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.     

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.     

Early oxygenation of the terrestrial environment during the Mesoproterozoic

Geochemical data from ancient sedimentary successions provide evidence for the progressive evolution of Earth's atmosphere and oceans. Key stages in increasing oxygenation are postulated for the Palaeoproterozoic era (～2.3?billion years ago, Gyr ago) and the late Proterozoic eon (about 0.8?Gyr ago), with the latter implicated in the subsequent metazoan evolutionary expansion. In support of this rise in oxygen concentrations, a large database shows a marked change in the bacterially mediated fractionation of seawater sulphate to sulphide of Δ(34)S?相似文献   

Variations in carbon isotopic composition in the subcontinental lithospheric mantle beneath the Yangtze and North China Cratons: Evidence from in-situ analysis of diamonds using SIMS

The components and evolution of subcontinental lithospheric mantle beneath the North China Craton and the Yangtze Craton is a current topic in the geological study of China and the carbon isotopic composition of diamond is one of the most direct probes into cratonic lithospheric mantle processes.In this paper,in-situ SIMS(Secondary Ion Mass Spectrometry) techniques were used to analyze the carbon isotope compositions at different internal growth zones of diamonds from Shandong and Liaoning in the North China Craton and Hunan in the Yangtze Craton.It was found that the carbon isotopic range of diamonds from the North China Craton are rather distinct from those of the Yangtze Craton;the former has a range of 6.0‰ to 2.0‰(relative to VPDB) with an average value of 3.0‰ in their core areas,which is consistent with global peridotitic diamonds;the diamonds from the Yangtze Craton,however,have a carbon isotopic range from 8.6‰ to 3.0‰ with an average value of 7.4‰ in their core areas,being more consistent with global eclogitic diamonds.The variations of carbon isotope ratios between different internal growth zones in individual diamonds were different in the three diamond localities studied.There was a clear correlation between changes in carbon isotopic composition and phases of diamond dissolution and new growth,while no correlation was observed between δ13C and internal inclusions.The variations suggest that the carbon isotopic compositions of mantle fluids were changing during the process of diamond crystallization,and that the heterogeneity of the carbon isotopic composition in mantle carbon reservoirs was a more important factor than carbon isotope fractionation in controlling the carbon isotopic compositions and their variation in diamonds.In addition,the preliminary results of in-situ nitrogen analyses demonstrated that the variation of carbon isotopic compositions between the core and outer growth zones does not correlate with nitrogen abundances,implying either that diamonds crystallized in an open environment or that the carbon isotopic composition and nitrogen contents in mantle fluids were controlled by other,not yet understood factors.The experimental results provide hints that the isotopic composition of carbon and its original sources were different in metasomatic fluids controlling diamond formation in the mantle beneath the North China Craton and the Yangtze Craton.     

Low marine sulphate and protracted oxygenation of the Proterozoic biosphere

Progressive oxygenation of the Earth's early biosphere is thought to have resulted in increased sulphide oxidation during continental weathering, leading to a corresponding increase in marine sulphate concentration. Accurate reconstruction of marine sulphate reservoir size is therefore important for interpreting the oxygenation history of early Earth environments. Few data, however, specifically constrain how sulphate concentrations may have changed during the Proterozoic era (2.5-0.54 Gyr ago). Prior to 2.2 Gyr ago, when oxygen began to accumulate in the Earth's atmosphere, sulphate concentrations are inferred to have been <1 mM and possibly <200 microM, on the basis of limited isotopic variability preserved in sedimentary sulphides and experimental data showing suppressed isotopic fractionation at extremely low sulphate concentrations. By 0.8 Gyr ago, oxygen and thus sulphate levels may have risen significantly. Here we report large stratigraphic variations in the sulphur isotope composition of marine carbonate-associated sulphate, and use a rate-dependent model for sulphur isotope change that allows us to track changes in marine sulphate concentrations throughout the Proterozoic. Our calculations indicate sulphate levels between 1.5 and 4.5 mM, or 5-15 per cent of modern values, for more than 1 Gyr after initial oxygenation of the Earth's biosphere. Persistence of low oceanic sulphate demonstrates the protracted nature of Earth's oxygenation. It links biospheric evolution to temporal patterns in the depositional behaviour of marine iron- and sulphur-bearing minerals, biological cycling of redox-sensitive elements and availability of trace metals essential to eukaryotic development.     

