Generation of isotopically and compositionally distinct water during thermochemical sulfate reduction (TSR) in carbonate reservoirs: Triassic Feixianguan Formation, Sichuan Basin, China

Thermochemical sulfate reduction (TSR), the reaction of petroleum with anhydrite in reservoirs resulting in the growth of calcite and the accumulation of H2S, has been documented in the Feixianguan Formation dolomite reservoir in the Sichuan Basin, China. Fluid inclusion salinity and homogenization temperature data have shown that TSR results in a decrease in salinity from a pre-TSR value of 25 wt. % down to 5 wt. % as a result of water created as a byproduct of progressive TSR. We have studied the isotopic character of the water that resulted from TSR in the Feixianguan Formation by analyzing the oxygen isotopes of TSR calcite and determining the oxygen isotopes of the water in equilibrium with the TSR calcite at the temperatures determined by aqueous fluid inclusion analysis. We have compared these TSR-waters to water that would have been in equilibrium with the bulk rock, also at the temperatures determined by aqueous fluid inclusion analysis. We have found that the TSR-waters are relatively depleted in oxygen isotopes (by up to 8‰ compared to what would be expected at equilibrium between the bulk rock and water) since this type of water was specifically derived from anhydrite. The generation of relatively large volumes of low salinity, low δ18O water associated with advanced TSR in the Feixianguan Formation has also been reported in the Permian Khuff Formation in Abu Dhabi and from sour Devonian fields in the Western Canada Basin. This suggests that TSR-derived water may be a common phenomenon, the effects of which on mesogenetic secondary porosity and reservoir quality have previously been underappreciated

Sulfur Cycling During Progressive Burial in Sulfate‐Rich Marine Carbonates

Abstract The isotopic composition of sulfate in the rock record has been frequently used to track the changes in the Earth's surface environments. By considering isotopic fractionation imparted by microbial sulfate reduction (MSR) and thermochemical sulfate reduction (TSR), in this study, we aim to develop a holistic understanding of the mixed effects of MSR and TSR on δ34S signals in sulfate‐rich carbonate systems. We report the occurrence of various types of sulfur‐bearing components from the Cambrian‐Ordovician carbonate system in the Tarim Basin, NW China, coupled with a well‐established diagenesis framework for these rocks. Our results indicate that most of the sulfur‐bearing species possess δ34S values slightly lower than both the source sulfate and the sulfide generated by TSR, yet these sulfur‐bearing species have substantially higher δ34S values than sulfide that resulted from MSR. Hence, a combination of sulfides sourced from MSR and TSR can adequately explain the sulfur isotope data in the studied interval. Building upon this hypothesis, we developed a new sulfur diagenesis model in order to quantify the accumulated H2S from the combined effects of MSR and TSR. Our new model can be used to explain the origin of sulfur‐bearing species in many other deep burial carbonate systems, including the Sichuan Basin, China, and the Gulf of Mexico, USA. We propose that greater attention should be paid to isotopic modulation through mixed diagenetic processes in order to gain a better mechanistic understanding of the primary geochemistry signals (e.g., δ34S) in marine carbonates

Organic matter provenance and depositional environment of marine-to-continental mudstones and coals in eastern Ordos Basin, China—Evidence from molecular geochemistry and petrology

Cyclothems, composed of interbedded mudstone, coal and sandstone layers, make up the Taiyuan and Shanxi Formations in the Late Carboniferous to Early Permian in North China under a marine-to-continental depositional environment. The cyclothems act as important fossil energy hosts, such as coalbeds, hydrocarbon source rocks and unconventional natural gas reservoirs. Organic geochemistry and petrology of mudstones and coals in the Taiyuan and Shanxi Formations in the eastern Ordos Basin were studied to reveal the organic matter sources and paleoenvironments. Total organic carbon (TOC) contents vary from 1.1 wt% (mudstone) to 72.6 wt% (coal). The samples are mainly within the oil window, with the Tmax values ranging from 433 to 469 °C. Organic petrology and source biomarkers indicate that the mudstones were sourced from a mixed organic matter input, and terrigenous organic matter predominates over aquatic organic matter. The coals are mostly sourced by terrigenous organic matter inputs. High concentrations of hopanes argue for a strong bacterial input. Some m/z 217 mass chromatograms have peaks at the hopanes' retention times as a result of high hopane to sterane ratios. These hopane-derived peaks do not interfere the identification of the steranes because the hopanes and the steranes have different retention times. Maturity-dependent biomarkers demonstrate that the samples have been thermally mature, which agree with the Tmax values. Anomalously low C29 20S/(20S + 20R) and C29 ββ/(ββ + αα) sterane ratios are present in all the samples, and are interpreted as due to the terrigenous organic matter input or the coal-related depositional environment. In addition, biomarkers and iron sulfide morphology indicate that the organic matter of the mudstones deposited in a proximal setting with shallow, brackish/fresh water bodies. With consideration of preservation of organic matter, the redox conditions are dysoxic. Redox oscillations resulted in the records of oxic conditions in some samples. Finally, the coals and the mudstones mainly generate gas and have poor oil generative potential

