Constraining the Ediacaran oceanic dissolved organic carbon reservoir: Insights from carbon isotopic records from a drill core from South China

The evolution of the atmospheric oxygen content through Earth’s history is a key issue in paleoclimatic and paleoenvironmental research. There were at least two oxygenation events in the Precambrian that involved fundamental changes in both biotic innovation and the surface environment. However, a large dissolved organic carbon (DOC) pool maintained in deep oceans during the Neoproterozoic may have extended the time interval between the two oxygenation events. To test the DOC hypothesis, we conducted detailed micro-drilled analyses of carbonate carbon isotopes (δ13C_carb) of a long Ediacaran drill core (the Wangji drill core), for which whole-rock δ13C_carb and organic carbon isotope (δ13C_org) records were available. The micro-drilled δ13C_carb values obtained in this study are consistent with whole-rock δ13C_carb results, precluding the influence of severe authigenic carbonate incorporation. Importantly, the multiple negative δ13C_carb excursions in the Wangji drill core were likely linked with upwelling events, during which DOC was supplied to the surface water and oxidized. Using box models, we estimate that ~3.6 × 1019 mol and ~2.0 × 1019 mol DOC were converted to bicarbonate during two negative δ13C_carb excursions spanning millions of years. The estimations are approximately 1000 times the modern marine DOC reservoir. Our results support a relatively high oxidation capacity (elevated atmospheric pO₂ and/or oceanic [\begin{document}${\rm{SO}}_4^{2 - }$\end{document}]) of the Earth’s surface during the early Ediacaran Period.     

大洋缺氧事件的碳稳定同位素响应

从碳稳定同位素组成及其分馏机理出发 ,系统探讨了大洋缺氧事件与海相碳酸盐和有机碳稳定同位素分馏之间的关系。缺氧事件期间 ,由于生物大批死亡和快速埋藏 ,其分解消耗海水中大量的溶解氧 ,引起大洋水体缺氧 ,富含 1 2 C的有机质从而得以大量保存 ;相应地大气和海水中富 1 3 C,同期海相碳酸盐岩碳同位素 δ值 (δ1 3C)正偏。在世界各地缺氧事件层内 ,无一例外地碳酸盐岩碳稳定同位素出现了不同程度的正偏 ,Cenomanian- Turonian 界线偏幅达～2‰。海相碳酸盐与有机质碳稳定同位素变化不仅可以提供地质历史中有机碳埋藏量的记录。研究全球碳循环变化 ,还可能追溯有机碳风化和埋藏速率的变化 ,定性地恢复大气 p CO2 变化。     

Stable isotopic evidence for methane seeps in Neoproterozoic postglacial cap carbonates

The Earth's most severe glaciations are thought to have occurred about 600 million years ago, in the late Neoproterozoic era. A puzzling feature of glacial deposits from this interval is that they are overlain by 1-5-m-thick 'cap carbonates' (particulate deep-water marine carbonate rocks) associated with a prominent negative carbon isotope excursion. Cap carbonates have been controversially ascribed to the aftermath of almost complete shutdown of the ocean ecosystems for millions of years during such ice ages--the 'snowball Earth' hypothesis. Conversely, it has also been suggested that these carbonate rocks were the result of destabilization of methane hydrates during deglaciation and concomitant flooding of continental shelves and interior basins. The most compelling criticism of the latter 'methane hydrate' hypothesis has been the apparent lack of extreme isotopic variation in cap carbonates inferred locally to be associated with methane seeps. Here we report carbon isotopic and petrographic data from a Neoproterozoic postglacial cap carbonate in south China that provide direct evidence for methane-influenced processes during deglaciation. This evidence lends strong support to the hypothesis that methane hydrate destabilization contributed to the enigmatic cap carbonate deposition and strongly negative carbon isotopic anomalies following Neoproterozoic ice ages. This explanation requires less extreme environmental disturbance than that implied by the snowball Earth hypothesis.     

