<td align="center">/</td>
<td align="center">4.95</td>
<td align="center">439</td>
<td align="center">0.68</td>
<td align="center">0.73</td>
<td align="center">0.79</td>
<td align="center">4.69</td>
</tr>
<tr>
<td align="center">A5</td>
<td align="center">4204.36</td>
<td align="center">Mudstone (core)</td>
<td align="center">P3</td>
<td align="center">1.35</td>
<td align="center">0.04</td>
<td align="center">1.96</td>
<td align="center">443</td>
<td align="center">0.75</td>
<td align="center">1.05</td>
<td align="center">0.64</td>
<td align="center">4.14</td>
</tr>
<tr>
<td align="center">A5</td>
<td align="center">4609.00</td>
<td align="center">Coal (core)</td>
<td align="center">P1</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">0.25</td>
<td align="center">0.89</td>
<td align="center">5.69</td>
</tr>
<tr>
<td align="center">A6</td>
<td align="center">4344.07</td>
<td align="center">Mudstone (core)</td>
<td align="center">P1</td>
<td align="center">0.66</td>
<td align="center">0.04</td>
<td align="center">0.60</td>
<td align="center">443</td>
<td align="center">0.76</td>
<td align="center">1.17</td>
<td align="center">1.07</td>
<td align="center">3.68</td>
</tr>
<tr>
<td align="center">B1</td>
<td align="center">3391.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P4</td>
<td align="center">0.60</td>
<td align="center">/</td>
<td align="center">0.23</td>
<td align="center">392</td>
<td align="center">0.51</td>
<td align="center">1.82</td>
<td align="center">1.30</td>
<td align="center">1.08</td>
</tr>
<tr>
<td align="center">B1</td>
<td align="center">3807.50</td>
<td align="center">Mudstone (core)</td>
<td align="center">P1</td>
<td align="center">1.66</td>
<td align="center">/</td>
<td align="center">2.74</td>
<td align="center">444</td>
<td align="center">0.68</td>
<td align="center">1.03</td>
<td align="center">0.73</td>
<td align="center">2.07</td>
</tr>
<tr>
<td align="center">B1</td>
<td align="center">3809.14</td>
<td align="center">Mudstone (core)</td>
<td align="center">P1</td>
<td align="center">1.77</td>
<td align="center">/</td>
<td align="center">1.21</td>
<td align="center">442</td>
<td align="center">0.70</td>
<td align="center">1.26</td>
<td align="center">0.94</td>
<td align="center">6.34</td>
</tr>
<tr>
<td align="center">B2</td>
<td align="center">4103.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P2</td>
<td align="center">0.37</td>
<td align="center">0.05</td>
<td align="center">0.86</td>
<td align="center">439</td>
<td align="center">0.69</td>
<td align="center">1.40</td>
<td align="center">1.38</td>
<td align="center">3.49</td>
</tr>
<tr>
<td align="center">B2</td>
<td align="center">4239.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P2</td>
<td align="center">0.42</td>
<td align="center">0.09</td>
<td align="center">0.98</td>
<td align="center">439</td>
<td align="center">0.73</td>
<td align="center">1.00</td>
<td align="center">1.09</td>
<td align="center">4.69</td>
</tr>
<tr>
<td align="center">B2</td>
<td align="center">4295.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P2</td>
<td align="center">0.81</td>
<td align="center">0.23</td>
<td align="center">2.22</td>
<td align="center">441</td>
<td align="center">0.74</td>
<td align="center">1.31</td>
<td align="center">0.75</td>
<td align="center">5.11</td>
</tr>
<tr>
<td align="center">B2</td>
<td align="center">4405.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P2</td>
<td align="center">0.66</td>
<td align="center">0.11</td>
<td align="center">3.10</td>
<td align="center">449</td>
<td align="center">0.81</td>
<td align="center">2.27</td>
<td align="center">0.29</td>
<td align="center">3.45</td>
</tr>
<tr>
<td align="center">B2</td>
<td align="center">4564.80</td>
<td align="center">Mudstone (core)</td>
<td align="center">P1</td>
<td align="center">0.38</td>
<td align="center">/</td>
<td align="center">0.40</td>
<td align="center">484</td>
<td align="center">0.78</td>
<td align="center">1.82</td>
<td align="center">0.46</td>
<td align="center">1.14</td>
</tr>
<tr>
<td align="center">B2</td>
<td align="center">4677.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P1</td>
<td align="center">0.32</td>
<td align="center">0.06</td>
<td align="center">1.94</td>
<td align="center">292</td>
<td align="center">0.87</td>
<td align="center">1.35</td>
<td align="center">1.67</td>
<td align="center">2.95</td>
</tr>
<tr>
<td align="center">B3</td>
<td align="center">4186.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P2</td>
<td align="center">0.62</td>
<td align="center">/</td>
<td align="center">0.43</td>
<td align="center">443</td>
<td align="center">0.72</td>
<td align="center">0.99</td>
<td align="center">1.02</td>
<td align="center">4.11</td>
</tr>
<tr>
<td align="center">B3</td>
<td align="center">4188.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P2</td>
<td align="center">0.59</td>
<td align="center">/</td>
<td align="center">0.42</td>
<td align="center">441</td>
<td align="center">0.71</td>
<td align="center">0.83</td>
<td align="center">0.90</td>
<td align="center">4.76</td>
</tr>
<tr>
<td align="center">B4</td>
<td align="center">3842.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P3</td>
<td align="center">0.31</td>
<td align="center">0.02</td>
<td align="center">0.30</td>
<td align="center">434</td>
<td align="center">/</td>
<td align="center">1.57</td>
<td align="center">1.71</td>
<td align="center">0.93</td>
</tr>
<tr>
<td align="center">B4</td>
<td align="center">3878.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P3</td>
<td align="center">0.28</td>
<td align="center">0.04</td>
<td align="center">0.37</td>
<td align="center">435</td>
<td align="center">/</td>
<td align="center">2.21</td>
<td align="center">1.35</td>
<td align="center">1.19</td>
</tr>
<tr>
<td align="center">C1</td>
<td align="center">3273.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P4</td>
<td align="center">1.38</td>
<td align="center">/</td>
<td align="center">1.58</td>
<td align="center">433</td>
<td align="center">0.54</td>
<td align="center">1.27</td>
<td align="center">1.11</td>
<td align="center">1.91</td>
</tr>
<tr>
<td align="center">C1</td>
<td align="center">3275.85</td>
<td align="center">Coal (core)</td>
<td align="center">P4</td>
<td align="center">56.49</td>
<td align="center">/</td>
<td align="center">217</td>
<td align="center">421</td>
<td align="center">0.54</td>
<td align="center">0.48</td>
<td align="center">1.05</td>
<td align="center">7.34</td>
</tr>
<tr>
<td align="center">C1</td>
<td align="center">3398.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P3</td>
<td align="center">0.60</td>
<td align="center">/</td>
<td align="center">0.37</td>
<td align="center">405</td>
