Late Neoproterozoic to early Cambrian sulphur cycle-An isotopic investigation of sedimentary rocks from the Yangtze Platform

The sulphur cycle responds to changes in seawater chemistry, biological evolution and tectonic activity. We follow an isotopic approach in order to constrain the state of the ocean/atmosphere system during late Neoproterozoic and early Cambrian. For this purpose, a sedimentary succession deposited on the Yangtze Platform, South China, was analysed for its sulphur isotopic composition in different S-bearing phases. Redox changes were defined by the degree of pyritization (DOP) values in order to show variations in the oxygenation of the depositional environment. The sulphur isotopic composition of late Neoproterozoic to early Cambrian seawater sulphate ranges from +30‰ to +35‰ as evident from trace sulphate in unaltered carbonates and phosphorites. The isotopic composition for pyrite and organic sulphur varies between -16‰ and +23‰. The apparent sulphur isotopic fractionation between seawater sulphate and pyrite as well as organically bound sulphur varies between 7‰ and 50‰. This large fractionation, as well as its variability suggests a biological origin for pyrite and organically bound sulphur. The temporal evolution of different geochemical proxy signals is comparable for different successions across the Yangtze Platform.     

东风山前寒武纪含铁建造金矿床的同位素地球化学特征

东风山金矿体赋存在含铁层之下的东风山群角岩层中。赋矿层位中富含磁黄铁矿、黄铁矿、锰铝榴石和锰铁闪石。通过对该矿床的硫、氧、碳和铅同位素研究,表明硫化物中的硫和地层铅主要来自深源,其次地层中的含硫有机物被生物分解形成的硫也产生一定影响。东风山群形成于早元古代。东风山金矿属高温热接触变质的同生床。     

δ13Ccarb and Ceanom excursions in the post-glacial Neoproterozoic and Early Cambrian interval in Guizhou,South China

Secular δ 13Ccarb and Ceanom profiles in the post-glacial Neoproterozoic and Early Cambrian interval are reported from Guizhou on the southeasten border of the Yangtze platform, South China. Overall, the δ 13Ccarb profile drifts to negative values in the post-glacial Nantuo and lower to middle Doushantuo Formations, and then to positive values in the upper Doushantuo and Dengying Formations of Neoproterozoic, followed by negative values in the Lower Cambrian Gezhongwu and Niutitang Formations. A detailed investigation of the relationship between the δ 13Ccarb and Ceanom profiles reveals that the main anoxic and oxic episodes are coupled with negative and positive δ 13Ccarb values, respectively. This may suggest a control of alternation between ocean stratification and mixing on variations in 13C abundance in the ancient ocean of the investigated areas.     

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.     

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.     

塔里木盆地西缘下寒武统玉尔吐斯组沉积地球化学及有机质富集机制研究

对塔里木盆地西缘下寒武统玉尔吐斯组3个典型的剖面开展岩石学及地球化学研究,探讨玉尔吐斯组沉积时期水体氧化-还原环境及初级生产力,为玉尔吐斯组烃源岩分布及资源潜力评价提供理论依据。玉尔吐斯组下部较高含量的Ba (>1000μg/g)说明其沉积时期表层水体初级生产力较高,产出的大量有机质埋藏于沉积物中,与玉尔吐斯组产出的大量浮游植物化石及较高的TOC值相一致。与之对应层位中,较高的δ15N (>8‰)说明水体中发生反硝化作用和/或厌氧氨氧化作用,表明有机物在从表层向深层水体沉降过程中发生降解作用,不断地消耗水体中的氧气,使得海洋内部形成偏还原的水体环境。同时,玉尔吐斯组下部硅质岩具有极低的Ge/Si值,表明正常海水是硅质的主要来源。硅质过饱和的水体促进沉积物快速胶结,可能对有机物的保存具有重要作用。     

