Palaeogeography, Palaeoclimatology, Palaeoecology 252 (2007) 291 – 303 www.elsevier.

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Abundance anomalies of aromatic biomarkers in the Permian–Triassic boundary section at Meishan, China — Evidence of end-Permian terrestrial ecosystem collapse
Chunjiang Wang a,⁎, Henk Visscher b
a b

Laboratory of Geochemistry and Environmental Science, Faculty of Geosciences, China University of Petroleum, Beijing 102249, China Laborotary of Palaeobotany and Palynology, Faculty of Science, Utrecht University, Budapestlaan 4, 3584 CD Utrecht, The Netherlands Accepted 30 November 2006

Abstract Several aromatic biomarkers detected in solvent extracts and kerogen pyrolysates from samples of the Global Stratotype Section and Point (GSSP) for the Permian–Triassic boundary at Meishan, China, show distinctive relative-abundance anomalies that may be related to the end-Permian biotic crisis on land. Enrichment of dibenzofuran homologues across the Permian–Triassic boundary may corroborate the concept of excessive soil erosion following loss of rooted vegetation. Enrichment of alkylphenol entities occurs just below the main marine mass extinction horizon and prior to the characteristic end-Permian δ13C decline. The alkylphenols were probably derived from lignin and may provide a molecular record of dieback of woody vegetation. Highly decreased relative abundances of dibenzothiophenes could be indicative of excessive supply of Fe2+. It is suggested that Fe2+ was land-derived and may have originated from soils. In addition to the Permian–Triassic boundary interval, biomarker abundance anomalies also occur around the Wuchiapingian–Changhsingian boundary in the basal part of the Meishan section. © 2007 Elsevier B.V. All rights reserved.
Keywords: Permian–Triassic boundary; Aromatic biomarkers; Biotic crisis; Soil erosion

1. Introduction End-Permian extinctions devastated both marine and terrestrial ecosystems (Erwin, 1993). Comparison of the timing of biotic crises on land and in the sea indicates that these were coincident events (Twitchett et al., 2001). Most of our understanding of the extinctions has been based on the study of marine biota, but in recent years the severity of the terrestrial crisis is increasingly recognized.
⁎ Corresponding author. Tel.: +86 10 89733399; fax: +86 10 89733422. E-mail address: wchj333@126.com (C. Wang). 0031-0182/$ - see front matter © 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.palaeo.2006.11.048

Palynological studies show that terrestrial ecosystems experienced preferential dieback of woody vegetation, while in many parts of the world surviving herbaceous lycopsids played a pioneering role in repopulating deforested terrain (Looy et al., 1999, 2001). Peat formation ceased to occur (Retallack et al., 1996). Evidence for terrestrial ecosystem collapse is also provided by a proliferation of fungal remains in Permian–Triassic transition sections from various parts of the world (Eshet et al., 1995; Visscher et al., 1996; Steiner et al., 2003). These remains have been interpreted as terrestrial microfossils reflecting massive decomposition of dead plant material. Further confirmation of the

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Fig. 1. Variation in relative abundance of dibenzofurans and dibenzothiophenes across the Meishan section. Lithological subdivision and age after Jin et al. (2000). L, Longtan Formation; ∑OF, C0–C3-dibenzofurans; ∑SF, C0–C3-dibenzothiophenes; ∑F, C0–C3-fluorenes; Ar, total ions of various series of aromatic compounds, including C0–C3-naphthalenes, C0–C3-biphenyls, C0–C3-phenanthrenes, C0–C3-dibenzofurans, C0–C3dibenzothiophenes, C0–C3-fluorenes, C0–C2-fluoranthenes and pyrenes, C0–C2-chrysenes, C0–C2-benzonaphthothiophenes, C0–C2-benzofluoranthenes and benzopyrenes, C26–C28 triaromatic-steranes. Individual compounds are quantified by calculating their peak area on the specific mass chromatogram of the series of compounds.