全球古元古代碳同位素正异常的数据分析与成因评述

归纳总结了前人关于全球古元古代(2.20 ～2.06 Ga)碳酸盐岩碳同位素正异常现象的基础数据及资料。在此基础上, 对前人关于该正异常成因的假说(生物演化- 大气充氧说、古元古代冰期期后说、超级地幔柱- 超大陆裂解说及蒸发环境说等)进行了评估, 认为以上假说虽然都有地质证据支持, 但其重要性还是有些差异。根据碳同位素分馏原理, 有机物的繁盛会使碳酸盐碳储库的同位素变正。生物演化导致大气充氧、古元古代冰期后形成的温暖环境和Kenorland超大陆裂解均为生物的繁盛提供了有利条件, 从而使碳酸盐碳储库的同位素变正。另外, 蒸发环境在全球多有分布, 它可能是造成部分局域封闭式环境碳同位素正异常的原因, 所以应对发现正异常的各区域进行详细的沉积环境分析。以4个区域的数据为对象, 分析了古元古代碳酸盐岩碳同位素正异常数据的可靠性; 通过Mn/Sr, δ¹³C和δ¹⁸O三者的关系图, 判断了沉积期后作用对于数据的改造程度。     

Isotopic evolution of the terminal Neoproterozoic and early Cambrian carbon cycle on the northern Yangtze Platform, South China

Profound geotectonic, climatic and biological changes occur during the terminal Neoproterozoic and its transition into the early Cambrian. These are reflected in temporal variations of the chemical and isotopic composition of seawater. We are studying a sequence of sedimentary rocks at the Shatan section, northern Yangtze Platform, Sichuan Province of China. This succession comprises, in ascending stratigraphic order, predominantly calcareous sediments of the Sinian upper Dengying Formation and black shales of the lower Cambrian Guojiaba Formation (time equivalent of Niutitang Fm.). Paleoenvironmental setting represents shallow-water shelf deposits. The objective of our study is to provide temporal records for the isotopic compositions of organic and carbonate carbon throughout this time interval. Organic carbon isotope values display a range between -35.8‰ and -30.1‰ with clear stratigraphic variations. Carbonate carbon isotope data vary between -3.5‰ and +0.5‰. These secular variations are interpreted to reflect perturbations of the global carbon cycle, specifically changes in the fractional burial of organic carbon. However, local conditions have further affected the isotopic signals.     

Carbon isotopic record from Upper Devonian carbonates at Dongcun in Guilin,southern China,supporting the worldwide pattern of carbon isotope excursions during Frasnian-Famennian transition

Carbon isotopic composition of carbonates and or-ganic matter in sediments has been a powerful tool for deducing perturbations in the global carbon cycle which, in many cases, is observed together with the occurrence of biological mass extinctions[1]. The Frasnian-Famennian (F-F) mass extinction[2,3], so-called F-F event or bio-crisis, has been recognized as one of the five major bioevents of Phanerozoic time[4—7], and more than 60% of all Frasnian genera were eliminated[3,11]. This event …     

Latitudinal variations in plankton delta 13C: implications for CO2 and productivity in past oceans

The stable-carbon isotopic composition of marine organic material has varied significantly over geological time, and reflects significant excursions in the isotopic fractionation associated with the uptake of carbon by marine biota. For example, low 13C/12C in Cretaceous sediments has been attributed to elevated atmospheric (and hence oceanic) CO2 partial pressures. A similar depletion in 13C present-day Antarctic plankton has also been ascribed to high CO2 availability. We report, however, that this high-latitude isotope depletion develops at CO2 partial pressures (pCO2 levels) that are often below that of the present atmosphere (340 microatmospheres) , and usually below that of equatorial upwelling systems (> 340 microatmospheres). Nevertheless, because of the much lower water temperatures and, hence, greater CO2 solubility at high latitude, the preceding pCO2 measurements translate into Antarctic surface-water CO2 (aq) concentrations that are as much as 2.5 times higher than in equatorial waters. We calculate that an oceanic pCO2 level of > 800 microatmospheres (over twice the present atmospheric pCO2) in a warmer low-latitude Cretaceous ocean would have been required to produce the plankton 13C depletion preserved in Cretaceous sediments.     