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。     

Terminal Proterozoic reorganization of biogeochemical cycles

The Proterozoic aeon (2,500-540 million years ago) saw episodic increases in atmospheric oxygen content, the evolution of multicellular life and, at its close, an enormous radiation of animal diversity. These profound biological and environmental changes must have been linked, but the underlying mechanisms have been obscure. Here we show that hydrocarbons extracted from Proterozoic sediments in several locations worldwide are derived mainly from bacteria or other heterotrophs rather than from photosynthetic organisms. Biodegradation of algal products in sedimenting matter was therefore unusually complete, indicating that organic material was extensively reworked as it sank slowly through the water column. We propose that a significant proportion of this reworking will have been mediated by sulphate-reducing bacteria, forming sulphide. The production of sulphide and consumption of oxygen near the ocean surface will have inhibited transport of O2 to the deep ocean. We find that preservation of algal-lipid skeletons improves at the beginning of the Cambrian, reflecting the increase in transport by rapidly sinking faecal pellets. We suggest that this rapid removal of organic matter will have increased oxygenation of surface waters, leading to a descent of the O2-sulphide interface to the sea floor and to marked changes in the marine environment, ultimately contributing to the Cambrian radiation.     

中扬子地区下寒武统烃源岩横向分布及主控因素分析

基于前人研究资料和野外露头剖面详细观测及样品实测数据,讨论了中扬子地区下寒武统烃源岩的横向分布特征,探讨了烃源岩横向分布的主控因素.研究认为:中扬子地区下寒武统烃源岩围绕中扬子碳酸盐台地呈环状分布;台地内没有烃源岩发育,向洋一侧烃源岩逐渐加厚.研究区下寒武统烃源岩的分布受控于早寒武世早期盆地原型的分布,烃源岩的发育受沉积相控制.烃源岩所发育的相带均为陆棚边缘盆地相,早寒武世沧浪浦期—龙王庙期的浅海陆棚相、滨浅海相、台缘滩相、台缘斜坡相、局限台地相等沉积相带的碎屑岩、碳酸盐岩有机质含量均较低,烃源岩发育极差.     

Rare earth elements and carbon isotope geochemistry of the Doushantuo Formation in South China: Implication for middle Ediacaran shallow marine redox conditions

The middle Ediacaran Shuram excursion, the largest negative δ 13 C carb excursion in Earth history, has been interpreted as indirect evidence for episodic oxidation and remineralization of deep ocean DOC (dissolved organic carbon). It has been hypothesized that such oxidation event may have occurred when anoxic DOC-laden deep water was brought to shallow shelves during oceanic upwelling, which is expected to cause localized anoxia in shallow environments. To test this prediction, we systematically analyzed rare earth elements (REE) and δ 13 C carb of the upper Doushantuo Formation carbonates in the Yangtze Gorges area of South China, which were deposited in an inner shelf environment and record a large negative δ 13 C carb excursion correlated to the Shuram event. The REE data show a significant positive shift in Ce/Ce* values, synchronous with a pronounced negative δ 13 C carb shift. This positive Ce/Ce* shift is interpreted to represent an oceanic anoxia event in shallow shelf environments, which may have been caused by the upwelling or impingement of oxygen-depleted and 12 C-enriched deep water onto shelves. This anoxia event coincides with a sharp decline in the abundance and diversity of Ediacaran acanthomorphic acritarchs, raising the possibility that these two geobiological events may be causally related.     

轮古西地区奥陶系碳酸盐岩古岩溶储层碳、氧同位素地球化学特征

中—下奥陶统鹰山组碳酸盐岩古岩溶储层是塔里木盆地轮古西地区的主要油气产层 .为了弄清储层的成因类型、储层古岩溶过程中的流体性质和古水文条件 ,为预测和评价此类储层提供有关的地球化学信息 ,讨论了储层形成过程中记录的碳、氧稳定同位素特征 .结果表明 :轮古西地区奥陶系鹰山组碳酸盐岩古岩溶储层中的δ13C和δ18O值的变化范围较大 ,δ13C值为 -0 .70‰～ -6.5 0‰ ,平均值 -1 .76‰ ;δ18O值为 -3 .75‰～ -1 7.1 0‰ ,平均值 -9.42‰ .碳酸盐岩基质、冲积岩和方解石胶结物的δ13C和δ18O分布具有一定的差异 .三类样品的δ18O值均具有明显偏负特征 ,表明在碳酸盐岩成岩过程中受到大气成因的淡水影响 ,反映了当时的风化壳岩溶成岩环境 .冲积岩样品的δ13C值的偏负程度较高 ,其物源可能来自石炭—二叠系地层     