severity of the crisis comes from worldwide occurrences of abnormal morphotypes of spores and pollen, which may be considered to reflect increased mutagenesis during a period of excessive environmental stress (Visscher et al., 2004; Foster and Afonin, 2005). Apart from floral turnover, dramatic changes on land are also indicated by widespread soil redeposition (Retallack, 2005) and changing fluviatile regimes due to massive loss of rooted plant life (Ward et al., 2000; Michaelsen, 2002; Arche and López-Gómez, 2005). Marine environmental changes that have been ascribed to effects of terrestrial ecosystem crisis are related to an elevated freshwater input into shallow seas (Kozur, 1998; Korte et al., 2003). In recent years, several molecular organic geochemical studies of the biological and environmental changes during the end-Permian biotic crisis have been carried out (Sephton et al., 1999, 2001; Schwab and Spangenberg, 2004; Sephton et al., 2005; Watson et al., 2005; Xie et al., 2005; Grice et al., 2005a,b; Wang et al., 2005a,b; Wang, 2007). Some of the results provide organic–geochemical

confirmation of the terrestrial crisis. In shallow-marine Permian–Triassic sections in northern Italy, an unusual abundance of oxygen-containing aromatic compounds (such as dibenzofurans) has been discovered close to the extinction interval. These compounds represent landderived diagenetic products of polysaccharides, and may be indicative of massive soil erosion (Sephton et al., 2005). Also in the Meishan section, China, the Global Stratotype Section and Point (GSSP) for the Permian– Triassic boundary (PTB), a variety of organic–geochemical features have been found. Anomalous distributions of pristane (Wang et al., 2005a) and hopane (Xie et al., 2005; Wang, 2007) near the PTB reflect dramatic changes in marine ecosystems. In order to obtain further information on possible effects of terrestrial ecological crises around the PTB, the present paper focuses on the detection and interpretation of aromatic biomarkers through this important reference section.

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2. Sampling and experimental 2.1. Samples The Permian–Triassic boundary section at Meishan is exposed in a series of abandoned limestone quarries near Meishan in Changxing County, Zhejiang Province, China. The quarries are labeled A, B, C, D, E and Z from west to east. Quarry D serves as the GSSP of the PTB. For locality and lithological description of the individual beds, see Yin et al. (1996, 2001, 2005). The section comprises the Changxing Formation and the lower part of the Yinkeng Formation (Fig. 1). Bed 27 is lithologically homogeneous but is subdivided into 27a,

27b, 27c and 27d on the basis of fossil assemblages; the PTB is defined at the base of Hindeodus parvus (conodont) horizon, i.e. the base of Bed 27c (Yin et al., 2001, 2005). The illite–montmorillonite claystone of Bed 25 is of volcanic origin and is regarded as the principal event horizon. Bed 24e represents the lastappearance datum of a wide variety of Late Permian faunal species (Jin et al., 2000). Apart from the PTB, the Meishan section also includes the proposed GSSP for the Wuchiapingian–Changhsingian boundary (WCB, located in the basal part of Bed 4; Jin et al., 2003). This boundary is characterized by the extinction of a significant number of marine faunal elements (Jin et al., 1995; Knoll et al., 1996; Bowring et al., 1998).

Fig. 2. Partial aromatic TIC and the integrated mass chromatogram (m/z 168 + 196 + 210 + 224) showing the relative abundance and distribution of dibenzofurans in Bed 24 and Bed 26. OF, dibenzofuran; MOF, C1-dibenzofurans; DMOF, C2-dibenzofurans; TMOF, C3-dibenzofurans; Ph, phenanthrene; M-Ph, methylphenanthrene.

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A total of 64 samples, collected from quarries B, C and D, was selected for this study (Fig. 1). Samples are representative of each individual bed, including various lithological types, so that the possible effect of lithology on molecular composition could be taken into account. 2.2. Experimental The samples were Soxhlet extracted (with solvent dichloromethane/methanol, 97:3), and the extracts were separated into maltene and asphaltene fractions by precipitation in heptane. The maltenes were fractionated by silica–alumna column chromatography into aliphatic, aromatic and polar fractions by silica–alumna column chromatography, using hexane, benzene, and alcohol as the developers, respectively. To obtain the kerogen, the extracted samples were subjected to cyclic treatments with hydrochloric and hydrofluoric acids. In preparation for pyrolysis, the kerogens were extracted with dichloromethane. The detection and identification of the aromatic compounds was performed on a Finnigan SSQ710 GC– MS using a HP-5MS (30 m × 0.25 mm × 0.25 μm) flexible quartz capillary column. EI mode, helium was used as carrier gas. After an initial period of 1 min at 80 °C, the column was heated to 250 °C at 7 °C/min, and