廉州湾红树林大型底栖动物食物来源研究

【目的】了解可能性食物源对红树林大型底栖动物的贡献率。【方法】利用碳氮稳定同位素技术,对广西廉州湾红树林大型底栖动物及可能性食物源的碳、氮同位素比值(δ~(13) C值、δ~(15) N值)进行分析,并通过贝叶斯稳定同位素混合模型,估算不同食物源对大型底栖动物的贡献率。【结果】大型底栖动物的δ~(13) C值为-23.37‰~-18.09‰,δ~(15) N值为6.59‰~17.00‰,δ~(13) C值、δ~(15) N值的变化范围较大,表明大型底栖动物食物来源较为复杂多样。7种可能性食物源的δ~(13) C值为-29.09‰~-21.53‰,δ~(15) N值为6.85‰~15.67‰,其中红树植物的δ~(13) C值最为贫化。大型底栖动物的营养级别均小于3,表明它们基本属于初级消费者。SIAR混合模型计算结果显示,颗粒有机物(POM)对大型底栖动物有较高的贡献率,其次为表层沉积物(SOM),大型藻类、附生植物的贡献率较低,红树植物叶片、落叶、树皮对大型底栖动物的贡献率最低。【结论】POM、SOM是广西廉州湾红树林大型底栖动物重要的食物源,红树植物不是大型底栖动物碳的主要来源。     

Snowball Earth termination by destabilization of equatorial permafrost methane clathrate

The start of the Ediacaran period is defined by one of the most severe climate change events recorded in Earth history--the recovery from the Marinoan 'snowball' ice age, approximately 635 Myr ago (ref. 1). Marinoan glacial-marine deposits occur at equatorial palaeolatitudes, and are sharply overlain by a thin interval of carbonate that preserves marine carbon and sulphur isotopic excursions of about -5 and +15 parts per thousand, respectively; these deposits are thought to record widespread oceanic carbonate precipitation during postglacial sea level rise. This abrupt transition records a climate system in profound disequilibrium and contrasts sharply with the cyclical stratigraphic signal imparted by the balanced feedbacks modulating Phanerozoic deglaciation. Hypotheses accounting for the abruptness of deglaciation include ice albedo feedback, deep-ocean out-gassing during post-glacial oceanic overturn or methane hydrate destabilization. Here we report the broadest range of oxygen isotope values yet measured in marine sediments (-25 per thousand to +12 per thousand) in methane seeps in Marinoan deglacial sediments underlying the cap carbonate. This range of values is likely to be the result of mixing between ice-sheet-derived meteoric waters and clathrate-derived fluids during the flushing and destabilization of a clathrate field by glacial meltwater. The equatorial palaeolatitude implies a highly volatile shelf permafrost pool that is an order of magnitude larger than that of the present day. A pool of this size could have provided a massive biogeochemical feedback capable of triggering deglaciation and accounting for the global postglacial marine carbon and sulphur isotopic excursions, abrupt unidirectional warming, cap carbonate deposition, and a marine oxygen crisis. Our findings suggest that methane released from low-latitude permafrost clathrates therefore acted as a trigger and/or strong positive feedback for deglaciation and warming. Methane hydrate destabilization is increasingly suspected as an important positive feedback to climate change that coincides with critical boundaries in the geological record and may represent one particularly important mechanism active during conditions of strong climate forcing.     

