Molecular characterization of organic matter in sediments from the Keg River formation (Elk Point group), western Canada sedimentary basin

Distributions of free and sulfur-bound biomarkers in organic-rich sediments from the lower and upper Keg River formation (Elk Point group, western Canada) reveal deposition of these sediments under reducing conditions, in agreement with the geological data. The predominance of aryl isoprenoids of Chlorobiaceae origin indicates that photic zone anoxia occurred during time of deposition. A series of novel aryl isoprenoids with a carboxylic acid function was identified by GC–MS and the structure of the predominant 3-methyl-5-(2′,3′,6′-trimethylphenyl)pentanoate was proven by synthesis of an authentic standard. The occurrence of these acids gives evidence that oxidative breakdown at least partially accounts for the diagenetic fate of aromatic carotenoids. Li/EtNH₂ desulfurization of two kerogen concentrates yielded only low amounts of sulfur-bound hydrocarbons, and suggests that either sulfur sequestration was not a predominant process or, more probably, that a major part of the hydrocarbons, initially sulfurized, were released upon maturation, giving further evidence that (poly)sulfide bonds are cleaved at relatively low levels of thermal stress.     

扬子地区古生代主要烃源岩有机质富集的环境动力学机制与差异

在扬子地块古生界发育了3套区域性的优质烃源岩,即:下寒武统、上奥陶统一下志留统、二叠系(中、上二叠统).下寒武统烃源岩主要由硅质岩(留茶坡组)和上部的硅质泥岩、碳质泥岩(或石煤)(牛蹄塘组)组成.早寒武世在台一盆转换带(或台地边缘)广泛发育的海底热液活动,喷流出大量的富硅流体,使大量硅岩得以在台缘外侧-盆地区沉淀;同时...     

Anthropogenic influence on the degradation of an urban lake - The Pampulha reservoir in Belo Horizonte, Minas Gerais, Brazil

The artificial reservoir Lagoa da Pampulha in central Brazil has been increasingly affected by sediment deposition and pollution from urban and industrial sources. This study investigates water chemistry and heavy metal concentrations and their fractionation in the lake sediment using ICP-OES, ICP-MS, and XRD analyses. Fractionation analysis was done by sequential extraction under inert gas as well as after oxidation. The lake exhibits a permanent stratification with an oxygen-free hypolimnion below 2 m depth. Nutrient concentrations are enriched for phosphorous components (SRP, PO₄). In the sediment it was not possible to detect oxygen. Carbon, sulfur, and most of the analyzed heavy metals are enriched in the top sediment layer with a pronounced downward decrease, indicating the presence of an anthropogenic influence. Statistical analysis, including correlations and a Principal Component Analysis (PCA) of depth-related total concentration data, helps to distinguish presumably anthropogenic heavy metals from geogenic components. Some samples with high element concentrations in the sediment also show elevated concentrations in their pore water. Analyses of element distribution between sediment and pore water suggest a strong bonding of heavy metals to the anoxic sediment. The trend towards elevated solubility in the pore water of oxidized samples is clear for most of the analyzed elements. Fractionation analysis reveals characteristic associations of selected elements to specific mineral bonding forms. In addition, it indicates that the behavior of heavy metals in the sediment is strongly influenced by organic substances. These substances provide buffering against oxidation, acidification, and metal release. The high nutrient loading causes reducing conditions in the lake sediment. These conditions trigger the accumulation of sediments rich in S²⁻, which stabilizes the fixation of heavy elements. In the future, care must be taken to reduce the supply of contaminants and to prevent the release of heavy metals from sediments dredged for remediation purposes.     

Isoprenoid constituents in kerogens as a function of depositional environment and catagenesis