<td align="center">0.57</td>
<td align="center">1.43</td>
<td align="center">1.16</td>
<td align="center">0.92</td>
</tr>
<tr>
<td align="center">C1</td>
<td align="center">3442.00</td>
<td align="center">Coal (core)</td>
<td align="center">P2</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">0.65</td>
<td align="center">0.02</td>
<td align="center">0.78</td>
<td align="center">3.32</td>
</tr>
<tr>
<td align="center">C1</td>
<td align="center">3444.81</td>
<td align="center">Mudstone (core)</td>
<td align="center">P2</td>
<td align="center">0.64</td>
<td align="center">/</td>
<td align="center">0.82</td>
<td align="center">436.00</td>
<td align="center">0.65</td>
<td align="center">1.35</td>
<td align="center">0.94</td>
<td align="center">5.20</td>
</tr>
<tr>
<td align="center">C1</td>
<td align="center">3627.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P1</td>
<td align="center">0.50</td>
<td align="center">/</td>
<td align="center">0.20</td>
<td align="center">410</td>
<td align="center">0.67</td>
<td align="center">1.40</td>
<td align="center">1.20</td>
<td align="center">0.92</td>
</tr>
<tr>
<td align="center">C2</td>
<td align="center">3652.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P3</td>
<td align="center">0.77</td>
<td align="center">/</td>
<td align="center">0.66</td>
<td align="center">437</td>
<td align="center">/</td>
<td align="center">1.18</td>
<td align="center">1.05</td>
<td align="center">1.66</td>
</tr>
<tr>
<td align="center">C2</td>
<td align="center">3961.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P1</td>
<td align="center">0.72</td>
<td align="center">/</td>
<td align="center">0.74</td>
<td align="center">446</td>
<td align="center">/</td>
<td align="center">1.37</td>
<td align="center">1.24</td>
<td align="center">1.17</td>
</tr>
<tr>
<td align="center">C3</td>
<td align="center">3753.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P4</td>
<td align="center">0.58</td>
<td align="center">0.31</td>
<td align="center">2.42</td>
<td align="center">430</td>
<td align="center">/</td>
<td align="center">1.33</td>
<td align="center">2.29</td>
<td align="center">1.21</td>
</tr>
<tr>
<td align="center">C3</td>
<td align="center">3922.00</td>
<td align="center">Mudstone (sidewall core)</td>
<td align="center">P3</td>
<td align="center">1.00</td>
<td align="center">0.21</td>
<td align="center">3.03</td>
<td align="center">434</td>
<td align="center">/</td>
<td align="center">1.66</td>
<td align="center">2.09</td>
<td align="center">3.41</td>
</tr>
<tr>
<td align="center">D1</td>
<td align="center">4094.50</td>
<td align="center">Mudstone (core)</td>
<td align="center">P3</td>
<td align="center">0.36</td>
<td align="center">0.01</td>
<td align="center">0.76</td>
<td align="center">432</td>
<td align="center">0.74</td>
<td align="center">0.38</td>
<td align="center">1.47</td>
<td align="center">2.40</td>
</tr>
<tr>
<td align="center">D1</td>
<td align="center">4095.26</td>
<td align="center">Coal (core)</td>
<td align="center">P3</td>
<td align="center">74.52</td>
<td align="center">/</td>
<td align="center">167.53</td>
<td align="center">437</td>
<td align="center">0.74</td>
<td align="center">0.29</td>
<td align="center">1.19</td>
<td align="center">7.85</td>
</tr>
<tr>
<td align="center">D1</td>
<td align="center">4096.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P3</td>
<td align="center">3.68</td>
<td align="center">0.03</td>
<td align="center">6.03</td>
<td align="center">436.00</td>
<td align="center">0.72</td>
<td align="center">0.15</td>
<td align="center">1.51</td>
<td align="center">6.39</td>
</tr>
<tr>
<td align="center">D1</td>
<td align="center">4097.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P3</td>
<td align="center">0.89</td>
<td align="center">0.04</td>
<td align="center">0.91</td>
<td align="center">444.00</td>
<td align="center">0.73</td>
<td align="center">0.26</td>
<td align="center">1.55</td>
<td align="center">8.02</td>
</tr>
<tr>
<td align="center">D1</td>
<td align="center">4157.00</td>
<td align="center">Mudstone (core)</td>
<td align="center">P3</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">0.65</td>
<td align="center">0.67</td>
<td align="center">4.84</td>
</tr>
<tr>
<td align="center">D1</td>
<td align="center">4658.00</td>
<td align="center">Carbonaceous mudstone (core)</td>
<td align="center">P1</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">/</td>
<td align="center">0.34</td>
<td align="center">0.44</td>
<td align="center">3.66</td>
</tr>
</tbody>
</table>
<table-wrap-foot>
<fn>
<p>Abbreviations: TOC &#x3d; total organic carbon content; &#x201c;A&#x201d; &#x3d; chloroform asphalt &#x201c;A&#x201d;; S<sub>1</sub>&#x2b;S<sub>2</sub> &#x3d; sum of free hydrocarbon and pyrolytic hydrocarbon; Tmax &#x3d; maximum pyrolysis temperature; Ro &#x3d; vitrinite reflectance; TT &#x3d; tricyclic terpane; Pr/Ph &#x3d; pristane/phytane; /&#x3d; missing data.</p>
</fn>
</table-wrap-foot>
</table-wrap>
</sec>
<sec sec-type="results" id="s3">
<title>3 Results</title>
<sec id="s3-1">
<title>3.1 Marine facies</title>
<p>The marine C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data were compiled from 20 basins in 11 countries (<xref ref-type="table" rid="T1">Table 1</xref>). Their C<sub>21</sub>/C<sub>20</sub>TT and C<sub>23</sub>/C<sub>21</sub>TT ratios vary from 0.98 to 2.83 and 1.20 to 3.57, respectively (<xref ref-type="fig" rid="F2">Figure 2</xref>). The relative abundances of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TTs display a pattern of C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT (e.g., <xref ref-type="fig" rid="F3">Figure 3A</xref>).</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>Cross-plots of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub> tricyclic terpane (TT) ratios in context of depositional environments. The solid boundary lines were established with confidence by the data. The dotted line is a speculated boundary between brackish and freshwater lacustrine facies.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g002.tif"/>
</fig>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>Four representative abundance patterns of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub> tricyclic terpanes (TTs) in six depositional environments <bold>(A)</bold>, Marine or Saline lacustrine facies; <bold>(B)</bold>, Brackish-freshwater lacustrine facies; <bold>(C)</bold>, Terrigenous or River-lake transitional facies; <bold>(D)</bold>, Marine-continental transitional facies.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g003.tif"/>
</fig>
</sec>
<sec id="s3-2">
<title>3.2 Saline lacustrine facies</title>