then to 300 at 2 °C/min, followed by an isothermal period of 15 min. Pyrolysis–GC analysis was carried out using a SGE II pyroprobe coupled to a HP5890 II Plus GC with a HP5 column (30 m × 0.32 mm × 0.25 μm), and with flame ionization detector (FID). The flash pyrolysis temperature was 610 °C (10 s). Helium was used as carrier gas. The GC was held isothermally at 30 °C for 5 min and then ramped at 5 °C/min to 300 where it was held for 10 min. The Py–GC–MS system was equipped by a CDS pyroprobe 2000 fitted with a CDS1500 valve interface held at 250 °C and coupled to a Finnigan Voyager GC800TOP GC–MS with a CPSIL5-CB column (30 m × 0.25 mm × 0.25 μm). Following heating to 610 °C at a rate of 20 °C/ms the sample was held at this temperature for 10 s in a flow of helium. The GC–MS conditions, EI mode, helium was used as carrier gas; the GC was held isothermally at 35 °C for 5 min and then ramped at 3 °C/min to 300 °C where it was held for 10 min. 3. Results and discussion 3.1. Enrichment of dibenzofurans around the PTB Dibenzofuran (DBF) homologues in the aromatic fractions of the samples have been detected from the

Fig. 3. Partial TIC and selected mass chromatograms (m/z 168+182+196+210+224) from Py–GC–MS analysis of kerogen showing the relative abundance and distribution of dibenzofuran entities in the Bed 24e. Squares are used to indicate dibenzofuran homologues: A, dibenzofuran; B–C, C1-dibenzofurans; E–F, C2-dibenzofurans; G–H, C3-dibenzofurans. Alkene/alkane pairs are indicated by inverted “V”. Mass spectra are shown in Fig. 4.

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base of the Changxing Formation up to the lower part of the Yinkeng Formation (Fig. 1). Quantification of the DBF record was based on gas chromatography–mass spectrometry (GC–MS) traces of total ion current (TIC) of the aromatic compound fraction and integrated mass chromatograms (m/z 168 + 196 + 210 + 224) showing the relative DBF abundance of dibenzofurans in the individual beds of the Meishan section. Examples for Bed 24 and Bed 26, shown in Fig. 2, indicate similar distribution patterns of the DBF entities, which occur irrespectively of differences in sedimentary facies or lithology (the two beds are composed of dark grey micrites and dark grey shale, respectively). There are only small differences in demethylation and isomerization of methyldibenzofurans (MDBFs) between different beds. These are probably related to lithologic variation because the DBF/MDBFs values in carbonates are higher than those in mudstones. In Fig. 1 we use the ∑OF/∑(OF + SF + F) and (OF + MOF)/tAr ratios to show the variation in relative abundance of DBF entities. Values of both ratios vary in a rather regular way: higher values in Beds 1–6, followed by lower values in Beds 7–19, and then increased values in Beds 20–32. Highest levels occur in Beds 23–26. It is obvious that the sediments from the

uppermost Changxing Formation and the lower Yinkeng Formation are significantly enriched in DBF entities, with the two ratios being higher than 0.50 and 0.20, respectively. DBF entities are also present in the kerogens derived from individual beds near the PTB at Meishan. Fig. 3 gives a partial TIC and selected mass chromatograms (m/z 168 + 182 + 196 + 210 + 224) showing the relative abundance and distribution of DBF entities obtained by Py–GC–MS analysis of kerogen from Bed 24e. Results of Py–GC analysis of kerogens are shown in Fig. 5. DBF entities are abundant in the interval from Bed 22 to Bed 30, except Bed 27. 3.2. Causes of the enrichment of dibenzofurans DBF and its derivatives may be common components in the aromatic fraction of extracts from terrestrial sediments, which are rich in plant organic matter (e.g. Fan et al., 1990; Radke et al., 2000). However, the Meishan strata represent typical marine sediments deposited in slope to shallow-water basin facies under predominant anoxic/dysoxic conditions (Wignall and Hallam, 1993; Yin and Tong, 1998; Wignall and Twitchett, 2002; Grice et al., 2005a; Wang et al., 2005a).