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。     

Effect of evaporite deposition on Early Cretaceous carbon and sulphur cycling

The global carbon and sulphur cycles are central to our understanding of the Earth's history, because changes in the partitioning between the reduced and oxidized reservoirs of these elements are the primary control on atmospheric oxygen concentrations. In modern marine sediments, the burial rates of reduced carbon and sulphur are positively coupled, but high-resolution isotope records indicate that these rates were inversely related during the Early Cretaceous period. This inverse relationship is difficult to reconcile with our understanding of the processes that control organic matter remineralization and pyrite burial. Here we show that the inverse correlation can be explained by the deposition of evaporites during the opening of the South Atlantic Ocean basin. Evaporite deposition can alter the chemical composition of sea water, which can in turn affect the ability of sulphate-reducing bacteria to remineralize organic matter and mediate pyrite burial. We use a reaction-transport model to quantify these effects, and the resulting changes in the burial rates of carbon and sulphur, during the Early Cretaceous period. Our results indicate that deposition of the South Atlantic evaporites removed enough sulphate from the ocean temporarily to reduce biologically mediated pyrite burial and organic matter remineralization by up to fifty per cent, thus explaining the inverse relationship between the burial rates of reduced carbon and sulphur during this interval. Furthermore, our findings suggest that the effect of changing seawater sulphate concentrations on the marine subsurface biosphere may be the key to understanding other large-scale perturbations of the global carbon and sulphur cycles.     

Mo isotopes in the Lower Cambrian formation of southern China and its implications on paleo-ocean environment

Over the past decade, as one of nontraditional stable isotopes, Mo isotope has developed rapidly and now become an important geochemical proxy to trace paleo-oceanic and atmospheric evolution through geological history. In this paper, Early Cambrian formations in southern China are investigated. The results indicate that δ 97/95Mo values of Early Cambrian seawater may have been larger than 1.4‰, values that are close to those of the modern ocean. It was also found that the variations in Mo isotope composition in samples from two sections （Huangjiawan and Gezhongwu in Guizhou） were closely related to changes in redox conditions during sedimentary processes. Combining our results with existing data, a preliminary model for the evolution of seawater Mo isotope composition through geological history was provided. It indicated that Mo isotopic variations were generally consistent with the evolution of atmospheric oxygen.     

Oxygen isotope geochemistry of phosphorite and dolomite and palaeo-ocean temperature estimation: A case study from the Neoproterozoic Doushantuo Formation, Guizhou Province,South China

The Neoproterozoic Doushantuo Formation at Weng'an in Guizhou Province of South China consists of phosphorites and dolomites.Three types of samples are recongnized for the phosphate-bearing rocks.In Type I samples, interstitial phosphates occur within the dolomite rocks, whereas in Type III samples, interstitial dolomites occur within the phosphorites; both of them may have diagenetic origin.The Type II samples are interbedded phosphorites and dolomites.Oxygen isotopic compositions of phosphate and coeval carbonate were analyzed.Phosphates of Type I and II samples show similar low δ18Ophos (SMOW) values of 10.9‰～12.1‰ and 10.7‰～12.8‰, respectively, whereas Type III phosphates show higher δ18Ophos (SMOW) values of 13.2‰～15.0‰.Dolomites from Type I and II samples have δ18Ocarb (PDB) and δ13Ccarb (PDB) values of -6.2‰～-3.4‰ and -2.2‰～-0.7‰, respectively, whereas interstitial dolomites from Type III samples show lower δ18Ocarb (PDB) and δ13Ccarb (PDB) values of -12.9‰～-8.6‰ and -4.4‰～-2.6‰.Petrology and oxygen isotope data suggest that diagenetic alteration may have partially affected the studied rocks, but the dolomites from Type I and phosphates from Type III samples represent the most pristine isotopic compositions of primary carbonates and phosphates precipitated from seawater.Calculations of palaeocean temperatures from the most 18O enriched dolomite and phosphate indicate a temperature range of 32.2 ℃ to 34.0 ℃ for the seawater of the Doushantuo Formation period.Ce anomaly also suggests more oxic conditions and possibly shallower water depth in the upper strata of the Doushantuo Formation at Weng'an, Guizhou Province.     