<p>Saline lacustrine facies is represented by the source rocks from the Junggar Basin in Northwestern China (<xref ref-type="bibr" rid="B7">Bian et al., 2010</xref>; <xref ref-type="bibr" rid="B62">Yu et al., 2017</xref>) and the oil samples from the Bohai Bay Basin in Eastern China (<xref ref-type="table" rid="T1">Table 1</xref>). Their C<sub>21</sub>/C<sub>20</sub>TT and C<sub>23</sub>/C<sub>21</sub>TT ratios vary from 1.00 to 2.08 and 1.15 to 1.52, respectively (<xref ref-type="fig" rid="F2">Figure 2</xref>), which slightly overlaps with samples classified as marine in origin (<xref ref-type="bibr" rid="B68">Zhu and Jin, 2003</xref>; <xref ref-type="bibr" rid="B62">Yu et al., 2017</xref>). The relative abundances of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TTs associated with saline lacustrine facies are similar to those of marine facies.</p>
</sec>
<sec id="s3-3">
<title>3.3 Brackish-freshwater lacustrine facies</title>
<p>Brackish-freshwater lacustrine facies is represented by the samples from the Muglad Basin (Sudan) (<xref ref-type="bibr" rid="B57">Xiao et al., 2019b</xref>), Bohai Bay Basin (<xref ref-type="bibr" rid="B33">Lv and Thesis, 2019</xref>) and Ordos Basin in Central China (this study, <xref ref-type="table" rid="T1">Table 1</xref>), which were deposited in semi-deep to deep brackish-freshwater lacustrine facies (<xref ref-type="bibr" rid="B64">Zhang et al., 2009</xref>; <xref ref-type="bibr" rid="B56">Xiao et al., 2019a</xref>; <xref ref-type="bibr" rid="B34">Ma et al., 2019</xref>). The C<sub>21</sub>/C<sub>20</sub>TT and C<sub>23</sub>/C<sub>21</sub>TT ratios fall into the ranges of 0.95&#x2013;3.03 and 0.36 to 1.34, respectively (<xref ref-type="fig" rid="F2">Figure 2</xref>). The relative abundances of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TTs display two patterns: C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT and C<sub>20</sub>&#x3c; C<sub>21</sub>&#x3e;C<sub>21</sub>TT (e.g., <xref ref-type="fig" rid="F3">Figure 3B</xref>).</p>
</sec>
<sec id="s3-4">
<title>3.4 Terrigenous source</title>
<p>Terrigenous organic matter can be transported by rivers and eventually deposited in lacustrine or marine environments. Terrigenous organic matter transported by rivers has been reported to be deposited in marine facies in the northern South China Sea (<xref ref-type="bibr" rid="B30">Li et al., 2011</xref>; <xref ref-type="bibr" rid="B13">Deng et al., 2019</xref>) and lacustrine facies in the Junggar Basin (<xref ref-type="bibr" rid="B20">Gao et al., 2017</xref>). On this condition, the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data are strongly controlled by the source instead of depositional environment. The C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data of terrigenous source in the Junggar Basin give C<sub>21</sub>/C<sub>20</sub>TT ratios of 0.50&#x2013;0.91, and C<sub>23</sub>/C<sub>21</sub>TT ratios of 0.25&#x2013;0.53 (<xref ref-type="fig" rid="F2">Figure 2</xref>), with a relative abundance of C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3e;C<sub>23</sub>TT (e.g., <xref ref-type="fig" rid="F3">Figure 3C</xref>).</p>
</sec>
<sec id="s3-5">
<title>3.5 Transitional facies</title>
<sec id="s3-5-1">
<title>3.5.1 Marine-continental transitional facies</title>
<p>Marine-continental transitional facies is represented by the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data from 11 basins in nine countries collected by <xref ref-type="bibr" rid="B70">Zumberge (1987)</xref> and <xref ref-type="bibr" rid="B20">Gao et al. (2017)</xref> (<xref ref-type="table" rid="T1">Table 1</xref>). The majority of the C<sub>21</sub>/C<sub>20</sub>TT ratios are lower than 1.0, while the C<sub>23</sub>/C<sub>21</sub>TT ratios are mostly greater than 1.0 (<xref ref-type="fig" rid="F2">Figure 2</xref>), showing an abundance pattern of C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3c;C<sub>23</sub>TT (e.g., <xref ref-type="fig" rid="F3">Figure 3D</xref>).</p>
</sec>
<sec id="s3-5-2">
<title>3.5.2 River-lake transitional facies</title>
<p>River-lake transitional facies is represented by the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data from the Junggar Basin (<xref ref-type="bibr" rid="B54">Wang et al., 2020</xref>) and Qaidam Basin (this study and <xref ref-type="bibr" rid="B8">Cao et al., 2008</xref>; <xref ref-type="table" rid="T1">Table 1</xref>) in China. Their C<sub>21</sub>/C<sub>20</sub>TT and C<sub>23</sub>/C<sub>21</sub>TT ratios vary from 0.52 to 1.04 and 0.51 to 1.03, respectively (<xref ref-type="fig" rid="F2">Figure 2</xref>), with a dominant C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3e;C<sub>23</sub>TT pattern.</p>
</sec>
</sec>
</sec>
<sec sec-type="discussion" id="s4">
<title>4 Discussion</title>
<sec id="s4-1">
<title>4.1 Origin of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns</title>
<p>TTs have drawn broad attention in literature since <xref ref-type="bibr" rid="B3">Anders and Robinson (1971)</xref> and <xref ref-type="bibr" rid="B18">Gallegos (1971)</xref> described the lower homologs (C<sub>19</sub>-C<sub>24</sub>) of TTs in the bitumen and oils of the Green River Shale (e.g., <xref ref-type="bibr" rid="B4">Aquino Neto et al., 1982</xref>; <xref ref-type="bibr" rid="B10">Chicarelli et al., 1988</xref>; <xref ref-type="bibr" rid="B12">De Grande et al., 1993</xref>; <xref ref-type="bibr" rid="B14">Dutta et al., 2006</xref>; <xref ref-type="bibr" rid="B50">Tao et al., 2015</xref>; <xref ref-type="bibr" rid="B40">Philp et al., 2021</xref>). Multiple compound sources/precursors for TTs have been proposed, such as prokaryotic cell membrane (e.g., <xref ref-type="bibr" rid="B38">Ourisson et al., 1982</xref>), diterpenes in terrigenous plants (e.g., <xref ref-type="bibr" rid="B15">Ekweozor et al., 1983</xref>) and the now-extinct algal-like Tasmanites (e.g., <xref ref-type="bibr" rid="B4">Aquino Neto et al., 1982</xref>; <xref ref-type="bibr" rid="B10">Chicarelli et al., 1988</xref>; <xref ref-type="bibr" rid="B12">De Grande et al., 1993</xref>; <xref ref-type="bibr" rid="B14">Dutta et al., 2006</xref>). So far, no clear precursor-product relationship has been established, which has at least partially impeded the direct application of TTs as source indicators (<xref ref-type="bibr" rid="B40">Philp et al., 2021</xref>).</p>
