二叠纪—三叠纪界线大火燃烧的地层记录:研究进展回顾与评述

黑碳和燃烧源多环芳烃作为大火燃烧的产物有很强的化学惰性及生物惰性,能够在地层中长期稳定地保存,所以成为恢复古代大火历史的最常用指标。近年来世界各地二叠系—三叠系(P-Tr)界线地层中相继发现了黑碳(木炭等)和燃烧源多环芳烃等记录,特别是在煤山P-Tr界线地层,黑碳和燃烧源多环芳烃含量在生物灭绝线附近(25～26层)出现极高的峰值,据此首次明确地提出了P-Tr界线大火事件。P-Tr界线大火的规模、性质如何,与P-Tr界线生物灭绝有什么关系等,值得深入讨论和研究。大火事件发生在陆地上,通过其燃烧及排放的烟尘等,把陆地、大气和海洋密切联系起来,有利于通过系统的整体观来研究当时的气候环境变迁。因此,在回顾和总结P-Tr界线地层中的大火燃烧记录基础上,评述了大火事件与生物灭绝及相关地质事件和环境变化之间的联系,以期引起国内外专家学者的关注,为P-Tr界线生物灭绝及相关研究提供新的思路。     

Significance of polycyclic aromatic hydrocarbons (PAHs) in Permian/Triassic boundary sections

In this study the abundances of several polycyclic aromatic hydrocarbons (PAHs Table 1, I–XXI) have been measured throughout three Permian/Triassic (P/Tr) sections from Meishan (South China), Kap Stosch area (East Greenland) and Peace River Basin (Western Canada). Dibenzothiophene (I) and dibenzofuran (II) were found to decrease in abundance just before or shortly after the P/Tr transition in all three sections while perylene (III) was observed to increase in abundance at the onset of the main extinction horizon (bed 25) in Meishan. Perylene has been attributed to a wood degrading fungal source and, therefore, it seems possible these phenomena are related to the demise of land plants. Further, distinct patterns of various combustion-derived PAHs occurring in each section imply that forest fire events occurred within the Late Permian and Early Triassic. In the Meishan section high amounts of combustion-derived PAHs [pyrene (IV), fluoranthene (V), benzo[a]anthracene (VI), benzofluoranthenes (sum, i.e. VII), benzo[a]pyrene (VIII), benzo[e]pyrene (IX) and coronene (X)] occur within bed 25, also containing ash attributed to the fallout from massive volcanic eruptions in Siberia and/or China.     

Origin of perylene in ancient sediments and its geological significance

The distributions of polycyclic aromatic hydrocarbons (PAHs) in sediments of three Upper Triassic to Middle Jurassic sedimentary sequences from the Northern Carnarvon Basin, Australia have been investigated. Perylene was found to be a major PAH component in the top Lower to base Middle Jurassic sediments that are immature or at low maturity. Its depth/age profiles are not related to the combustion-derived PAHs that have been believed to be produced during ancient vegetation fires before deposition. This suggests a diagenetic origin for perylene. The concentration of perylene in the sediments is proportional to the amount of terrestrial input, decreasing with distance from the source of land sediments. Its carbon isotope composition is slightly heavier than higher-plant derived PAHs, but still in the range of the terrestrially sourced PAHs including higher-plant PAHs and combustion-derived PAHs as suggested previously. Fungi are proposed to be the major precursor carriers for perylene in sediments based on the facts that (1) perylenequinone structures have been previously suggested to be the natural precursors for perylene; (2) perylenequinone pigments exist in many fungal bodies; (3) fungi have played an important role during geological processes.     

Analysis of platinum-group elements in drill core samples from the Meishan Permian-Triassic boundary section,China

There is a long-standing controversy of what triggered the extinction at the Permian-Triassic boundary, the most severe mass extinction in the geologic record, including flood basaltic volcanism and/or bolide impact hypothesis. In order to clarify various pieces of evidence for the mass extinction event at the Permian-Triassic boundary, some researchers from some laboratories throughout the world have made a comprehensive study on a group of samples from the Meishan area of China. Some fresh core samples from the Permian-Triassic boundary in the Meishan area were analyzed in this study. The results showed that there is no Ir anomaly, Moreover, the PGEs patterns of those samples show obvious differentiation characteristics, that is different from the case encountered in meteorites. So no evidence supports the hypothesis of extraterrestrial impact. In contrast, the PGEs patterns are similar to those of Siberian and Emeishan basalts, which indicates that those PGEs are derived mainly from the basalts, lending a support to the correlation between mass extinction at the Permian-Triassic boundary and flood basaltic volcanism. This study has also confirmed the results for samples from section C prior to the analysis of the samples.     

