藏南海相白垩纪碳酸盐碳稳定同位素演化与古海洋溶解氧事件

系统测量藏南白垩纪海相碳酸盐样品的碳稳定同位素,建立了该区白垩纪碳稳定同位素演化曲线.在与欧洲同期碳酸盐岩对比基础上,发现白垩纪三次正向偏移和两次负向偏移具有良好的全球相关性.Albian-Cenomanian界线、CenomanianTuronian界线和Turonian-Coniacian界线δ13C正向偏移与该时期的全球大洋缺氧事件相关;Turonian中期δ13C负向偏移则是全球缺氧事件造成大规模有机碳埋藏,从而引起温室效应减弱而Santonian早期负向偏移对应于富氧事件的发生.     

贵州瓮安陡山沱组碳同位素特征及古海洋意义

通过对贵州瓮安含磷岩系剖面进行碳同位素分析,对震旦纪陡山沱期的成磷事件、生物事件及古海洋环境的变化进行了研究。瓮安大塘剖面陡山沱组碳酸盐岩碳同位素值表现为正偏移的趋势,与其他地区同期碳同位素变化趋势相似。这与大冰期后生物生产率的提高有关,其中的负偏移与环境的波动相关,环境的快速变化刺激了生物的进化。穿岩洞剖面上磷矿段的黑色碳质磷块岩获得的较低的有机碳同位素值与浮游生物吸收12 C有关,体现了生物有机质聚磷作用。该时期的碳酸盐岩碳同位素值的正偏移、磷矿的沉积与生物事件之间有一定的关联性,大洋深部的缺氧事件使底水富磷质;随着古海洋流通性的提高,富磷海水随上升洋流运移到浅海沉积成矿,并为生物圈供应营养物质,进而引发生物竞争及推动进化。     

南海北部陆坡NH-1孔沉积物中碳酸盐碳同位素特征及其地球化学意义

源于深部天然气藏渗漏或天然气水合物分解释放的甲烷,可导致海洋沉积物中生成δ13C明显负偏的碳酸盐矿物.对NH-1孔沉积物样品的碳酸盐含量、全岩碳酸盐及生物碳酸盐δ13C、有机碳含量等参数进行了分析.结果表明:沉积物中碳酸盐含量较高(平均6.90%);全岩碳酸盐δ13C(-6.09‰～-0.48‰)与正常海相碳酸盐相比明显负偏;浮游有孔虫(G.rube)壳体碳酸盐δ13C(-0.834‰～0.004‰)明显低于正常值.结合海域的地质特点,认为这很可能是沉积物中较高甲烷通量背景条件下自生碳酸盐的形成所导致的.有机碳、氮数据与全岩碳酸盐δ13C的相关性分析指示了有机质也可能是全岩碳酸盐δ13C偏低的根源之一.因此,NH-1孔碳酸盐碳同位素特征是较高甲烷通量背景下甲烷缺氧氧化-硫酸盐还原及有机质缺氧氧化-硫酸盐还原等地球化学过程的综合反映.全岩碳酸盐δ13C含量可用于指示沉积物中自生碳酸盐矿物及较高甲烷通量的存在.     

大洋碳循环的地质演变

地球表面各圈层中，大洋是碳循环活跃而容量最大的碳储库，在地质历史上经历了重大的变化. 元古代大气圈的氧化，引起了海洋碳酸盐沉积的型变和有机碳δ¹³C变重；中生代早、中期钙质骨骼浮游生物的繁盛，导致了海水碳酸盐沉积向深海转移和海洋碳同位素加重；元古代末期和新生代晚期的大气CO₂浓度急剧减低，又使得无机碳与有机碳同位素差值大幅度减小. 大洋碳储库的地质演变史反映了地圈、生物圈的相互作用，是认识地球系统变化机制的重要切入点；认识地球表层系统中碳循环在地质尺度上的变化，是查明温室效应如何影响人类生存环境长期趋势的前提.     

塔里木盆地奥陶系碳酸盐岩碳氧稳定同位素地球化学特征

中-下奥陶统碳酸盐岩储层是塔里木盆地塔中地区的主要油气产层.利用碳氧稳定同位素的分布特征和变化规律,可分析影响碳酸盐岩沉积环境和成岩作用的因素.中-下奥陶统的碳酸盐岩可在垂向上把δ13C和δ18O值的变化趋势划分为三段,二者的变化趋势是一致的.中-上奥陶统岩层碳氧稳定同位素比值明显下降,证明中-下奥陶统经历过一次短暂的抬升暴露和随后的大面积海水加深淹没事件.海水淹没时期,大量C转到海水之中,海水中沉淀出的碳酸盐岩的δ13C值相对较低.     