<p>Here, the analysis of a large amount of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data from various depositional environments provides some insights into the origin of the observed C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns. Previous studies have shown that the organic matter in typical marine and shallow-water terrestrial facies mainly originated from plankton and terrestrial plants (e.g., <xref ref-type="bibr" rid="B51">Tissot and Welte, 1978</xref>). Accordingly, the C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT pattern likely corresponds to a dominant plankton input, while the C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3e;C<sub>23</sub>TT pattern may correspond to a dominant contribution of terrigenous plants. The former correspondence can be evidenced by the Neoproterozoic oil shale (900&#x2013;873&#xa0;Ma; maturity: 0.6&#x2013;0.7%Ro) in North China, in which the terrigenous plant input can be ignored (<xref ref-type="bibr" rid="B63">Zhang et al., 2007</xref>). This oil shale contains cyanobacteria and green algae, and shows a C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT abundance pattern in the rock extracts, suggesting that planktons are the biological source for the TTs with C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT abundance pattern.</p>
<p>The analysis also indicates that neither plankton nor terrigenous plants alone can generate the TTs with C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3c;C<sub>23</sub>TT or C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3e;C<sub>23</sub>TT patterns, which have been observed in marine-continental transitional and brackish-freshwater lacustrine facies, respectively. As these two depositional environments commonly receive blended input of plankton and terrigenous plants, mixing from different sources is likely the cause of the C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3c;C<sub>23</sub>TT and C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3e;C<sub>23</sub>TT patterns. This hypothesis is well supported by the numerical modeling of a mixing between plankton and terrigenous plants at various mixing ratios (<xref ref-type="fig" rid="F4">Figure 4</xref>). Representative C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns in the terrigenous plants domain (i.e., Point A in <xref ref-type="fig" rid="F4">Figure 4A</xref>) and the plankton domain (i.e., Points B or C in <xref ref-type="fig" rid="F4">Figure 4A</xref>) determined by this study, were used as end-members for the mixing modeling.</p>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>Numerical simulation for the origin of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub> tricyclic terpane (TT) abundance patterns by mixing plankton and terrigenous plants at various mixing ratios. Points <bold>(A&#x2013;C)</bold> are the representative end-member C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT distributions for the mixing modeling. With the change of mixing ratios between A and B (C), the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance pattern changes along Line A-B (C). Points D and E are the representative C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns of A-B mixture and A-C mixture, respectively.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g004.tif"/>
</fig>
<p>As illustrated in <xref ref-type="fig" rid="F4">Figure 4</xref>, with the change of mixing ratios between A and B, the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance pattern changes from C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3e;C<sub>23</sub>TT to C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3c;C<sub>23</sub>TT (e.g., D in <xref ref-type="fig" rid="F4">Figures 4A, B</xref>) when the mixing ratio (expressed as A%/B% ratio) decreases from 100/0 to 75/25, and further to C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT when the mixing ratio is lower than 44/56 (<xref ref-type="fig" rid="F4">Figure 4B</xref>). Similarly, mixing between A and C can generate the C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3e;C<sub>23</sub>TT pattern (e.g., E in <xref ref-type="fig" rid="F4">Figures 4A, C</xref>) when the mixing ratios (expressed as A%/C% ratio) are in the range of 81/19&#x2013;42/58 (<xref ref-type="fig" rid="F4">Figure 4C</xref>). Notably, almost all C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data in this study fall into a range from the terrigenous plants domain to the plankton domain (<xref ref-type="fig" rid="F5">Figure 5</xref>), suggesting that C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns are strongly controlled by the two end-member biological sources and their mixing contributions. Thus, the input mixing of plankton and terrigenous plants at different proportions should be responsible for the formation of various C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns.</p>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>Cross-plot of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub> tricyclic terpane (TT) ratios with two defined end-member domains of plankton and terrigenous plants. Almost all C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data in this study fall into a range from the terrigenous plants domain to the plankton domain.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g005.tif"/>
</fig>
</sec>
<sec id="s4-2">
<title>4.2 Environmental implication of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns</title>
<p>Depositional environments control the input proportions of plankton and terrigenous plants, which is proposed to control the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns in sedimentary rocks. The analysis of available C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT data from known depositional environments clearly show that the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns in different depositional environments are distinct from each other, with C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT in typical marine and saline lacustrine facies, C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3e;C<sub>23</sub>TT in freshwater lacustrine facies, C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3e;C<sub>23</sub>TT in river-lake transitional facies, and C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3c;C<sub>23</sub>TT in marine-continental transitional facies. As illustrated in <xref ref-type="fig" rid="F2">Figure 2</xref>, the C<sub>23</sub>/C<sub>21</sub>TT ratio not only increases progressively from freshwater lacustrine, to saline lacustrine, to marine facies, but also increases progressively from terrigenous source, to river-lake transitional, to marine-continental transitional facies. The C<sub>23</sub>/C<sub>21</sub>TT ratio appears to increase gradually with elevated salinity of depositional water. The increase in salinity usually indicates a decrease in fresh-water input and therefore a decrease in terrigenous input, which results in the C<sub>23</sub>/C<sub>21</sub>TT ratios approaching their source signatures of halophilic plankton. Accordingly, the boundary between brackish and freshwater lacustrine facies is expected to lie around a C<sub>23</sub>/C<sub>21</sub>TT ratio of 1.0 (<xref ref-type="fig" rid="F2">Figure 2</xref>). Furthermore, the C<sub>21</sub>/C<sub>20</sub>TT ratios in marine and lacustrine facies are obviously greater than those in transitional facies (<xref ref-type="fig" rid="F2">Figure 2</xref>), suggesting that the C<sub>21</sub>/C<sub>20</sub>TT ratio seems to increase with elevated depths of depositional water. In general, the greater the depositional depth, the farther offshore, and the less terrigenous input. Thus, their C<sub>21</sub>/C<sub>20</sub>TT ratios approach the signatures of planktons (halophilic plankton or freshwater plankton).</p>