浙江长兴煤山剖面P/T界线附近粘土矿物研究

通过对浙江长兴煤山(D)剖面二叠系-三叠系 (P/T)界线附近地层中的粘土矿物分析,显示粘土矿物的组合及含量的变化同粘土矿物的结晶度没有必然的联系,而同地层组段的变化相一致,粘土矿物组合的变化反映了当时的气候、物源及地理条件的变化;同时,伊利石的结晶度也不具有地层梯度的特征。但是,无论是粘土矿物组合还是伊利石结晶度,在P/T界线附近都发生了明显的变化,表明本区当时海洋酸碱度和温度的剧烈变化,这可能导致了二叠纪末期海洋生物的大规模灭绝。     

Black carbon in soils from different land use areas of Shanghai,China: Level,sources and relationship with polycyclic aromatic hydrocarbons

Black carbon (BC) in soils plays a key role of carrying hydrophobic pollutants like polycyclic aromatic hydrocarbons (PAHs). However, little is known about the spatial distribution, sources of BC and its relationship with PAHs in urban soils. We studied BC, total organic carbon (TOC) and PAHs concurrently in 77 soils collected from downtown area, suburban and rural area and industrial area of Shanghai, China. BC was determined by both chemical oxidation (dichromate oxidation, BC_Cr) and chemo-thermal oxidation (CTO-375, BC_CTO). BC sources were identified qualitatively by BC/TOC concentration ratios and BC-cogenerated high molecular weight (HMW) PAH isomer ratios and quantitatively by principal component analysis followed by multiple linear regression (PCA-MLR). Results showed that BC_Cr concentration (4.65 g/kg on average) was significantly higher than BC_CTO (1.91 g/kg on average) in Shanghai soils. BC_Cr concentrations in industrial area were significantly higher than those in other two. Stronger correlation was found between PAHs and TOC, BC_Cr than that between PAHs and BC_CTO, which indicates the possibility of PAHs being carried by charcoal and other organic matters thus negating its exclusive dependence on soot. Charcoal was therefore suggested to be taken into account in studies of BC and its sorption of PAHs. BC/TOC ratios showed a mixed source of biomass burning and fossil fuel combustion. PCA scores of BC-cogenerated HMW PAHs isomer ratios in potential sources and soil samples clearly demonstrated that sources of BC in urban soils may fall into two categories: coal and biomass combustion, and traffic (oil combustion and tire wear). PCA-MLR of HMW PAHs concentrations in soil samples indicated that coal and oil combustion had the largest contribution to BC in urban soils while tire wear and biomass combustion were important in downtown and rural area, respectively, which indicated they were main sources of HMW PAHs and presumably of BC.     

广西东攀二叠系-三叠系界线剖面基于岩石磁参数的米兰科维奇旋回特征和地层对比

二叠纪-三叠纪之交发生了地质历史上最大的生物集群绝灭。通过对广西东攀二叠系-三叠系界线剖面不同的磁学数据进行频谱分析,其结果均具一致的功率谱峰,对比煤山剖面的同位素年龄将厚度频率35.7∶15.6∶7.7cm/cycle换算为时间周期95∶41.6∶20.5kyr/cycle,分别与米兰科维奇旋回偏心率、斜度、岁差相当,从而将地层研究的精度提高到万年级,为生物绝灭和众多地质事件提供时间上的约束。不同的磁学参数分别受控于不同的天文周期,磁性矿物种类主要受偏心率旋回控制,同时也受斜度周期的影响,而岁差周期则是促使岩石携磁能力高频变化的原因。不同二叠系—三叠系剖面(集中在界线附近)的磁化率曲线具有一致特征,可作为界线点确定的辅助依据。     