东濮凹陷沙河街组三段湖相沉积与地球化学特征

通过对典型井位濮115井沙三段地层进行岩芯观察和薄片鉴定, 结合碳、氧稳定同位素和元素地球化学特征研究, 对东濮凹陷沙河街组三段碳酸盐岩及陆源碎屑与碳酸盐的混合沉积作用机理和成因进行讨论。结果表明: 研究井段地层中碳酸盐组分为自生矿物, 碳酸盐岩和碎屑岩中碳酸盐的碳、氧同位素分异明显, 碳酸盐岩中δ¹⁸O偏正, δ¹³C偏负; 碎屑岩中δ¹⁸O偏负, δ¹³C偏正; 混积岩为二者的线性混合。同位素特征指示碳酸盐岩在强蒸发、弱淡水注入的条件下形成, 湖水相对封闭, 水体较浅, 底层水体可能呈氧化状态; 碎屑岩形成于弱蒸发、多淡水注入的相对开放湖体中, 湖平面较高, 底层水体可能缺氧; 混积岩则形成于两者的过渡阶段。频繁变动的碳、氧同位素组成可能指示对应沉积期的气候条件和湖平面, 并指示湖盆底层水体氧化还原状态的频繁变动。研究井段陆源碎屑含量逐渐减少, 可能指示湖平面整体上处于下降期, 与之相对应的沉积期湖盆相对封闭的阶段占主导。     

北京大学未名湖沉积物中公元1747年以来气候变化的氧碳同位素记录

对北京大学未名湖底泥层做了²¹⁰Pb计年法和¹³⁷Cs时标法定年以及氧碳同位素分析。结果表明厚度约50cm的底泥层形成于公元1747—1997年之间,湖泥中碳酸盐的氧碳同位素组成和有机物含量记录了北京地区公元1747年以来的气候变化：1866年以前冬季风盛行,气候比较寒冷干燥;1887年以后夏季风盛行,气候比较温暖湿润,其中1907—1926年是近250年以来气候最为温暖湿润的时期;介于两者之间的1867—1886年是气候急剧转型的时期,也是自然灾害频繁出现的时期。     

Evidence from carbon isotope measurements for diverse origins of sedimentary hydrocarbons

The organic matter found in sedimentary rocks must derive from many sources; not only from ancient primary producers but also from consumers and secondary producers. In all of these organisms, isotope effects can affect the abundance and distribution of 13C in metabolites. Here, by using an improved form of a previously described technique in which the effluent of a gas chromatograph is continuously analysed isotopically, we report evidence of the diverse origins of sedimentary organic matter. The record of 13C abundances in sedimentary carbonate and total organic carbon can be interpreted in terms of variations in the global carbon cycle. Our results demonstrate, however, that isotope variations within sedimentary organic mixtures substantially exceed those observed between samples of total organic carbon. Resolution of isotope variations at the molecular level offers a new and convenient means of refining views both of localized palaeoenvironments and of control mechanisms within the global carbon cycle.     

塔里木盆地奥陶纪碳同位素波动特征与对比

在牙形石生物地层的基础上,利用塔里木盆地塔北隆起钻井全岩碳同位素数据,结合其他学者公布的碳同位素曲线,探讨了塔里木盆地奥陶纪碳同位素波动特征,并与世界其他地区进行对比。塔里木盆地奥陶纪特马豆克阶－达瑞威尔阶早期碳同位素波动较弱,缺乏可全球对比的波动标志。达瑞威尔阶中期和凯迪阶早期发育明显的碳同位素正漂移,分别对应于国际上的中达瑞威尔阶碳同位素正漂移（MDICE）和加顿伯格碳同位素正漂移（GICE）,能够进行全球对比。桑比阶早期牙形石 Pygodus anserinus 带内发育波动幅度达1.4‰的正漂移,其可能仅在部分地区分布,暂时命名为早桑比阶碳同位素正漂移（ESICE）。凯迪阶中后期碳同位素波动特征目前还不清楚,晚奥陶世赫南特阶碳同位素正漂移（HICE）在塔里木盆地也未见报道。MDICE 和 GICE 可作为塔里木盆地中上奥陶统的等时对比标志。     