<p>Based on the good correspondences between C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns and typical depositional environments, the cross-plot of C<sub>23</sub>/C<sub>21</sub>TT vs. C<sub>21</sub>/C<sub>20</sub>TT in context of depositional environments (<xref ref-type="fig" rid="F2">Figure 2</xref>) can be used as a discriminating diagram for environmental identification. C<sub>23</sub>/C<sub>21</sub>TT and C<sub>21</sub>/C<sub>20</sub>TT are expected to be the parameters to assess water salinity and depositional depth, respectively.</p>
</sec>
<sec id="s4-3">
<title>4.3 Validity of the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method</title>
<p>The Ordos Basin undergone (1) an early Paleozoic shallow oceanic-platform stage and 2) a late Paleozoic offshore-plain stage during the Paleozoic (<xref ref-type="bibr" rid="B27">Li, 2004</xref>). During the Middle Ordovician, the Majiagou Formation was deposited within a semi&#x2013;closed epicontinental sea environment (<xref ref-type="bibr" rid="B28">Li et al., 2018</xref>). From the Late Ordovician to the Early Carboniferous, the basin was uplifted by the Caledonian orogeny and underwent 130 million years of erosion (<xref ref-type="bibr" rid="B60">Yang et al., 2012</xref>; <xref ref-type="bibr" rid="B59">Xu et al., 2018</xref>). The following Hercynian orogeny caused the Late Paleozoic Ordos Basin subsidence. Large scale of transgression occurred from the east and west of the basin during the Benxi period and the seawater connected together during the Late Taiyuan period. With the gradual regression during the Shanxi period, continental deposition began to dominate, resulting in the development of marine-continental transitional facies, delta facies and lacustrine facies (<xref ref-type="bibr" rid="B48">Sun, 2017</xref>).</p>
<p>Thirteen core samples from the Ordovician-Permian in the Ordos Basin (<xref ref-type="fig" rid="F6">Figure 6</xref>; <xref ref-type="table" rid="T2">Table 2</xref>) and ten coal or carbonaceous mudstones from the Eocene in the East China Sea Basin (<xref ref-type="table" rid="T3">Table 3</xref>) were used to verify the validity of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method.</p>
<fig id="F6" position="float">
<label>FIGURE 6</label>
<caption>
<p>Tectonic units and composite stratigraphic columnar section of the Ordos Basin (modified from <xref ref-type="bibr" rid="B31">Li et al., 2021</xref>). The samples were collected from the Yishan Slope with the ages ranging from the Ordovician to Permian.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g006.tif"/>
</fig>
<sec id="s4-3-1">
<title>4.3.1 Marine facies</title>
<p>The four samples including gypsum bearing mudstones, massive limestone and calcareous mudstone (<xref ref-type="table" rid="T2">Table 2</xref>) from the Majiagou Formation were all identified as marine facies (<xref ref-type="fig" rid="F7">Figure 7</xref>), which is consistent with the present understanding of epicontinental sea environment (<xref ref-type="bibr" rid="B28">Li et al., 2018</xref>). Furthermore, the suggestion that the C<sub>23</sub>/C<sub>21</sub>TT ratio is a salinity indicator in this study is also evidenced by these samples. The Majiagou Formation is divided into six members, numbered from bottom to top as Ma1 to Ma6. The Ma1, Ma3 and Ma5 members were deposited with evaporite production during low sea level, while the Ma2, Ma4 and Ma6 members were deposited with carbonate production during high sea level (<xref ref-type="bibr" rid="B57">Xiao et al., 2019b</xref>). Thus, the depositional water salinity of Ma3 is higher than that of Ma4. It should be noted that the C<sub>23</sub>/C<sub>21</sub>TT ratios in Ma3 extract are indeed greater than those in Ma4 extract (<xref ref-type="table" rid="T2">Table 2</xref>; <xref ref-type="fig" rid="F7">Figure 7</xref>).</p>
<fig id="F7" position="float">
<label>FIGURE 7</label>
<caption>
<p>Environmental identification for the samples from the Ordovician and Permian in the Ordos Basin.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g007.tif"/>
</fig>
</sec>
<sec id="s4-3-2">
<title>4.3.2 Brackish-freshwater lacustrine facies</title>
<p>The depositional environments of the Permian Shanxi Formation in the southern Ordos basin have been determined by previous studies to be continental facies including delta and lacustrine facies (e.g., <xref ref-type="bibr" rid="B53">Wang et al., 2007</xref>; <xref ref-type="bibr" rid="B48">Sun, 2017</xref>; <xref ref-type="bibr" rid="B31">Li et al., 2021</xref>). Four dark mudstones from the Shanxi Formation in XY1 and XY2 wells (See locations in <xref ref-type="fig" rid="F6">Figure 6</xref>) were extracted for environmental identification. As shown in <xref ref-type="fig" rid="F7">Figure 7</xref>, the C<sub>21</sub>/C<sub>20</sub>TT and C<sub>23</sub>/C<sub>21</sub>TT ratios of these mudstones plot within the brackish-freshwater lacustrine facies, consistent with the regional depositional environments.</p>
</sec>
<sec id="s4-3-3">
<title>4.3.3 Transitional facies</title>
<sec id="s4-3-3-1">
<title>4.3.3.1 Cordaitean fossil leaves</title>
<p>Cordaitean fossil leaves are known from early Carboniferous to early Permian deposits, representing the depositional environments including floodplains, river levees, coastal plains or swamp (<xref ref-type="bibr" rid="B69">Zodrow et al., 2000</xref>; <xref ref-type="bibr" rid="B61">Yang, 2007</xref>). The carbonaceous mudstone containing the Cordaitean fossil leaves (<xref ref-type="fig" rid="F8">Figure 8A</xref>; <xref ref-type="table" rid="T2">Table 2</xref>) was identified as river-lake transitional facies by our biomarker method (<xref ref-type="fig" rid="F7">Figure 7</xref>). This is consistent with the depositional environments indicated by the Cordaitean fossil leaves.</p>
<fig id="F8" position="float">
<label>FIGURE 8</label>
<caption>