地层单位与全球界线层型:概念、术语、有关规定与研究实例

全球二叠系-三叠系界线(PTB)层型及点("金钉子")定位我国浙江省长兴县煤山D剖面,极大地推动了PTB及二叠系和三叠系研究进展。在简要介绍地层单位与全球界线层型与点建立的相关概念、术语和有关规定、地层划分的主要种类及其地层单位术语的基础上,以全球二叠系—三叠系界线层型及点(中国浙江省长兴县煤山D剖面)为研究实例,综述了该金钉子剖面牙形石生物地层和年代地层研究现状。煤山D剖面构建了目前全球最完整的PTB地层牙形石带序列,为研究二叠纪末大灭绝后生物残存和复苏过程提供了重要的时间坐标系,也为相关的地质事件研究奠定了坚实的基础。     

Changes of palaeoenvironmental conditions recorded in Late Devonian reef systems from the Canning Basin,Western Australia: A biomarker and stable isotope approach

Although the Late Devonian extinctions were amongst the largest mass extinction events in the Phanerozoic, the causes, nature and timing of these events remain poorly restrained. In addition to the most pronounced biodiversity loss at the Frasnian–Famennian (F–F) boundary and the end Famennian, there were also less extensively studied extinction pulses in the Middle to Late Givetian and the Frasnian. Here we used a combination of palynological, elemental, molecular and stable isotope analyses to investigate a sedimentary record of reef-systems from this time period in the Canning Basin, Western Australia.The acquired data generally showed distinct variations between sediments from (i) the time around the Givetian–Frasnian (G–F) boundary and (ii) later in the Frasnian and indicated a distinct interval of biotic stress, particularly for reef-builders, in the older sediments. Alterations of pristane/phytane ratios, gammacerane indices, Chlorobi biomarkers, δD_kerogen and chroman ratios describe the change from a restricted marine palaeoenvironment with an anoxic/euxinic hypolimnion towards a presumably open marine setting with a vertically mixed oxic to suboxic water column. Simultaneous excursions in δ¹³C profiles of carbonates, organic matter (OM) and hydrocarbons in the older sediments reflect the stratification-induced enhancement of OM-recycling by sulfate reducing bacteria. Alterations in sterane distributions and elevated abundances of methyltrimethyltridecylchromans (MTTCs) and perylene indicate an increased terrigenous nutrient input via riverine influx, which would have promoted stratification, phytoplankton blooms and the development of lower water column anoxia.The detected palaeoenvironmental conditions around the G–F boundary may reflect a local or global extinction event. Our data furthermore suggest a contribution of the higher plant-expansion and photic zone euxinia to the Late Devonian extinctions, consistent with previous hypotheses. Furthermore, this work might contribute to the understanding of variations in Devonian reef margin and platform-top architecture, relevant for petroleum exploration and development in the global Devonian hydrocarbon resources.     

Sulfur isotopic evidence for chemocline upward excursions during the end-Permian mass extinction

The latest Permian was a time of major change in ocean chemistry, accompanying the greatest mass extinction of the Phanerozoic. To examine the nature of these changes, samples from two well-studied marine sections that span the Permian-Triassic boundary have been analyzed: the Meishan and Shangsi sections located in Southern China. Isotopic analysis of the carbonate-associated sulfate in these samples provides a detailed record of several isotopic shifts in δ³⁴S_CAS approaching and across the PTB, ranging from +30 to −15‰ (VCDT), with repeated asynchronous fluctuations at the two locations. We interpret the patterns of isotopic shifts, in conjunction with other data, to indicate a shallow unstable chemocline overlying euxinic deep-water which periodically upwelled into the photic zone. These chemocline upward excursion events introduced sulfide to the photic zone stimulating a bloom of phototrophic sulfur oxidizing bacteria. We hypothesize that elemental sulfur globules produced by these organisms and ³⁴S-depleted pyrite produced in the euxinic water column were deposited in the sediment; later oxidation led to incorporation as CAS. This created the large changes to the δ³⁴S_CAS observed in the latest Permian at these locations.     