The ratio of the abundance of the C_19:1 isoprenoids 1-pristene and 2-pristene to the abundance of (nC_17:1 + nC_17:0) is significantly lower in pyrolysates of kerogens from highly anoxic depositional environments than in pyrolysates of kerogen if similar types and levels of catagenesis from more oxic organic facies. ¹³C-NMR analysis shows that the occurrence of lower relative concentrations of isoprenoid precursors also correlates with the occurrence of low proportions of oxygen-bonded carbon and high proportion of aliphatic carbon in kerogens. The ratio of 1-pristene to (n-C_17:1 + nC_17:0) can be correlated laterally and statigraphically within a basin. There is no clearly discernible dependence of relative isoprenoid concentration of kerogen type for oil-generative kerogens, although immature lignites have high 1-pristene/(nC_17:1 + nC_17:0) ratios.The 1-pristene/(nC_17:1 + nC_17:0) ratios in kerogens pyrolysates from the same organic facies decrease logarithmically with increasing catagenesis and can be correlated directly with measured vitrinite reflectance values. Geologic and experimental data imply that 1-pristene precursors are lost from kerogen more rapidly than the precursors of the C₁₈ isoprenoid.The lower relative isoprenoid concentrations observed in anoxically deposited kerogens appear to be the result of the enhanced preservation of normal alkyl groups and the enhanced formation of free isophrenoids early in the sequence of kerogen alteration. These results are significant to the use of isoprenoids as geochemical marker oils, bitumens, and kerogens and to the determination of the structure and diagenesis of isoprenoid precursors.     

Hypersaline and anoxia in the Devonian Frasnian-Famennian transition :Molecular fossil and mineralogical evidence from Guangxi ,South China

Abundant normal alkanes, isoprenoid hydrocarbons, terpanes and steranes were detected in 23 samples taken from the carbonate platform to basin facies in the Devonian Frasnian-Famennian (F-F) transition of Guangxi, South China. They were mainly derived from the phytoplankton or bacteria and algae. Molecular stratigraphic parameters, abundant micron gypsums and pyrite framboids show that hypersaline and anoxia prevailed in the F-F transition, the highly stressed environments occurred near the F-F boundary. Orbital cyclostratigraphic studies indicate that the hypersaline and anoxia prevailed in the F-F transition spanned an interval at least from the Palmatolepis linguiformis conodont Zone to the Middle Palmatolepis triangularis conodont Zone and lasted about 1.2 Ma. The Devonian marine ecosystem underwent Early Devonian gradual optimization, Middle Devonian to the F-F transitional stepwise deterioration and late Famennian recovery. A positive feedback among higher surface ocean temperatures, hypersaline, water column anoxia, enhanced nutrient regeneration, phytoplankton productivity and eutrophication was probably substantial in the F-F transition in Guangxi, South China, even in other regions of the world, such as Holy Cross Mountains of Poland, Montagne Noire in southern France, Alberta in Canada. The point that should be emphasized is that the decisive and direct causes of the F-F transitional mass extinction would be the stepwise deterioration of the marine ecosystem since the Middle Devonian other than a bolide impact on the earth. The hypersaline and anoxia prevailed in the F-F transition favor the formation and preservation of hydrocarbon source rocks in South China.     

Ocean acidification and photic‐zone anoxia at the Toarcian Oceanic Anoxic Event: Insights from the Adriatic Carbonate Platform

Severe global climate change led to the deterioration of environmental conditions in the oceans during the Toarcian Stage of the Jurassic. Carbonate platforms of the Western Tethys Ocean exposed in Alpine Tethyan mountain ranges today offer insight into this period of environmental upheaval. In addition to informing understanding of climate change in deep time, the effect of ancient carbon cycle perturbations on carbonate platforms has important implications for anthropogenic climate change; the patterns of early Toarcian environmental deterioration are similar to those occurring in modern oceans. This study focuses on the record of the early Toarcian Oceanic Anoxic Event (ca 183.1 Ma) in outcrops of the north‐west Adriatic Carbonate Platform in Slovenia. Amidst environmental deterioration, the north‐west Adriatic Platform abruptly transitioned from a healthy, shallow‐water environment with diverse metazoan ecosystems to a partially drowned setting with low diversity biota and diminished sedimentation. An organic carbon‐isotope excursion of ?2.2‰ reflects the massive injection of CO₂ into the ocean‐atmosphere system and marks the stratigraphic position of the Toarcian Oceanic Anoxic Event. A prominent dissolution horizon and suppressed carbonate deposition on the platform are interpreted to reflect transient shoaling of the carbonate compensation depth to unprecedentedly shallow levels as the dramatic influx of CO₂ overwhelmed the ocean’s buffering capacity, causing ocean acidification. Trace metal geochemistry and palaeoecology highlight water column deoxygenation, including the development of photic‐zone anoxia, preceding and during the Toarcian Oceanic Anoxic Event. Ocean acidification and reduced oxygen levels likely had a profoundly negative effect on carbonate‐producing biota and growth of the Adriatic Platform. These effects are consistent with the approximate doubling of the concentration of CO₂ in the ocean‐atmosphere system from pre‐event levels, which has previously been linked to a volcanic triggering mechanism. Mercury enrichments discovered in this study support a temporal and genetic link between volcanism, the Toarcian Oceanic Anoxic Event and the carbonate crisis.     