柴达木盆地第三纪盐湖沉积环境分析

目的分析柴达木盆地第三纪盐湖的沉积环境。方法利用稳定同位素分馏理论及其分析技术，分析了现代青海湖稳定同位素的组成特征，并与柴达木盆地第三纪盐湖的沉积环境特点进行了对比。结果柴达木盆地第三纪咸化湖泊沉积碳酸盐岩中富集δ13C与δ18O，具有较高的Z值，并且大多与海洋碳酸盐岩碳氧同位素区间值重叠，说明第三纪咸化湖泊的盐度与海相相当或高于海水；柴达木盆地硫酸盐的δ34值大大超过海洋硫酸盐的δ34S值，且在第三纪盐湖的演化过程中具有化学分层特征，在湖盆下部产生了强烈的硫同位素分馏现象，导致较高δ34S值蒸发岩沉积的形成。结论柴达木盆地第三系盐湖沉积地层中可发育较丰富的油气资源。     

碳酸盐岩碳、氧同位素分析激光微取样技术

碳酸盐岩碳、氧同位素分析激光微取样技术是利用高能聚焦激光束与碳酸盐岩样品作用,热分解产生CO₂气体,经真空提纯净化后送质谱仪分析测定其C、O同位素值。其空间分辨率优于20μm,能有效地对碳酸盐岩各细微组分结构分别取样,以满足同位素地质学研究的需要。经标样测定,δ¹³C和δ¹⁸O的最好分析精度可达±0.22‰(σ),与常规磷酸分解法分析精度相;δ¹³C无明显分馏现象,δ¹⁸O分馏明显,但对同种矿物是一个常量(方解石偏负1.72‰;白云石偏负1.59‰)易于校正。激光微取样主要应用于碳酸盐储集岩样品碳、氧同位素分析,能较好地解释油气储层孔隙演化和成岩过程。     

湖相碳酸盐碳、氧同位素与团簇同位素的研究进展

总结近年来传统碳、氧同位素及新兴团簇同位素在湖相碳酸盐中的研究进展,梳理湖相环境中碳酸盐同位素组成变化的影响因素及两种同位素方法在地质研究中的应用,探讨当前研究中存在的问题。湖相碳酸盐氧同位素组成受温度的影响较小,主要与湖盆水体的蒸发量和大气降水量有关,碳同位素组成则受湖水蒸发咸化作用以及湖泊有机质与无机质相互作用的共同控制;团簇同位素仅受温度单一因素的影响,是良好的碳酸盐温度计。指出湖相碳酸盐碳、氧同位素研究的两大方向:一是解决团簇同位素理论研究中存在的问题,尤其是埋藏改造过程中团簇同位素温度的重置机理;二是将传统的碳、氧同位素指标与新兴的团簇同位素指标相结合,进行多指标的地球化学综合分析,有效地避免二者在地质研究中的局限性。     

再建气候环境演化历史的碳同位素技术

稳定碳同位素是再建气候环境变化历史最重要手段。简要回顾了碳同位素分馏的主要影响因素。介绍了碳同位素变化与生态环境变迁的可能关系 ;重点探讨了利用碳同位素再建古大气CO2 的原理和方法     