Fig. 4. Mass spectra corresponding to the retention times of compounds A to G in Fig. 3. The exact positions of the methyl substituents are unknown.

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In marine PTB sections in northern Italy, abundant DBF entities were found in solvent extracts and kerogen pyrolysates from organic-rich marls at the top of the shallow-marine Bellerophon Formation, just below the Tesero horizon (Sephton et al., 1999, 2001, 2005; Watson et al., 2005). Microscopic sedimentary organic matter in these marls was essentially land-derived. The furan-containing compounds are interpreted as the remains of dehydrated polysaccharides originating from eroded soils of terrestrial ecosystems (Sephton et al., 2005). At Meishan, overall organic matter composition is different from that in northern Italy. Because of its amorphous character and the rarity of distinctive land plant debris, microscopic sedimentary organic matter of the Changxing Formation and the Yinkeng Formation is

considered to be predominantly marine (Wang et al., 2005a). In palynomorph assemblages, terrestrial components are rare (Li et al., 2004). Dominance of marine organic matter may be supported by molecular and compound-specific carbon-isotopic studies of nalkanes, isoprenoid HCs, aryl isoprenoids and 2methylhopanes (Wang et al., 2005a; Grice et al., 2005a; Xie et al., 2005). In theory, DBFs might be partly derived from marine organisms including algae, fungi and bacteria. However, there are no records that these organisms actually produce precursor compounds for furan structures. Interestingly, the enrichment of DBF moieties at Meishan does not correlate with other biomarker indices, such as the pristane/phytane ratio (Wang et al., 2005a), and the hopane/sterane and moretane/hopane ratios

Fig. 5. a: Py–GCs of the kerogens from Beds 26–30 in the lowermost Yinkeng Formation. B, benzene; T, toluene; b: Py–GCs of the kerogens from Beds 23–24e at the top of the Changxing Formation; c: Py–GCs of the kerogens from selected beds in the middle part of the Changxing Formation. X, xylene; P, phenol; MP, C1-phenol; DMP, C2-phenol; DMN, C2-naphethalene; OF, dibenzofuran; MOF, C1-dibenzofurans; DMOF, C2-dibenzofurans; TMOF, C3-dibenzofurans. Compounds marked with filled squares could not be identified.

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Fig. 5 (continued ).

(Wang, 2007) around the PTB. This lack of correlation substantiates the concept that the DBFs were not derived from marine biota. Consequently, in view of the fact that elevated DBF concentrations are indicative of terrestrial organic matter, accumulations around the PTB in the Meishan marine sediments are likely to be the result of excessive input of land-derived degradation products of polysaccharides. Because of the scarcity of particulate landderived organic matter in the deeper-marine Meishan sediments, influx of submicroscopic DBFs should have been directly from terrestrial sources. In terrestrial ecosystems, polysaccharides, particularly cellulose of vascular plants, form the bulk of organic matter added to soils. Furan structures can be produced through microbially mediated dehydration of soil polysaccharides (Huang et al., 1998). Therefore, similar to the situation in northern Italy (Sephton et al., 2005), DBF

enrichment in Beds 23–26 at Meishan may point to massive soil erosion following end-Permian destruction of land vegetation. Soil-derived end-Permian DBF enrichment provides independent evidence of terrestrial ecosystem collapse that may have been caused by atmospheric acidification and enhanced UV-B radiation resulting from stratospheric ozone depletion induced by the Siberian Trap volcanism (Campbell et al., 1992; Wignall, 2001; Visscher et al., 2004; Sephton et al., 2005). In contrast to the Italian sections, DBF occurrences at Meishan are not restricted to the PTB interval. Occurrences of DBFs throughout the Changxing Formation may therefore corroborate the concept of a prolonged period of ecosystem destabilization preceding ecosystem collapse. Particularly the WCB interval in the lowermost part of the section may be characterized by increased input of soil organic matter.

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Fig. 5 (continued ).