Source apportionment of elevated PAH concentrations in sediments near deep marine outfalls in Esquimalt and Victoria,BC, Canada: Is coal from an 1891 shipwreck the source?

Previous studies have suggested that coal from the 1891 shipwreck of a collier off Victoria, BC, Canada is responsible for elevated parent (unsubstituted) PAH concentrations in sediments near deep marine outfalls from Esquimalt and Victoria in the Strait of Juan de Fuca. To resolve this question, we analysed a comprehensive suite of resolved and unresolved complex mixture (UCM) alkanes, tricyclic terpane, hopane and sterane biomarkers, and parent and alkyl polycyclic aromatic hydrocarbons (PAHs) in samples of coal, wastewater and sediments. Composition patterns, principal components analysis (PCA) models and PAH and biomarker ratios all indicate that coal from the collier does not make a dominant contribution to any sediment sample. Mass balance calculations based on the n-C₂₄ content and 24/4 tetracyclic terpane to 26/3R tricyclic terpane ratio in coal provide a particularly good match between predicted and observed alkyl PAH concentrations for sediments with high alkyl naphthalenes and phenanthrene/anthracenes and low UCM, but the predicted coal contribution substantially underestimates the measured parent PAHs for all sediment samples. Methylbenz[a]anthracene/chrysene profiles for sediments with a dominance of parent PAHs are very close to coal tar, with a marked predominance of methylbenz[a]anthracenes and the possible 10-methylbenz[a]anthracene as a major constituent, while the methylchrysenes predominate in coal. Hence, coal from the collier could account for most alkyl PAHs in the sediments, but dredged sediment containing pyrolised coal waste from a former coal gas plant in Victoria Harbour is a more likely source for the samples with elevated parent PAHs. PAH ratios indicate that these sources are superimposed on combustion PAHs introduced by a combination of atmospheric deposition and delivery via stormwater and the outfalls. Parent PAH distributions also suggest that PAHs in wastewater that originate from oils and soot in liquid fossil fuel combustion are dispersed and degraded, while the larger wood char particles (containing PAHs more protected from degradation) settle closer to the outfalls. Overall, results suggest that PAHs have predominant sources in wood combustion, coal and possibly coke, with a likelihood of much lower bioavailability than would be expected from wastewater dominated by oils and soot from vehicle combustion.     

浙江煤山二叠-三叠系界线剖面有机和无机碳同位素变化与古环境

浙江长兴煤山 D剖面 196个碳酸盐岩样品无机和有机碳同位素δ13Ccarb和δ13Corg变化趋势表明,煤山地区晚二叠世末为比较封闭的局限海沉积环境,早三叠世初期经局限和开阔海环境交替出现渐变为海水循环良好的广海沉积环境.长兴期的海进作用使海洋初始生产率升高,可能是引起长兴组葆青段碳同位素变重的主要原因;海洋 CO2浓度增高可能是长兴组煤山段δ13Corg出现负漂移的原因.二叠纪末期全球性海平面下降以及火山作用可能是使生态系统崩溃、引起二叠-三叠系 (P- T)界线附近生物绝灭的外部原因,也是使海洋中 12C输入量增加导致过渡层碳同位素变轻的主要原因.二叠纪晚期生物绝灭经历了由渐变到突变的过程.δ13Corg在生物绝灭后才出现大幅度负漂移,可能是由于营光合作用的浮游植物不一定因海洋缺氧以及其他生物的绝灭而停止生长,当海水酸度超过浮游生物忍耐限度时,才导致浮游生物大量死亡.殷坑组δ13Corg和δ13Ccarb呈上升趋势,说明经历过 P- T生物大绝灭后,早三叠世海洋生产率逐渐升高,生物开始复苏.     