奥陶系海相碳酸盐锶同位素组成及受成岩流体的影响

综合了已有的全球奥陶系海相碳酸盐的锶同位素分析结果及演化趋势,测试了塔里木盆地北部奥陶系4种类型共计51个非沉积碳酸盐矿物的锶同位素组成,通过对照研究,得出如下认识:(1)奥陶纪全球海水87Sr/86Sr比值具有随时间单调下降的总体趋势,其原因与晚寒武世-奥陶纪的全球淹没事件,以及广阔陆表海和有关的沉积物对放射性成因锶的封存作用有关;(2)塔里木盆地塔中地区海相碳酸盐的锶同位素演化趋势总体上与全球一致,说明全球海平面变化仍然是塔里木盆地海相碳酸盐锶同位素组成与演化的主要控制因素;(3)塔里木盆地塔中地区上奥陶统部分海相碳酸盐87Sr/86Sr比值的降低可能与深部流体的影响有关;(4)塔里木盆地塔中地区上奥陶统部分海相碳酸盐样品87Sr/86Sr比值的升高与晚奥陶世盆地抬升过程造成的表生成岩环境中近地表大气淡水作用带来的富放射性成因锶的影响有关;(5)分布于塔里木盆地北部奥陶系风化壳中非沉积碳酸盐具有很高的87Sr/86Sr比值,最低值也显著高于0.7079左右的晚奥陶世末海水的锶同位素组成,说明大气淡水及壳源组分在奥陶系水岩反应中具有极为重要的意义;(6)奥陶系风化壳中的4种非沉积成因方解石中,与不整合面附近古喀斯特作用有关的方解石的87Sr/86Sr比值最高,显著高于各种成因的裂隙(构造或非构造成因裂隙)中的方解石,说明在非海相流体的影响中,不整合面附近的大气淡水作用是最为重要的.     

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。     

Changes in carbon dioxide during an oceanic anoxic event linked to intrusion into Gondwana coals

The marine sedimentary record exhibits evidence for episodes of enhanced organic carbon burial known as 'oceanic anoxic events' (OAEs). They are characterized by carbon-isotope excursions in marine and terrestrial reservoirs and mass extinction of marine faunas. Causal mechanisms for the enhancement of organic carbon burial during OAEs are still debated, but it is thought that such events should draw down significant quantities of atmospheric carbon dioxide. In the case of the Toarcian OAE (approximately 183 million years ago), a short-lived negative carbon-isotope excursion in oceanic and terrestrial reservoirs has been interpreted to indicate raised atmospheric carbon dioxide caused by oxidation of methane catastrophically released from either marine gas hydrates or magma-intruded organic-rich rocks. Here we test these two leading hypotheses for a negative carbon isotopic excursion marking the initiation of the Toarcian OAE using a high-resolution atmospheric carbon dioxide record obtained from fossil leaf stomatal frequency. We find that coincident with the negative carbon-isotope excursion carbon dioxide is first drawn down by 350 +/- 100 p.p.m.v. and then abruptly elevated by 1,200 +/- 400 p.p.m.v, and infer a global cooling and greenhouse warming of 2.5 +/- 0.1 degrees C and 6.5 +/- 1 degrees C, respectively. The pattern and magnitude of carbon dioxide change are difficult to reconcile with catastrophic input of isotopically light methane from hydrates as the cause of the negative isotopic signal. Our carbon dioxide record better supports a magma-intrusion hypothesis, and suggests that injection of isotopically light carbon from the release of thermogenic methane occurred owing to the intrusion of Gondwana coals by Toarcian-aged Karoo-Ferrar dolerites.     

Geochemical evidence for widespread euxinia in the later Cambrian ocean

Widespread anoxia in the ocean is frequently invoked as a primary driver of mass extinction as well as a long-term inhibitor of evolutionary radiation on early Earth. In recent biogeochemical studies it has been hypothesized that oxygen deficiency was widespread in subsurface water masses of later Cambrian oceans, possibly influencing evolutionary events during this time. Physical evidence of widespread anoxia in Cambrian oceans has remained elusive and thus its potential relationship to the palaeontological record remains largely unexplored. Here we present sulphur isotope records from six globally distributed stratigraphic sections of later Cambrian marine rocks (about 499 million years old). We find a positive sulphur isotope excursion in phase with the Steptoean Positive Carbon Isotope Excursion (SPICE), a large and rapid excursion in the marine carbon isotope record, which is thought to be indicative of a global carbon cycle perturbation. Numerical box modelling of the paired carbon sulphur isotope data indicates that these isotope shifts reflect transient increases in the burial of organic carbon and pyrite sulphur in sediments deposited under large-scale anoxic and sulphidic (euxinic) conditions. Independently, molybdenum abundances in a coeval black shale point convincingly to the transient spread of anoxia. These results identify the SPICE interval as the best characterized ocean anoxic event in the pre-Mesozoic ocean and an extreme example of oxygen deficiency in the later Cambrian ocean. Thus, a redox structure similar to those in Proterozoic oceans may have persisted or returned in the oceans of the early Phanerozoic eon. Indeed, the environmental challenges presented by widespread anoxia may have been a prevalent if not dominant influence on animal evolution in Cambrian oceans.     