煤中硫的形成及其控制因素

为脱硫、降硫提供科学理论依据，本文选择了内蒙古乌达矿务局９号煤层和１０号煤层为研究对象，系统地研究了煤中硫的形成及其分布的控制因素。结果表明：煤中硫含量的变化主要受控于泥炭聚积期沉积环境的变化，乌达矿区９号煤层和１０号煤层是在海侵的背景下形成的，在泥炭聚积期，由于不同水系的发育，控制了煤层间距的变化，更重要的是控制了煤中硫含量的分布，在海水影响下聚积的泥炭比在淡水环境聚积的泥炭含更多的硫。中硫煤和高硫煤中硫的来源主要是侵入泥炭沼泽的海水中的硫酸盐。另外，据研究结果，提出了乌达矿区煤中黄铁矿和有机硫化合物的形成模式。     

Stratigraphic implications of Sinian-Early Cambrian volcanic ash beds on the Yangtze Platform

Volcanic ash beds from shallow- to deep-water facies strata of the Sinian-Early Cambrian (Meishucunian) on the Yangtze Platform consist of bentonites and tuffites which are readily recognized in the field by their physical features and confirmed by geochemical analyses.Geochemistry suggests that the volcanic ash beds in Meishucunian time are rhyolite and rhyodacite while those in the Qiongzhusian and Sinian are andesite and trachyandesite.The ash beds in the time-equivalent strata, even in different areas display rather similar geochemical features, whereas the ash beds in different strata even in the same areas show large chemical difference.The results suggest that these ash beds can be used for intra- and extra-basinal correlations of the Sinian-Early Cambrian interval on the Yangtze Platform.Additionally, these ash beds suggest high potentials for further U-Pb dating strategies.     

Paleoceangraphic significance of redox-sensitive metals of black shales in the basal Lower Cambrian Niutitang Formation in Guizhou Province, South China

TheLowerCambrianblackshalesequenceoccursinSouthChinaalonganarc parallellinearbeltex tendingmorethan 16 0 0km .Theseorganic richblackshalesformedinvariousmarineenvironmentsandtypicallycontainhigheramountsofmolybdenum ,nickel,vanadium ,andanumberofothereconomical lyimportantmetalsthandoanyothersedimentaryrocks[1,2 ] .Therefore ,thestudyoftheseblackshaleshasnotonlypaleoceangraphicimplicationbutalsoe conomicsignificance .Marinesedimentssuchasblackshalearecom plexmixturesofdetritalphasesandseawat…     

Types and biotic successions of Ordovician reefs in China

Ordovician reefs are located in the South China,Tarim,and North China blocks,in low-latitude epicontinental marine regions and mostly consist of large-scale carbonate platforms.During the Paleozoic,faunal radiation reef biota diverged and thrived in diverse paleogeographic settings.Algal reefs of the Early Ordovician,Calathium-lithistid sponge-algal reefs of the late Early Ordovician to early Middle Ordovician,and coral-stromatoporoid-algal reefs of the early Late Ordovician,indicate change from Cambrian to Paleozoic biota.Coral-stromatoporoid-algal reefs were the basic communities after 100 Ma.The macroevolution of biotic struc-tures generally shows increased complexity;the evolution of China’s reef biota parallels that worldwide.Important aspects are:(1) The Calathium-algal reefs from the early Tremadocian Nantzinkuan Formation,Zhangjiajie,western Hunan are the pioneer reefs,and the Darriwillian Yijianfang Formation,Bachu are the relic reefs.(2) The bryozoan-dominated reefs of the late Tremadocian Fenhsiang Formation,Middle Yangtze Platform are unique.(3) The early coral-stromatoporoid-algal reefs are highly restricted in China.(4) The algal reefs from the latest Katian on the western margin of the Yangtze Platform,represent an abnormal reef-building environment during the initial stages of Gondwanan glaciations.     