Carbon isotope kinetics of gaseous hydrocarbons generated from different kinds of vitrinites

Kinetics study of gaseous hydrocarbons generated from vitrinites based on pyrolysis of gold tube closed system shows that the activation energies of methane generated from telocollinite are higher than that from desmocol-linite due to structure differences. But carbon isotope ratios of generated methane in pyrolysates of vitrinites at the same temperature points are similar. Carbon isotope ratio of methane may decrease in the early stage of gas generation and then increase in the later stage. But at higher temperature, δ13C1 decreases slightly or almost keeps stable with increasing temperature. Since it is known that carbon isotope distillation is controlled by time, temperature and carbon isotope ratio of bulk organic matter, the character of side chains connected to macromolecule of vitrinite and distribution of activation energies have no obvious effect on carbon isotope fraction. Decreasing trend of δ13C1 in the early stage may be caused by contagious structure of vitrinite or differences of activation energies between 12C-12C and 12C-13C are not strictly constant at different ranges of activation energy area.     

重庆北碚嘉陵江组第三—第四段碳酸盐岩碳同位素组成对古海水代表性

早三叠世海水的碳同位素组成是近年来地学研究的热点之一,但全球早三叠世碳同位素组成并没有获得统一的认识。上扬子地区早三叠世晚期普遍发育蒸发岩,地表剖面则因表生成岩作用而形成一套夹盐溶角砾岩及次生灰岩的碳酸盐地层,其地球化学信息不同程度地偏离海水,因而样品成岩蚀变性对古海水碳同位素组成的代表性的评估显得十分重要。本文以中、下三叠统界线清楚的重庆北碚剖面为对象,研究了下三叠统嘉陵江组第三、第四段和中三叠统雷口坡组底部样品的元素组成,碳、氧同位素组成及彼此之间的相互关系,选择Mn含量和氧同位素作为条件评价碳酸盐岩的成岩蚀变性及其对海水碳同位素组成的代表性,在此基础上建立了早三叠世晚期海水的碳同位素演化曲线。研究表明:(1)北碚剖面嘉陵江组第三、第四段(嘉三、嘉四段)及雷口坡组底部碳酸盐岩的Mn、Fe含量与碳同位素组成之间具有良好的负相关性,氧同位素组成和碳同位素组成之间则具有良好的正相关性,大量样品具有低δ18 O值、低δ13 C值以及较高Mn、Fe含量的特征,说明其碳同位素组成偏离海水。(2)以δ18 O-7.5‰、方解石的Mn质量分数100×10-6、白云石的Mn质量分数120×10-6为评价条件,北碚剖面嘉三、嘉四段(含雷口坡组底部)的73个样品中有38个需要在建立海水碳同位素曲线时剔除,占全部样品的52%。其中嘉四段需要剔除的样品占嘉四段样品的78%,而嘉三段的该数值为11%,说明作为原始沉积的灰岩段对海水地球化学信息保存较好,而分布盐溶角砾岩及次生灰岩的层位对海水地球化学信息保存很差。(3)氧同位素作为成岩蚀变评价标准比Mn含量更为苛刻,并可基本覆盖Mn含量评价条件,说明对于嘉三—嘉四段这样的石灰岩—白云岩—蒸发岩地层的地表剖面的样品来说,选择氧同位素作为评价条件可较好地对碳同位素的原生性进行控制。(4)白云岩对海水地球化学信息总体上保存较好,与相邻石灰岩相比,白云岩具有更高的δ18 O和δ13 C值,但其原因仍然需要进一步研究,可能与同位素分馏系数的差别以及白云岩形成于盐度更高的流体有关,因而白云岩所代表的海水地球化学信息可能不完全与伴生石灰岩相同。(5)除绿豆岩附近出现了短时间的变化超过4‰的大幅度波动以外,早三叠世晚期海水的碳同位素演化相对平稳,大致在-0.3‰~-1.8‰的范围内波动,呈现一个低幅的"V"字形,显示早三叠世晚期地球生态的恢复与碳循环系统的重建。     