<p>Depositional environment indicators in the core samples and thin sections from the Taiyuan Formation in the Ordos Basin [<bold>(A)</bold>, Cordaites fossil, L47-1 well, 4120m; <bold>(B)</bold>, Cordaites fossil, L81 well; <bold>(C)</bold>, Pyrite crystal, HT7 well, 4435.0m; <bold>(D, E)</bold>, Fuzulinid fossil and limestone gravels, L66 well, 4040.5&#xa0;m; <bold>(F, G)</bold>, Nodular siderite, L65 well, 4296.3&#xa0;m].</p>
</caption>
<graphic xlink:href="feart-11-1128692-g008.tif"/>
</fig>
</sec>
<sec id="s4-3-3-2">
<title>4.3.3.2 Fuzulinid fossil</title>
<p>The Fuzulinid fossil with 1&#xa0;mm&#x223c;4&#xa0;mm in size and limestone gravels (<xref ref-type="fig" rid="F8">Figures 8D, E</xref>) constitute a storm deposition which indicates a sub-tidal depositional environment. This sample was identified by the biomarker method to be deposited within a marine-continental transitional facies (<xref ref-type="fig" rid="F7">Figure 7</xref>). As sub-tidal belongs to marine-continental transitional facies, the identification result of our biomarker method is thus correct.</p>
</sec>
<sec id="s4-3-3-3">
<title>4.3.3.3 Coal and carbonaceous mudstone</title>
<p>It is widely known that coal and carbonaceous mudstone are the indicators of shallow-water environment (e.g., swamp). The C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method not only identified the coal and carbonaceous mudstone as shallow-water environment (i.e., transitional environments defined by C<sub>21</sub>/C<sub>20</sub>TT&#x3c;1.0) as expected, but further determined their specific depositional environments: marine-continental transitional or river-lake transitional environments (<xref ref-type="fig" rid="F9">Figure 9A</xref>).</p>
<fig id="F9" position="float">
<label>FIGURE 9</label>
<caption>
<p>Cross-plots of C<sub>23</sub>/C<sub>21</sub>TT vs. C<sub>23</sub>/C<sub>21</sub>TT <bold>(A)</bold> and C<sub>21</sub>/C<sub>20</sub>TT vs. Pr/Ph <bold>(B)</bold> in the Pingbei area, East China Sea Basin. Note: TT&#x3d; tricyclic terpane; Pr/Ph &#x3d; pristane/phytane; I: Marine-continental transitional facies; II: River-lake transitional facies; III: Terrigenous source; IV: Marine facies; V: Saline lacustrine facies or marine facies; VI: Brackish-freshwater lacustrine facies.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g009.tif"/>
</fig>
</sec>
<sec id="s4-3-3-4">
<title>4.3.3.4 Siderite and pyrite</title>
<p>Although siderite can occur in various depositional environments, layered nodular siderite without pyrite in mudstone (<xref ref-type="fig" rid="F8">Figures 8F, G</xref>) was considered to be deposited in delta front, where iron oxides and terrigenous organic matter transported by river water are condensed and precipitated in a large amount (<xref ref-type="bibr" rid="B46">Shen et al., 2017</xref>). The two siderite bearing mudstones were identified by the biomarker method to be deposited within a river-lake transitional facies (<xref ref-type="fig" rid="F7">Figure 7</xref>). According to the sedimentary model of rock series containing siderite and pyrite created by <xref ref-type="bibr" rid="B46">Shen et al. (2017)</xref>, the mudstone containing pyrite was expected to be deposited in lagoon or tidal flat. The pyrite bearing mudstone was identified by the biomarker method to be deposited within a marine-continental transitional facies (<xref ref-type="fig" rid="F7">Figure 7</xref>). It is clear that these two identification results using the biomarker method are both correct.</p>
<p>Compared with siderite, pyrite was considered to be precipitated in a relatively deeper environment (<xref ref-type="fig" rid="F10">Figure 10</xref>). Notably, the C<sub>23</sub>/C<sub>21</sub>TT ratio of pyrite bearing mudstone is greater than those of siderite bearing mudstones (<xref ref-type="table" rid="T2">Table 2</xref>; <xref ref-type="fig" rid="F7">Figure 7</xref>), indicating that the suggestion of C<sub>23</sub>/C<sub>21</sub>TT ratio as a depth indicator is reasonable. This suggestion was also evidenced by the negative correlation between pristane/phytane (Pr/Ph) and C<sub>21</sub>/C<sub>20</sub>TT ratios (<xref ref-type="fig" rid="F9">Figure 9B</xref>). Pr/Ph ratios, which have been widely used to assess the redox of depositional environment, decrease with elevated anoxic conditions (<xref ref-type="bibr" rid="B43">Rashid, 1979</xref>). As shown in <xref ref-type="fig" rid="F9">Figure 9B</xref>, the Pr/Ph ratios decrease along the C<sub>21</sub>/C<sub>20</sub>TT values. The increase in C<sub>21</sub>/C<sub>20</sub>TT ratios indicates an increase in depositional depths, which further indicates an increase in anoxic conditions.</p>
<fig id="F10" position="float">
<label>FIGURE 10</label>
<caption>
<p>Schematic diagram of the facies change of sedimentary iron ore deposits (modified from <xref ref-type="bibr" rid="B42">Qiu, 1987</xref>).</p>
</caption>
<graphic xlink:href="feart-11-1128692-g010.tif"/>
</fig>
</sec>
</sec>
</sec>
<sec id="s4-4">
<title>4.4 Applicability of the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method</title>
<p>The C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method only requires a small amount of rock extracts, depending on the lower limit of GC-MS analysis. At present, the rock extracts more than 10&#xa0;&#x3bc;g is guaranteed to obtain high-quality <italic>m/z</italic>191 mass chromatogram. Take the mudstone samples from the Pingbei area for example, the TOC and S<sub>1</sub>&#x2b;S<sub>2</sub> values of mudstone samples vary from 0.23% to 3.68% and from 0.20&#xa0;mg/g to 6.03&#xa0;mg/g (<xref ref-type="table" rid="T3">Table 3</xref>), which were classified as &#x201c;poor&#x201d; to &#x201c;fair&#x201d; level source rocks. Although the chloroform asphalt &#x2018;A&#x2019; extracted from the mudstones are as low as 0.01% (<xref ref-type="table" rid="T3">Table 3</xref>), the high-quality <italic>m/z</italic> 191 mass chromatogram with C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT signature has been obtained from every mudstone sample (e.g., <xref ref-type="fig" rid="F1">Figure 1</xref>). This indicates that our method is not necessarily restricted to hydrocarbon source rocks, but can be applied to a broad spectrum of rocks.</p>
<p>TTs are characterized by higher thermal stability than hopanes and steroterpenes (<xref ref-type="bibr" rid="B39">Peters et al., 1990</xref>; <xref ref-type="bibr" rid="B17">Farrimond et al., 1999</xref>; <xref ref-type="bibr" rid="B56">Xiao et al., 2019a</xref>). Thermal evolution during maturation and high-maturation stages makes little effect on the abundance patterns of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT (<xref ref-type="bibr" rid="B9">Chen et al., 2017</xref>; <xref ref-type="bibr" rid="B57">Xiao et al., 2019b</xref>). As shown in <xref ref-type="table" rid="T2">Table 2</xref>, although the rocks have evolved into the maturities ranging from 1.6% to 2.4%Ro, C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method are still effective in environmental identification. Furthermore, C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT distributions are stable even in the severely biodegraded oils with 25-norhopane series, showing strong resistance to biodegradation (<xref ref-type="bibr" rid="B56">Xiao et al., 2019a</xref>).</p>