Coupled evolution of nitrogen cycling and redoxcline dynamics on the Yangtze Block across the Ediacaran-Cambrian transition

The authors acknowledge funding support from the NSF FESD and Earth-Life Transitions programs (T.L.), the NASA Astrobiology Institute under Cooperative Agreement No. NNA15BB03A issued through the Science Mission Directorate (T.L.), the key project of the Natural Science Foundation of China (C.-F.C.) (No. 41730424), and the program of China Scholarships Council (Y.C.) (No. 201504910582). Nitrogen and carbon isotope analyses were funded by startup funds from Virginia Tech to B.C.G.The Ediacaran-Cambrian transition is characterized by the evolution of complex eukaryotes and rapid diversification of metazoans. However, linkages between environmental triggers and evolutionary patterns remain unclear. Here, we present high-resolution records of carbon and nitrogen isotopic data (δ13C, δ15N) for a drill core extending from the early Ediacaran Doushantuo Formation to the early Cambrian Jiumenchong Formation, located on the slope of the Yangtze Block. Our data show that sedimentary bulk nitrogen isotope values (δ15Nbulk) decrease progressively from the early Ediacaran to the early Cambrian, broadly concurrent with nitrogen isotope data from other sections throughout the Yangtze Block. During the early Ediacaran, however, δ15Nbulk values from our study are higher (maximum 11.2‰) compared to those from more restricted coeval sections, suggesting a higher degree of denitrification in our slope section. The early Ediacaran δ15Nbulk data from the Yangtze Block may thus provide indirect evidence for an upwelling system that led to a shallower redoxcline in slope environments of the Upper Yangtze region. Widespread light δ15Nbulk values from the early Cambrian (minimum −7.5‰) paired with excess silicate-bound nitrogen throughout much of the Yangtze Block are most parsimoniously interpreted as non-quantitative assimilation of ammonium (NH4+) with relatively high concentrations of NH4+ accumulating in the deep basin. Overall, the spatial and temporal trends in nitrogen cycling across the Yangtze Block suggest that fixed nitrogen was more bioavailable in the Ediacaran-Cambrian Yangtze Basin compared to previously studied Mesoproterozoic sections, although nitrogen speciation in the photic zone may have varied with time. Environmental factors such as oxygen levels and nitrogen bioavailability may have shaped the evolutionary trajectory of life on the Yangtze Block and potentially elsewhere across the Ediacaran-Cambrian transition.PostprintPeer reviewe

Genome of the pitcher plant <i>Cephalotus </i>reveals genetic changes associated with carnivory

Carnivorous plants exploit animals as a nutritional source and have inspired long-standing questions about the origin and evolution of carnivory-related traits. To investigate the molecular bases of carnivory, we sequenced the genome of the heterophyllous pitcher plant Cephalotus follicularis, in which we succeeded in regulating the developmental switch between carnivorous and non-carnivorous leaves. Transcriptome comparison of the two leaf types and gene repertoire analysis identified genetic changes associated with prey attraction, capture, digestion and nutrient absorption. Analysis of digestive fluid proteins from C. follicularis and three other carnivorous plants with independent carnivorous origins revealed repeated co-options of stress-responsive protein lineages coupled with convergent amino acid substitutions to acquire digestive physiology. These results imply constraints on the available routes to evolve plant carnivory

Characterization and Expression of Glutamate Dehydrogenase in Response to Acute Salinity Stress in the Chinese Mitten Crab, Eriocheir sinensis

Glutamate dehydrogenase (GDH) is a key enzyme for the synthesis and catabolism of glutamic acid, proline and alanine, which are important osmolytes in aquatic animals. However, the response of GDH gene expression to salinity alterations has not yet been determined in macro-crustacean species.GDH cDNA was isolated from Eriocheir sinensis. Then, GDH gene expression was analyzed in different tissues from normal crabs and the muscle of crabs following transfer from freshwater (control) directly to water with salinities of 16‰ and 30‰, respectively. Full-length GDH cDNA is 2,349 bp, consisting of a 76 bp 5'- untranslated region, a 1,695 bp open reading frame encoding 564 amino acids and a 578 bp 3'- untranslated region. E. sinensis GDH showed 64-90% identity with protein sequences of mammalian and crustacean species. Muscle was the dominant expression source among all tissues tested. Compared with the control, GDH expression significantly increased at 6 h in crabs transferred to 16‰ and 30‰ salinity, and GDH expression peaked at 48 h and 12 h, respectively, with levels approximately 7.9 and 8.5 fold higher than the control. The free amino acid (FAA) changes in muscle, under acute salinity stress (16‰ and 30‰ salinities), correlated with GDH expression levels. Total FAA content in the muscle, which was based on specific changes in arginine, proline, glycine, alanine, taurine, serine and glutamic acid, tended to increase in crabs following transfer to salt water. Among these, arginine, proline and alanine increased significantly during salinity acclimation and accounted for the highest proportion of total FAA.E. sinensis GDH is a conserved protein that serves important functions in controlling osmoregulation. We observed that higher GDH expression after ambient salinity increase led to higher FAA metabolism, especially the synthesis of glutamic acid, which increased the synthesis of proline and alanine to meet the demand of osmoregulation at hyperosmotic conditions