3.3. Lowered abundance of dibenzothiophenes around the PTB and WCB The relative abundance of S- and O-heterocyclic families in sedimentary organic matter notably varies with depositional environment. Alkyldibenzothiophenes (DBTs or SF) are particularly abundant in marine organic-rich deposits where they dominate over alkylfluorenes (F) and alkyldibenzofurans (DBF or OF) (Radke et al., 2000). The latter seem to prevail in organic-rich freshwater deposits and coal measures (Fan et al., 1990; Radke et al., 2000). The relative abundances of the three series of compounds are usually used as proxies for depositional conditions such as redox status. In Fig. 1, the relative abundance of DBT entities shows an opposite trend to that of DBF entities. The Beds 7–19, characterized by the absence of terrestrial organic matter and deposited under reducing condi-

tions as evidenced by low Pr/Ph values and low abundance of DBFs, are enriched in DBT entities. In marked contrast, the relative abundance of DBTs is lowered in Beds 1–6 and Beds 23–32, (SF + MSF)/tAr values being basically lower than 0.1. These low values would suggest that these beds were formed under oxygenated and freshwater depositional conditions. Such an interpretation conflicts with the well-established anoxic depositional conditions around the PTB (Wignall and Hallam, 1993; Yin and Tong, 1998; Wignall and Twitchett, 2002; Grice et al., 2005a; Wang et al., 2005a), and around the WCB (Wang, 2007). Thus, the formation of DBT entities in the Meishan section needs a re-evaluation. Organic sulfur-containing compounds such as DBTs are predominantly formed by the reaction of reduced inorganic sulfur species with functionalized organic molecules during deposition and early diagenesis

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(Hughes, 1984; Sinninghe Damsté and De Leeuw, 1990). A critical factor controlling the formation of DBTs should be the input of Fe2+ relative to that of S2−. In carbonate depositional environments, the supply of S2− is generally excessive over Fe2+ owing to extensive development of sulphate-reducing bacteria, which enable organic molecules with functional groups (mainly double bonds) to combine with S2− to form organic S-containing compounds, including DBTs. Conversely, in situations of excessive Fe2+ supply, S2− will prefer to react with Fe2+ to form FeS2 while formation of DBTs is inhibited. It is likely, therefore, that increased Fe2+ input has played an important role in lowering DBT concentrations in the PTB and WCB intervals of the Meishan section. Soils were a plausible source of Fe2+. Loss of rooted vegetation may have resulted in excessive Fe2+ transport by river action to marine depositional environments. Alternatively, there may have been a role for the iron cycle, in which iron-

containing soil dust is transported from land through the atmosphere to the oceans (Jickells et al., 2005). 3.4. Enrichment of alkylphenols preceding the marine mass extinction level In the Meishan section, also the aromatic group of alkylphenols shows variation in relative abundances. Fig. 5a, b, and c shows the variation in relative abundance and in distribution of alkylphenol entities in selected beds from the middle part of the Changxing Fm. to the lower part of the Yinkeng Fm. Notably the interval of Bed 23 to Bed 24e is enriched in alkylphenol entities (Fig. 5b). Fig. 6 gives the partial TICs and selected mass chromatograms (m/z 94 + 108 + 122 + 136) based on Py–GC–MS analysis of kerogen samples from two key beds below and above the mass extinction level (the base of Bed 25). It is clear that the distribution of alkylphenol entities in Bed 24e and Bed 26 are very

Fig. 6. Partial TICs and selected mass chromatograms (m/z 94 + 108 + 122 + 136) from Py–GC–MS analysis of kerogens. It is clear that the alkylphenols are much more abundant (as main peaks) in Bed 24e than in Bed 26. A, phenol (P); B–C, C1-phenols (MP); E–G, C2-phenols (DMP); H–J, C3-phenols (TMP). Mass spectra are shown in Fig. 7.