</sec>
</sec>
<sec id="s5">
<title>5 Case study: Environmental identification for a complex depositional system in the East China Sea Basin</title>
<p>To test the robustness of the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method for environmental identification, it has been applied to a complex depositional system: the Pingbei area in the East China Sea Basin (<xref ref-type="fig" rid="F11">Figure 11</xref>).</p>
<fig id="F11" position="float">
<label>FIGURE 11</label>
<caption>
<p>Generalized stratigraphy of the Pinghu Formation <bold>(A)</bold>, the paleogeomorphology at the bottom of P1 Member [<bold>(B)</bold>, modified from <xref ref-type="bibr" rid="B29">Li et al., 2019</xref>), the sandstone percentages (including siltstone, obtained by seismic inversion] in the P1 <bold>(C)</bold>, P 2<bold>(D)</bold>, P3 <bold>(E)</bold> and P4 <bold>(F)</bold> members in the Pingbei area in the East China Sea Basin.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g011.tif"/>
</fig>
<sec id="s5-1">
<title>5.1 Geological background of the Pingbei area</title>
<p>The Pingbei area was a hinged margin of a rift basin during the Eocene (<xref ref-type="bibr" rid="B47">Soreghan and Cohen, 1996</xref>). The petroleum system in the area is within the upper-middle Eocene Pinghu Formation, which consists of alternate sandstone, mudstone and thin coal seams. From bottom to top, the Pinghu Formation is further divided into the P1, P2, P3 and P4 members (<xref ref-type="fig" rid="F11">Figure 11A</xref>).</p>
<p>Due to the scarcity of wells and the lack of typical facies indicators in drill core, the depositional environments of the Pinghu Formation have been strongly debated among three possibilities: delta environment (e.g., <xref ref-type="bibr" rid="B45">Shen et al., 2016</xref>; <xref ref-type="bibr" rid="B23">Jiang et al., 2020</xref>), tidal flat environment (e.g., <xref ref-type="bibr" rid="B67">Zhao et al., 2008</xref>) and mixed delta and tidal flat environment (e.g., <xref ref-type="bibr" rid="B66">Zhang et al., 2017</xref>; <xref ref-type="bibr" rid="B1">Abbas et al., 2018</xref>).</p>
</sec>
<sec id="s5-2">
<title>5.2 Depositional environments of Pinghu Formation in the Pingbei area</title>
<p>The Ro values in the Pinghu Formation in the area vary from 0.51% to 0.87% (<xref ref-type="table" rid="T3">Table 3</xref>), indicating a low-mature to mature stage. The C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub> TT abundance patterns cannot be affected by this maturity range, and are thus available to identify depositional environments. The C<sub>21</sub>/C<sub>20</sub>TT and C<sub>23</sub>/C<sub>21</sub>TT ratios were plotted in the discriminating diagram to identify the depositional environment of each member in the Pinghu Formation (<xref ref-type="fig" rid="F12">Figure 12</xref>). Paleogeomorphologic map (<xref ref-type="fig" rid="F11">Figure 11B</xref>) and seismic inversion data (<xref ref-type="fig" rid="F11">Figures 11C&#x2013;F</xref>) are also reported here as additional evidence to (1) support the environmental identification by the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method, and (2) help characterize the spatial distribution of depositional environment (<xref ref-type="fig" rid="F12">Figures 12B, D, F, H</xref>).</p>
<fig id="F12" position="float">
<label>FIGURE 12</label>
<caption>
<p>Environmental identification for the P1 <bold>(A)</bold>, P2 <bold>(C)</bold>, P3 <bold>(E)</bold> and P4 <bold>(G)</bold> members, and depositional environment distribution of the P1 <bold>(B)</bold>, P2 <bold>(D)</bold>, P3 <bold>(F)</bold> and P4 <bold>(H)</bold> members in the Pingbei area.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g012.tif"/>
</fig>
<sec id="s5-2-1">
<title>5.2.1 P1 member</title>
<p>The depositional environments of P1 Member in zones A, B and C (see locations in <xref ref-type="fig" rid="F11">Figure 11B</xref>) are identified as river-lake transitional, freshwater lacustrine and saline-lacustrine/marine facies (<xref ref-type="fig" rid="F12">Figure 12A</xref>), respectively. Organic matter in the carbonaceous mudstone (<xref ref-type="table" rid="T3">Table 3</xref>) in Zone D (<xref ref-type="fig" rid="F11">Figure 11B</xref>) was originated from a terrestrial source through river transportation (<xref ref-type="fig" rid="F12">Figure 12A</xref>). Based on the environmental identification and paleogeomorphologic map of this period (<xref ref-type="fig" rid="F11">Figure 11B</xref>), the depositional environment in Zone D is expected to be marine facies.</p>
<p>Notably, the spatial distribution of these facies is consistent with an environmental transition from continental facies in the north to marine facies in the south (<xref ref-type="fig" rid="F12">Figure 12B</xref>). The Baoyun High formed in the rifting stage (<xref ref-type="fig" rid="F11">Figures 11A, B</xref>) probably isolated the northern freshwater deposition and southern saline water deposition. The interpretation of a freshwater lake in Zone B is acceptable because Zone B was located at the Wuyun Subsag during the P1 period (<xref ref-type="fig" rid="F11">Figure 11B</xref>).</p>
</sec>
<sec id="s5-2-2">
<title>5.2.2 P2 member</title>
<p>The depositional environments of P2 Member are identified as a continental depositional system including freshwater lacustrine facies in the subsag and river-lake transitional facies around the subsag (<xref ref-type="fig" rid="F12">Figures 12C, D</xref>). This environmental identification is supported by the evidence from seismic sedimentology: a large-scale fluvial-induced delta with a bird-foot shaped distribution of sand bodies occurred in the study area (<xref ref-type="fig" rid="F11">Figure 11D</xref>).</p>
</sec>
<sec id="s5-2-3">
<title>5.2.3 P3 member</title>
<p>The spatial distribution and sand body shapes revealed by seismic inversion indicate a wave-altered delta in the north and a speculative delta in the south (<xref ref-type="fig" rid="F11">Figure 11E</xref>), suggesting a transitional facies dominated in the area. For comparison, the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method also identified a transitional facies, but provides much more detailed depositional information: river-lake transitional facies in Zone A, marine facies in Zone B, and marine-continental transitional facies in C and D zones (<xref ref-type="fig" rid="F12">Figures 12E, F</xref>).</p>