Iron speciation in cherts from the Laobao Formation, South China: Implications for anoxic and ferruginous deep-water conditions

Cherts in the Laobao Formation in the Silikou section, South China were deposited in terminal Ediacaran deep-water. The speciations of iron in cherts, such as pyrite Fe (Fe_P), HCl-extractable Fe (Fe_H), and total Fe (Fe_T), and their interrelationships, are proxies for distinguishing oxic, anoxic but ferruginous, and sulfidic conditions, which is an effective method for studying the terminal Ediacaran ocean environment. For chert samples from the Laobao Formation, pyrite concentrations are generally low (<0.56%), degree of pyritization (DOP) ranges from <0.01 to 0.78 and most are <0.45; (Fe_P+Fe_H)/Fe_T ratios are between 0.27 and 0.84 and most exceed 0.38, and most of FeT/Al ratios range from 0.55 to 5.87 (averaging 1.1). Relatively high content of highly reactive Fe and low content of pyrite indicate a scarcity of H₂S and Fe-enriched deep-water. These features suggested that the deposition setting of Laobao cherts was anoxic and ferruginous. Terminal Ediacaran deep-water in the South China Basin was most likely anoxic and ferruginous, which played a key role in the emergence and evolution of early multicellular life.     

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.     

Change in the sedimentary environment of Wanquan River Estuary,Hainan Island,China

Pb geochronology and sediment core profiles of organic carbon, total sulfur and organic carbon isotope (d 13C) values were used to reconstruct the local environ-mental history of the Shamei Lagoon, located in the Wan-quan River Estuary, eastern Hainan Island, China. Totalsulfur and d 13C values decreased upwards in the top 30 cm of a sediment core that spanned the last 200 years of deposi-tion. Total sulfur concentration and d 13C values respectively decreased upward from 1.92% to 0.36%, and -20.63?to -23.64? The C/S ratio in the 19th century and earlier was relatively stable in the range of 0.47—0.80, and there was a positive correlation between organic carbon and total sulfur. Since around 1900 AD, the C/S ratio increased rapidly to a maximum of 3.94, but no simple correlation was found be-tween organic carbon and total sulfur during this more re-cent period. These results indicated that before 1800 AD, the lagoon had a fully marine character, and the location of to-day抯 Wanquan River Estuary was an open embayment.From 1800 to 1900, the salinity of Shamei Lagoon decreased noticeably. The amount of seawater which could enter thelagoon decreased gradually as the Yudai spit grew. Today,seawater scarcely affects the lagoon; it is essentially a fresh-water basin.     

Hydrogen sulphide release to surface waters at the Precambrian/Cambrian boundary

Animal-like multicellular fossils appeared towards the end of the Precambrian, followed by a rapid increase in the abundance and diversity of fossils during the Early Cambrian period, an event also known as the 'Cambrian explosion'. Changes in the environmental conditions at the Precambrian/Cambrian transition (about 542 Myr ago) have been suggested as a possible explanation for this event, but are still a matter of debate. Here we report molybdenum isotope signatures of black shales from two stratigraphically correlated sample sets with a depositional age of around 542 Myr. We find a transient molybdenum isotope signal immediately after the Precambrian/Cambrian transition. Using a box model of the oceanic molybdenum cycle, we find that intense upwelling of hydrogen sulphide-rich deep ocean water best explains the observed Early Cambrian molybdenum isotope signal. Our findings suggest that the Early Cambrian animal radiation may have been triggered by a major change in ocean circulation, terminating a long period during which the Proterozoic ocean was stratified, with sulphidic deep water.     