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Fig. 7. Mass spectra corresponding to the retention times of compounds A to J in Fig. 6. A, phenol; B, 2-me-phenol; C, 4- + 3-me-phenol. The exact positions of the methyl substituents in C2- and C3-phenols are unknown.

similar. However, the relative abundances of alkylphenols, as compared with n-alkanes, are different. TIC traces indicate that alkylphenols are much more abundant in Bed 24e than in Bed 26. The alkylphenol-rich interval is also characterized by the onset of other important geochemical changes, such as the onset of DBF enrichment (Fig. 1), the hopane distribution anomaly (Wang, 2007), and the onset of the characteristic end-Permian negative shift in δ13Ccarb (Li, 1999; Jin et al., 2000; Cao et al., 2002; Wang et al., 2005b). Accordingly, the geochemical significance of the enrichment of alkylphenol entities in Beds 23–24 needs further explanation. Phenols are the main units in the chemical structure of suberine (Kolattukudy, 1980). Alkylphenols, along with methoxy-substituted alkylphenols and alkylated catechols, are typical pyrolysis products of lignins and altered lignins (Saiz-Jimenez and De Leeuw, 1986; SaizJimenez et al., 1987; Nip et al., 1987; Hatcher and Clifford, 1997). They are also major components of the pyrolysates of coals (Khorasania and Michelsen, 1991). Because the distribution of alkylphenol entities in Beds 23–24 is basically similar to that in coals, enrichment is

here considered to be indicative of a significant input of lignin-derived organic material to the marine environment. As evidenced by a predominantly amorphous nature, the remains of woody plants must have been heavily biodegraded. Only a small amount could be identified as a typical lignin-derived maceral (vitrinite) (Wang et al., 2005a). In theory, there may be many other potential precursors of alkylphenols, including marine algae (Van Heemst et al., 1999). However, since alkylphenol enrichment is restricted to Beds 23–24, a predominant marine origin would be difficult to explain. Enrichment of alkylphenols occurs just before the main marine mass extinction event recognized at the base of Bed 25 (Jin et al., 2000). Considering a terrestrial origin of the alkylphenols, their enrichment in marine sediments may record the onset of ecological crisis on land characterized by collapse of woody vegetation. The duration of this molecular record could be in the order of several hundred thousands years, but is considerably shorter than the record of DBF enrichment, which can be traced up to Bed 30 (Fig. 1). Interestingly, the enrichment interval of the

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alkylphenol entities basically precedes the onset of the characteristic negative shift in δ13 Ccarb (Li, 1999; Jin et al., 2000; Cao et al., 2002), δ13 Ckerogen value (Cao et al., 2002; Wang et al., 2005b), and in δ 13 C values of individual biomarkers (Wang et al., 2005a,b), which ranges in the Meishan section from the top of Bed 24e to the base of Bed 26. This timing is in accordance with high-resolution palynomorph records from East Greenland, which indicate rapid conversion from closedcanopied gymnosperm woodland to open lycopsiddominant vegetation at the end of the Permian (Looy et al., 2001; Visscher et al., 2004). 4. Conclusions Molecular geochemical study of aromatic fractions in solvent extracts and kerogen pyrolysates from samples from the Permian–Triassic transition section at Meishan reveals an enrichment of dibenzofuran in Beds 22–32 around the Permian–Triassic boundary. Dibenzofurans are probably degradation products of polysaccharides in soils. Their enrichment in marine sediments is suggested to be the result of excessive soil erosion following collapse of terrestrial ecosystems. Alkylphenol entities are notably enriched in Beds 23– 24e, just below the main marine mass extinction horizon (base of Bed 25), and prior to the characteristic negative δ13 Ccarb excursion. The alkylphenols are probably derived from lignin and may provide an important molecular record of massive dieback of woody vegetation. Highly decreased relative abundances of dibenzothiophenes in Beds 1–6 and Beds 23–32 could be indicative for excessive supply of Fe2+ around the Wuchiapingian–Changhsingian and Permian–Triassic boundaries, respectively. It is suggested that Fe2+was land-derived and may have originated from soils. Acknowledgments We would like to thank Prof. Jin Yugan of Nanjing Institute of Geology and Palaeontology, Chinese Academy of Sciences, for his helpful discussions and suggestions, Dr. Peng Ping-an of Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, for Py– GC–MS analysis, Dr. Su Xuefeng of Huabei Institute of Petroleum Sciences, China National Petroleum Corporation, for Py–GC analysis. We thank Dr. Thomas Algeo, Dr. Mark Sephton and an anonymous reviewer for their constructive comments. This work was supported by the National Natural Science Foundation of China (Grant No. 40272056).

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