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 …     

Sinian-Cambrian stratigraphic framework for shallow- to deep-water environments of the Yangtze Platform: an integrated approach

The Sinian (Terminal Proterozoic) and Early Cambrian shallow- to deep-water sequences of the Yangtze Platform were investigated. Based on integrated lithostratigraphic, biostratigraphic, and other approaches, the shallow-water sequence from the base of the Sinian (base of the Doushantuo Formation) to the top of the Qiongzhusian (top of the Yu'anshan Formation) was subdivided into 12 stratigraphic intervals. These 12 intervals were applied in turn to the subdivision and correlation of the sequences present in various facies of the Yangtze Platform. The high-resolution stratigraphic framework here developed can serve as a time frame for ongoing multidisciplinary analyses of the "Cambrian explosion".     

Sulfur and carbon isotopic variations in Neoproterozoic sedimentary rocks from southern China

A new set of δ34Ssulfide, δ34Ssulfate and δ13Ccarbonate values has been reported from Neoproterozoic sedimentary rocks in southern China. The interglacial black shales of the Datangpo Fm. display higher δ34Ssulfide values with >+20‰ average, but the postglacial black shales from the Doushantuo Fm. show negative δ34Ssulfide values. However, the Jinjiadong Fm., the same post-glaciation as the Doushantuo Fm., has positive δ34Ssulfide values, implying that the δ34S value of sedimentary sulfides would be controlled by lithofacies and paleogeographic environments. The δ34Ssulfate values relative to δ13Ccarbonate were obtained by extraction of trace sulfate from the successive carbonate sequences in the Yangtze Gorges sections. A preliminary interpretation suggests that the oceanic environment may fluctuate dramatically at the post-glacial Doushantuo stage and, then, recover its stability at the Dengying stage on the basis of the high resolution δ34S and δ13C curves of seawater.     

Mercury isotope variations in surface soils in different contaminated areas in Guizhou Province, China

Guizhou Province is known as a heavily Hg-polluted area in China due to its special geochemical background and complicated Hg emission sources.In this study,we investigated the Hg isotope compositions of surface soil samples in the Hg mining area,zinc smelting area,coal combustion area,which are known to be the typical pollution regions of Hg in this province.We also compared the Hg isotopic fingerprints of primary Hg sources,such as hydrothermal Hg-bearing ores,coals and atmospheric Hg samples.According to our study,Hg stored in surface soils in different pollution regions in Guizhou Province displays a wide range of both mass dependent fractionation(MDF,δ202Hg) and mass independent fractionation(MIF,△199Hg).δ 202 Hg varies by 2.0‰ and △199Hg varies by 0.25‰ in the investigated surface soils.This study demonstrated that using a "MDF-MIF" two dimensional Hg isotope system could be particularly useful in discriminating Hg sources in soils.     

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.     

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.     

Anomalous 17O compositions in massive sulphate deposits on the Earth

The variation of delta 18O that results from nearly all physical, biological and chemical processes on the Earth is approximately twice as large as the variation of delta 17O. This so-called 'mass-dependent' fractionation is well documented in terrestrial minerals. Evidence for 'mass-independent' fractionation (delta 17O = delta 17O-0.52 delta 18O), where deviation from this tight relationship occurs, has so far been found only in meteoritic material and a few terrestrial atmospheric substances. In the rock record it is thought that oxygen isotopes have followed a mass-dependent relationship for at least the past 3.7 billion years, and no exception to this has been encountered for terrestrial solids. Here, however, we report oxygen-isotope values of two massive sulphate mineral deposits, which formed in surface environments on the Earth but show large isotopic anomalies (delta 17O up to 4.6%). These massive sulphate deposits are gypcretes from the central Namib Desert and the sulphate-bearing Miocene volcanic ash-beds in North America. The source of this isotope anomaly might be related to sulphur oxidation reactions in the atmosphere and therefore enable tracing of such oxidation. These findings also support the possibility of a chemical origin of variable isotope anomalies on other planets, such as Mars.