Zircon Hf-O-Li isotopes of granitoids from the Central Asian Orogenic Belt: Implications for supercontinent evolution

Deep lithospheric processes associated with the formation of major orogens, including the removal of lower crust and underlying mantle through delamination associated with orogen building are poorly constrained. With a view to evaluate the potential link between deep geodynamic processes and magmatic events, we performed in situ zircon Hf-O-Li isotopic analyses of granitoids from the Eastern and Western Junggar, Altai and Beishan orogens, within the Central Asian Orogenic Belt (CAOB). The ε_Hf(t) and δ¹⁸O values of magmatic zircons crystallized during 443 Ma and 252 Ma indicate diverse and heterogeneous magma sources. The corresponding δ⁷Li peaks at ~440 Ma and ~250 Ma, suggesting two distinct high-temperature magmatic events. Based on a comparison with global data, we argue that large-scale delamination formed through Gondwana and Pangaea supercontinent assembly, may have occurred at Ordovician to Silurian boundary (OSB) and Permian to Triassic boundary (PTB), which we term as super-delamination. The subsequent widespread magmatism and volcanism might have made significant impact on the Earth surface ecosystems, ultimately leading to the OSB and PTB mass extinction events. We propose super-delamination as a potential mechanism to explain the link between Earth's internal and external processes, thus providing novel insights into the trigger for mass extinction events.     

三叠纪—侏罗纪之交准噶尔盆地南缘野火记录及全球对比

三叠纪—侏罗纪之交(距今约201 Ma)是地球历史上的关键时期,中大西洋火成岩省(Central Atlantic magmatic province,CAMP)快速地侵位和喷发,给全球的表生系统带来巨大的环境压力,其中之一是被广泛报道的同期野火事件.但此前的报道多集中在CAMP直接作用范围区内,对其是否具有全球性,以...     

Temporal trends of aliphatic and polyaromatic hydrocarbons in the Bohai Sea, China: Evidence from the sedimentary record

This work reports the historical trends and sources of aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) in two ²¹⁰Pb dated sediment cores extracted from the central mud areas of Bohai Sea (Bohai). The TOC/TN ratio of the bulk organic matter (OM) and the composition of the n-alkanes suggest that the sedimentary organic matter was of mixed marine and terrigenous sources. The coarser sediment grain size and decreasing C/N ratios since ∼1976 could be attributed to the relocation of the Yellow River mouth causing a decreased influence of Yellow River derived sediments and associated OM into the central Bohai. The concentration of total 16 PAHs in the two cores ranged from 34.2-202 ng/g (mean, 91.5) for BC1, and from 53.3-186 ng/g (mean, 103) for BC2, with a high abundance of 2-3 ring PAHs. Perylene in the two cores mainly originated from terrigenous sources via riverine discharge and thus could be potentially related to changes in the sediment load from the Yellow River into the Bohai over time. Petroleum inputs could be revealed by ratios of methylphenanthrenes to phenanthrene (MP/P) and the patterns of more stable geochemical biomarkers (hopanes and steranes) along the two cores, in addition to the presence of unresolved complex mixtures (UCM) in the surface layers. Source diagnostic ratios of PAHs indicated a pyrogenic origin from biomass and coal combustion with a minor petroleum contribution. Downcore trends of compositional PAHs profiles were in agreement with the socio-economic development in China in the past decades. This temporal variation of sedimentary PAHs can also reflect a different evolution stage of energy structure in China as compared with those of the western developed countries.     

European ammonoid diversity questions the spreading of anoxia as primary cause for the Cenomanian/Turonian (Late Cretaceous) mass extinction

Ammonoid diversity patterns show that the spreading of oceanic anoxia is not the initial and major kill mechanism for the Cenomanian/Turonian mass extinction as usually suggested. In the Anglo-Paris Basin and the Vocontian Basin, the drop of ammonoid species richness starts around the middle/late Cenomanian boundary, i.e. 0.75 myr before the occurrence of anoxic deepwater sediments. The stepwise extinction of first heteromorphs and then acanthoceratids is incompatible with the rise of the oxygen minimum zone. Moreover, shelf environments of these basins remained well oxygenated during the Cenomanian/Turonian boundary interval. Thus, we stress that other causative mechanisms initiated the ammonoid extinction even if anoxia subsequently participated in the demise of marine ecosystems. Editorial handling: M.J. Benton & J.-P. Billon-Bruyat     

Characterization of Iron Grains near the P/T Boundary in the Meishan Section of China

The Meishan section of China has been confirmed as the ＂Global Stratotype Section and Point＂ of the P/T boundary. In the section, the authors found several types of iron grains, including pyrite, pure iron grains and goethite. From the research of macro minerals, it is easy to find that the grains rich in iron appear from the bottom of the event layer of the section. In other words, it is probably residue of the geochemical catastrophe of that time. Therefore, it is important to trace the source of these iron grains and their relationships, which probably provides evidence for volcanic eruption or impact-volcanoes and has directive significance to the crisis during the P/T transitional period. Through the study of the characterization and relationships of these iron grains, the authors make a preliminary discussion on the P/T mass extinction.     