</sec>
<sec id="s5-2-4">
<title>5.2.4 P4 member</title>
<p>The depositional environment of P4 Member in Zone A is identified as marine-continental transitional facies (<xref ref-type="fig" rid="F12">Figure 12G</xref>), which is consistent with the interpretation of wave-altered deltas by seismic inversion (<xref ref-type="fig" rid="F11">Figure 11F</xref>). The depositional environments in B and C zones are identified as marine/saline lacustrine and marine-continental transitional facies (<xref ref-type="fig" rid="F12">Figure 12G</xref>). These environments indicate that the Pingbei area was dominated by saline-water deposition during the P4 period (<xref ref-type="fig" rid="F12">Figure 12H</xref>).</p>
</sec>
<sec id="s5-2-5">
<title>5.2.5 Environment evolution of Pinghu Formation</title>
<p>Based on the above depositional environments identified by the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TTs, the environmental evolution process of the Pinghu Formation was reconstructed. The P1 Member in the area is characterized by a coexistence of continental system in the north and marine system in the south which were isolated by the Baoyun High (<xref ref-type="fig" rid="F12">Figure 12B</xref>). During the P2 period, freshwater deposition range obviously expanded and the area was dominated by a continental depositional system (<xref ref-type="fig" rid="F12">Figure 12D</xref>), suggesting a regression has occurred since the P1 period. This regression can be characterized by a synchronous decrease of C<sub>23</sub>/C<sub>21</sub>TT values from the P1 to P2 members in B1 and C1 wells (<xref ref-type="fig" rid="F13">Figures 13A, B</xref>). Subsequently, the depositional environments in the area gradually evolved into a marine depositional system (<xref ref-type="fig" rid="F12">Figures 12F, H</xref>), suggesting a transgression occurred during the P3 and P4 periods in the area. This transgression was also characterized by a synchronous increase of C<sub>23</sub>/C<sub>21</sub>TT values from the P2 to P4 members (<xref ref-type="fig" rid="F13">Figure 13</xref>).</p>
<fig id="F13" position="float">
<label>FIGURE 13</label>
<caption>
<p>The profile of C<sub>23</sub>/C<sub>21</sub>TT ratios along depths for the rock samples in the B2 <bold>(A)</bold>, C1 <bold>(B)</bold> and A1 <bold>(C)</bold> wells. The C<sub>23</sub>/C<sub>21</sub>TT ratios in these three wells vary synchronously along stratum.</p>
</caption>
<graphic xlink:href="feart-11-1128692-g013.tif"/>
</fig>
<p>In summary, the depositional environments of the Pinghu Formation in the Pingbei area were controlled by a complex marine-continental transitional system to a large extent. The C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT biomarker method not only identified the depositional environments supported by evidence from seismic sedimentology, paleogeomorphology and other conventional methods (e.g., <xref ref-type="bibr" rid="B45">Shen et al., 2016</xref>), but also provided much more depositional details. Take the freshwater lacustrine facies hidden in the marine-continental transitional environment for example, it has not been recognized by previous studies but was easily identified by our method. Thus, the C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns are robust for environmental identification even for the complex systems strongly affected by eustasy, which generally resulted in coexistence of and/or fast transition between diverse depositional environments.</p>
</sec>
</sec>
</sec>
<sec sec-type="conclusion" id="s6">
<title>6 Conclusion</title>
<p>Based on the analysis of a large quantity of published data and this study from a range of depositional environments worldwide, we propose that the relative abundance of C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TTs in sedimentary rocks and oils are controlled by the relative contribution of plankton and terrigenous plants. The C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT abundance patterns in marine and saline lacustrine, freshwater lacustrine, shallow-water terrestrial, and marine-continental transitional facies are very distinct, characterized by C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3c;C<sub>23</sub>TT, C<sub>20</sub>&#x3c;C<sub>21</sub>&#x3e;C<sub>23</sub>TT, C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3e;C<sub>23</sub>TT and C<sub>20</sub>&#x3e;C<sub>21</sub>&#x3c;C<sub>23</sub>TT, respectively. The C<sub>23</sub>/C<sub>21</sub>TT ratio increases with increasing salinity of depositional water, while the C<sub>21</sub>/C<sub>20</sub>TT ratio increases with increasing depth of depositional water.</p>
<p>A discrimination diagram has been developed in this study for environmental identification. The C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT ratios can not only identify depositional environments, but also restore the environmental evolution through the analysis of salinity and depth variation. The effectiveness, applicability and robustness of this C<sub>20</sub>-C<sub>21</sub>-C<sub>23</sub>TT method have been demonstrated by the samples with typical environmental indicators and a case study in a complex depositional system in the East China Sea Basin.</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/<xref ref-type="sec" rid="s12">Supplementary Material</xref>; further inquiries can be directed to the corresponding author.</p>
</sec>
<sec id="s8">
<title>Author contributions</title>
<p>AW: Idea, Writing; CL: Data collection, Sample testing, Writing; LL: Review, Supervision, Language polishing; RP: Seismic inversion.</p>
</sec>
<sec id="s9">
<title>Funding</title>
<p>This work was supported by the National Natural Science Foundation of China (No. 41402115); the Natural Science Basic Research Program of Shaanxi (2020JQ-591).</p>
</sec>
<ack>
<p>The authors sincerely thank the SINOPEC Shanghai Offshore Oil &#x26; Gas Company for contributing data. Prof. Qu Hongjun at Department of Geology, Northwest University is thanked for his informative and valuable discussions on research methods of depositional environment.</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="disclaimer" id="s11">
<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 id="s12">
<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.2023.1128692/full#supplementary-material">https://www.frontiersin.org/articles/10.3389/feart.2023.1128692/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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