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…     

兰州市和太原市环境空气中NMHCs的碳同位素组成特征

研究了兰州市和太原市环境空气中非甲烷烃(NMHCs)的污染状况及来源。利用Tenax-TA吸附管采样,热解析-色谱-同位素质谱联用仪(TD-GC-IRMS)测定了两个城市夏季不同功能区环境空气中NMHCs的稳定碳同位素组成。得出,兰州市和太原市居民区苯的δ(13C)分别为-26.4‰和-25.0‰;正烷烃的δ(13C)分别为-33.9‰~-26.1‰,-32.8‰~-27.4‰;两市交通枢纽区环境空气中检测出的C4—C7之间的NMHCs化合物相同,δ(13C)相差不大,兰州市为-30.8‰~-25.6‰,太原市为-31.0‰~-26.4‰。结果表明,两市交通枢纽区苯主要来源于汽车尾气和油类挥发,工业区石化行业类主要排放的NMHCs污染物为苯和烷烃类化合物,电厂等大型企业主要排放异丁烯、顺-2-戊烯等。控制汽车尾气、油类挥发、工业排放是降低环境空气中NMHCs污染的关键。     

Characterization of Ordovician carbonate reservoirs, southeastern Saskatchewan, Canada

The discovery of the prolific Ordovician Red River reservoirs in 1995 in southeastern Saskatchewan was the catalyst for extensive exploration activity which resulted in the discovery of more than 15 new Red River pools. The best yields of Red River production to date have been from dolomite reservoirs. Understanding the processes of dolomitization is, therefore, crucial for the prediction of the connectivity, spatial distribution and heterogeneity of dolomite reservoirs.The Red River reservoirs in the Midale area consist of 3～4 thin dolomitized zones, with a total thickness of about 20 m, which occur at the top of the Yeoman Formation. Two types of replacement dolomite were recognized in the Red River reservoir: dolomitized burrow infills and dolomitized host matrix. The spatial distribution of dolomite suggests that burrowing organisms played an important role in facilitating the fluid flow in the backfilled sediments. This resulted in penecontemporaneous dolomitization of burrow infills by normal seawater. The dolomite in the host matrix is interpreted as having occurred at shallow burial by evaporitic seawater during precipitation of Lake Almar anhydrite that immediately overlies the Yeoman Formation. However, the low δ18O values of dolomited burrow infills (-5.9‰～ -7.8‰, PDB) and matrix dolomites (-6.6‰～ -8.1‰, avg. -7.4‰ PDB) compared to the estimated values for the late Ordovician marine dolomite could be attributed to modification and alteration of dolomite at higher temperatures during deeper burial, which could also be responsible for its 87Sr/86Sr ratios (0.7084～0.7088) that are higher than suggested for the late Ordovician seawaters (0.7078～0.7080). The trace amounts of saddle dolomite cement in the Red River carbonates are probably related to "cannibalization" of earlier replacement dolomite during the chemical compaction.     

Carbon and oxygen isotopes analyses for the Sinian carbonates in the Helan Mountain, North China

We conducted detailed studies of the Sinian carbonates from the Helan Mountain, Ningxia by both field investigation and laboratory analyses of carbon and oxygen isotopes. The carbon isotopic compositions of the Sinian Zhengmuguan Formation shows variations with regularity in the five studied sections, the δ ¹³C values all gradually decrease from bottom to top, with a total range from ?4.51‰ to 0.11‰, and the biggest negative excursion reaches up to ?6.88‰. In addition, abundant macro-body fossils were also found from the Tuerkeng Formation in this study, similar to those found from the Dengying Formation in the South China Block. This observation firmly constrained the age for the Zhengmuguan and Tuerkeng formations to the Sinian period. Here we interpreted that the Zhengmuguan Formation formed during a glacial period when the extremely cold climate substantially decreased the amount of burial of organic matter in the ocean and thus led to the general negative δ ¹³C excursion. The increasing δ ¹³C values in the Tuerkeng Formation dolomites imply the ending of the glacial period in the Zhengmuguan epoch, biological recovery and increase of organic matter burial in the ocean occurred during this period. Comparing our obtained carbon and oxygen isotopes of the Zhengmuguan and Tuerkeng formations with those of coeval carbonate successions from other places all over the world, the Zhengmuguang-aged glacial deposits might be deposited after the Gaskiers glaciation. This study provides important information for paleo-ocean, paleogeographic and biological evolution in the North China Block during the Ediacaran period and adds new carbon and oxygen isotopes data for the global Sinian carbon-oxygen isotopes dataset.