Variations of sulfur and carbon isotopes in seawater during the Doushantuo stage in late Neoproterozoic

The Doushantuo Formation of the Sinian System in the Yangtze area is the first sedimentary stratigraphic unit after the Neoproterozoic Snowball Earth event[1], named the Nantuo Glaciation in south China. There are not only phosphorite and manganese mineralized beds[2], but also a series of biome which represents the biological radiation in Neoproterozoic[3] found in this formation. It is important to study the palaeoenvironment and the early biological evolution implied in the Doushantuo …     

The influence of rivers on marine boron isotopes and implications for reconstructing past ocean pH

Ocean pH is particularly sensitive to atmospheric carbon dioxide content. Records of ocean pH can therefore be used to estimate past atmospheric carbon dioxide concentrations. The isotopic composition of boron (delta11B) contained in the carbonate shells of marine organisms varies according to pH, from which ocean pH can be reconstructed. This requires independent estimates of the delta11B of dissolved boron in sea water through time. The marine delta11B budget, however, is still largely unconstrained. Here we show that, by incorporating the global flux of riverine boron (as estimated from delta11B measurements in 22 of the world's main rivers), the marine boron isotope budget can be balanced. We also derive ocean delta11B budgets for the past 120 Myr. Estimated isotope compositions of boron in sea water show a remarkable consistency with records of delta11B in foraminiferal carbonates, suggesting that foraminifera delta11B records may in part reflect changes in the marine boron isotope budget rather than changes in ocean pH over the Cenozoic era.     

Climate as the dominant control on C<Subscript>3</Subscript> and C<Subscript>4</Subscript> plant abundance in the Loess Plateau: Organic carbon isotope evidence from the last glacial-interglacial loess-soil sequences

Two modes of photosynthesis predominate in terres-REPORTS trial plants: the C3 and C4 modes[1]. The C3 mode is used by all of trees, bushes, and cold season grasses. The C4 mode is used by the most of tropical and warm season grasses. They are disadvantaged relative to C3 plants at high CO2/O2 ratios because of the additional energy ex-pense needed to concentrate CO2 in the bundle-sheath cells. At low CO2/O2, however, C4 plants can achieve a relatively high quantum yield by suppressin…     

Carbon and sulfur isotopic compositions of basal Datangpo Formation, northeastern Guizhou, South China: implications for depositional environment

Isotopic compositions of Mn-carbonate and organic carbon from the same individual samples and sulfur isotopic compositions of pyrites in the basal Datangpo Formation were analyzed. Highly 34S-enriched pyrites （834Spyrite =31.7-59.4‰） were precipitated in rel- atively occlusive pore water under anoxic condition in sediments, which is consistent with the observation of large and scattered pyrite framboids. The sulfidic deep ocean was not ＂oxidized＂ in the early Datangpo interglacial interval, thus the level of seawater sulfate remained low and marine δ34Ssulphate remained high. Low δ13Ccar （average -7.4‰） and abnormal relationship between δ13Ccar and fractionation （ΔCar-ors） imply that the negative δ13CCar excursion may have resulted from oxidation of part of a large organic carbon reservoir. High Δcar-org （average 25.1‰） implicates high CO2 level in the atmosphere. Small standard deviation （1.0‰） of δ13CCar values indicates the Mn-carbonate was precipitated near the water-sediment interface under dysoxic conditions rather than in occlusive pore water in sediments.     

Methane seeps, methane hydrate destabilization, and the late Neoproterozoic postglacial cap carbonates

Natural gas (methane) hydrates, the crystalline solids composed mainly of methane and water, are present in marine sediments of the continental margins and polar permafrost under a delicate balance of temperature (< 7℃) and hydrostatic pressure (> 50×10…