Deccan volcanism linked to the Cretaceous-Tertiary boundary mass extinction: New evidence from ONGC wells in the Krishna-Godavari Basin

A scientific challenge is to assess the role of Deccan volcanism in the Cretaceous-Tertiary boundary (KTB) mass extinction. Here we report on the stratigraphy and biologic effects of Deccan volcanism in eleven deep wells from the Krishna-Godavari (K-G) Basin, Andhra Pradesh, India. In these wells, two phases of Deccan volcanism record the world’s largest and longest lava mega-flows interbedded in marine sediments in the K-G Basin about 1500 km from the main Deccan volcanic province. The main phase-2 eruptions (∼80% of total Deccan Traps) began in C29r and ended at or near the KTB, an interval that spans planktic foraminiferal zones CF1–CF2 and most of the nannofossil Micula prinsii zone, and is correlative with the rapid global warming and subsequent cooling near the end of the Maastrichtian. The mass extinction began in phase-2 preceding the first of four mega-flows. Planktic foraminifera suffered a 50% drop in species richness. Survivors suffered another 50% drop after the first mega-flow, leaving just 7 to 8 survivor species. No recovery occurred between the next three mega-flows and the mass extinction was complete with the last phase-2 mega-flow at the KTB. The mass extinction was likely the consequence of rapid and massive volcanic CO₂ and SO₂ gas emissions, leading to high continental weathering rates, global warming, cooling, acid rains, ocean acidification and a carbon crisis in the marine environment.     

The prelude of the end-Permian mass extinction predates a postulated bolide impact

The mass extinction at the Permian–Triassic Boundary (PTB) is said to have been abrupt and probably caused by an extraterrestrial impact. However, evidence from the Global Stratotype Section and Point (GSSP) of the base of the Induan at Meishan, China, shows that the biotic crisis began prior to the level, in beds 25 and 26 at which the postulated impact event occurred. Evidence of such an earlier biotic crisis occurs in other sections in South China, and in central and western Tethyan regions. This event is characterized by the extinction of a range of faunas, including corals, deep-water radiolarians, most fusulinids and pseudotirolitid ammonoids, and many Permian brachiopods. In all sections, this extinction level is usually a few decimeters to meters below that of the main mass extinction in the event beds (25 and 26) at Meishan, and their correlatives elsewhere. This earlier extinction event happened before the postulated bolide impact at the level of beds 25 and 26, and constrains interpretation of the mechanisms that brought about this greatest mass extinction. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Molecular characterization of dissolved black nitrogen via electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Combustion produces a complex mixture of polycondensed aromatic compounds known as black carbon (BC). Such products can become remobilized from char and soil in the form of dissolved BC (DBC). Ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI–FT-ICRMS) analysis of a variety of soil and char leachates showed that a significant proportion of DBC compounds contained one or more nitrogen atoms. While the presence of black nitrogen (DBN) in dissolved organic matter (DOM) has been reported, its molecular features were uncharacterized. Here we present results of FT-ICRMS characterization of DBN, where assigned formulae were validated on the basis on their ¹³C isotope signatures and fragmentation patterns obtained via collision induced dissociation. Possible chemical structures were assigned for several DBN formulae and suggest that nitrogen was incorporated into the core ring system as a pyrrole-type moiety. Most DBN compounds existed as part of homologous series where homologs differed by a mass corresponding to CO₂, suggesting that they were polysubstituted with carboxylic acid groups. The environmental contribution of such novel, aromatic, combustion-derived nitrogen compounds with respect to global nitrogen cycling remains elusive. The biogeochemical implications of the input of such fire-derived products to aquatic ecosystems as part of climate change therefore need to be assessed.