Cretaceous oceanic anoxic event 2 triggered by a massive magmatic episode

Oceanic anoxic events (OAEs) were episodes of widespread marine anoxia during which large amounts of organic carbon were buried on the ocean floor under oxygen-deficient bottom waters. OAE2, occurring at the Cenomanian/Turonian boundary (about 93.5 Myr ago), is the most widespread and best defined OAE of the mid-Cretaceous. Although the enhanced burial of organic matter can be explained either through increased primary productivity or enhanced preservation scenarios, the actual trigger mechanism, corresponding closely to the onset of these episodes of increased carbon sequestration, has not been clearly identified. It has been postulated that large-scale magmatic activity initially triggered OAE2 (refs 4, 5), but a direct proxy of magmatism preserved in the sedimentary record coinciding closely with the onset of OAE2 has not yet been found. Here we report seawater osmium isotope ratios in organic-rich sediments from two distant sites. We find that at both study sites the marine osmium isotope record changes abruptly just at or before the onset of OAE2. Using a simple two-component mixing equation, we calculate that over 97 per cent of the total osmium content in contemporaneous seawater at both sites is magmatic in origin, a approximately 30-50-fold increase relative to pre-OAE conditions. Furthermore, the magmatic osmium isotope signal appears slightly before the OAE2-as indicated by carbon isotope ratios-suggesting a time-lag of up to approximately 23 kyr between magmatism and the onset of significant organic carbon burial, which may reflect the reaction time of the global ocean system. Our marine osmium isotope data are indicative of a widespread magmatic pulse at the onset of OAE2, which may have triggered the subsequent deposition of large amounts of organic matter.     

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.     

Uncovering the Neoproterozoic carbon cycle

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter. Neoproterozoic carbonate records contain unusual and large negative isotopic anomalies within long periods (10-100 million years) characterized by δ(13)C in carbonate (δ(13)C(carb)) enriched to more than +5 per mil. Classically, δ(13)C(carb) is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments, which can be linked to oxygen accumulation through the stoichiometry of primary production. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of δ(13)C(carb) and δ(13)C in organic carbon (δ(13)C(org)) will covary, offset by the fractionation imparted by primary production. The documentation of several Neoproterozoic δ(13)C(carb) excursions that are decoupled from δ(13)C(org), however, indicates that other mechanisms may account for these excursions. Here we present δ(13)C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple δ(13)C(carb) excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret δ(13)C(carb) anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals.     

Stable isotopic geochemistry of organic carbon and pyrite sulfur from the Early Cambrian black shales in Northwestern Hunan, China

The early Cambrian black shale sequence in Northwestern Hunan Province has been investigated for its stable isotopic geochemistry of organic carbon and pyrite sulfur. The relatively low δ 13C values of organic matter, -29.7‰～-34.2‰, are interpreted as caused by the high CO2 concentration in atmosphere/ocean and an anoxic depositional environment in early Cambrian. Variable, but significantly positive δ 34S values, 10.2‰～ 28.2‰, for sedimentary pyrite reveals bacterial sulfate reduction as the pyrite-forming process but under sulfate-limited conditions. A protected anoxic basin, which had very limited access to open ocean, and its sediments, where metabolizable organic matter was rich and bioturbation was absent, are supposed to be the sulfate-limited environments and might have existed in South China in the early Cambrian.     

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.     

Massive dissociation of gas hydrate during a Jurassic oceanic anoxic event

In the Jurassic period, the Early Toarcian oceanic anoxic event (about 183 million years ago) is associated with exceptionally high rates of organic-carbon burial, high palaeotemperatures and significant mass extinction. Heavy carbon-isotope compositions in rocks and fossils of this age have been linked to the global burial of organic carbon, which is isotopically light. In contrast, examples of light carbon-isotope values from marine organic matter of Early Toarcian age have been explained principally in terms of localized upwelling of bottom water enriched in 12C versus 13C (refs 1,2,5,6). Here, however, we report carbon-isotope analyses of fossil wood which demonstrate that isotopically light carbon dominated all the upper oceanic, biospheric and atmospheric carbon reservoirs, and that this occurred despite the enhanced burial of organic carbon. We propose that--as has been suggested for the Late Palaeocene thermal maximum, some 55 million years ago--the observed patterns were produced by voluminous and extremely rapid release of methane from gas hydrate contained in marine continental-margin sediments.