寒武纪第十期早期海洋氧化还原波动：来自U 同位素的证据

寒武纪晚期到奥陶纪早期的海洋动物多样性整体水平较低,生物地球化学研究认为可能与海洋氧化还原状态波动有关,但仍证据较少。保存良好的海相碳酸盐岩沉积被认为能够记录古代海水的地球化学信息,其铀同位素组成 (δ238U) 可用来反映全球海洋的氧化还原状态。文章测定了华南瓦儿岗剖面寒武系第十阶底部海相碳酸盐岩的δ238U值,结果显示在寒武纪第十期早期U同位素组成可能存在三次负漂移,对应的δ238U值分别为-0.8‰、-0.55‰和-0.60‰,指示三个海洋缺氧时段。通过U同位素质量平衡模型计算得出,三个缺氧时段全球海洋底层水体分别约有22％、3.5%和5%的缺氧面积。初步推断第一次缺氧可能与风化输入营养元素增强致初级生物生产力提高有关,而其后的两次缺氧可能与原先的海底缺氧水体在海侵阶段上涌扩散有关。     

绿硫细菌色素的高效液相色谱分析及其应用

绿硫细菌(green sulfur bacteria)的特征色素及其衍化产物,如细菌叶绿素d、细菌叶绿素e、绿硫菌烯(chlorobactene)和异海绵烯(isorenieratene)等可以作为标志物,指示水体真光层的无氧事件,以及水生生态系统在缺氧环境下的演变过程。但是,由于缺少色素标准品,相关研究工作受到制约。为此,本研究培养了两种典型绿硫细菌——Chlorobium phaeovibrioides(DSM269,褐色菌株)和Prosthecochloris vibrioformis(DSM260,绿色菌株),并应用高效液相色谱仪分析了两种细菌所产色素情况。结果在两株细菌中检测到了细菌叶绿素d(DSM260)、细菌叶绿素e(DSM269)和异海绵烯(DSM269),并获得各类色素的特征吸收光谱和保留时间。依据上述方法,对底层水体缺氧问题突出的长江口南部邻近海域表层沉积物样品进行了初步分析,但未检测到绿硫细菌色素。考虑到长江口邻近海域底层水体缺氧问题正在不断加剧,有必要将绿硫细菌色素作为一类重要的指标作进一步研究。     

Terminal Ediacaran anoxia in deep-ocean: Trace element evidence from cherts of the Liuchapo Formation,South China

Here we report a detailed trace element study of the cherts from Liuchapo Formation, which is a terminal Ediacaran (551-542 Ma) succession in South China deposited in deep-water basinal setting. The REE of Liuchapo cherts shows similar features as observed for anoxic modern seawater (but not for hydrothermal fluids), characterized by positive La anomaly (La_N/Ce_N = 0.83–1.91, average 1.37), moderately negative Ce anomaly (0.53–1.1, average 0.73), positive Gd anomaly (average 1.08), positive Y anomaly (average 1.21), and depleted LREE and MREE. In addition, the Liuchapo cherts have low ΣREE (3.36–56.13 ppm, average 20.6 ppm), low Al₂O₃, Ti, Th and Zr concentrations, and high Y/Ho ratios (up to 43.9). The redox-sensitive trace elements concentrations in the cherts do not correlate with detrital input proxies. All of these features suggest that the redox-sensitive trace elements in the cherts were authigenically concentrated in water column and their concentrations thus are excellent indicators of ancient redox conditions. Very low Th/U ratios, high V/(V+Ni) and Fe_⊤/Al ratios, enrichments of redox-sensitive trace elements (U, V, Mo), and low concentration of Mn in the cherts imply anoxia in the deep seawater. Our data reveal that the terminal Ediacaran ocean was not completely oxidized and the deep ocean was still anoxic, at least in South China. We propose that although the oxidative events existed in the terminal Ediacaran oceans, decomposition of organic matter prolonged anoxia in the deep ocean. Supported by National Natural Science Foundation of China (Grants Nos. 40532012, 40873007, 40603021) and Chinese Academy of Sciences (Grant No. KZCX3-SW-141)