Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China:Evidence from Formation Water and Natural Gas Geochemistry

Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin （CUTB） show that gas invasion at the late stage is accompanied by an increase of the contents of HeS and CO2 in natural gas, by the forming of the high total dissolved solids formation water, by an increase of the content of HCO3^-, relative to Cl^-, by an increase of the 2nd family ions （Ca^2＋, Mg^2＋, Sr^2＋ and Ba^2＋） and by a decrease of the content of SO4^2-, relative to Cl^-. The above phenomena can be explained only by way of thermochemicai sulfate reduction （TSR）. TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula： ∑CH＋CaSO4＋H-2O→H2S＋CO2＋CaCO3. （1） Dissolved SO4^2- in the formation water is consumed in the above reaction, when HeS and CO2 are generated, resulting in a decrease of SO4^2- in the formation water and an increase of both HeS and CO2 in the natural gas. If formation water exists, the generated CO2 will go on reacting with the carbonate to form bicarbonate, which can be dissolved in the formation water, thus resulting in the enrichment of Ca^2＋ and HCO3^-. The above reaction can be described by the following equation： CO2＋HeO＋CaCO3→Ca^2＋＋2HCO3^-. The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃, which is the minimum for TSR to occur. At the same time, dolomitization, which might be a direct result of TSR, has been found in both the Cambrian and the lower Ordovician. The above evidence indicates that TSR is in an active reaction, providing a novel way to reevaluate the exploration potentials of natural gas in this district.

Rates of bacterial sulfate reduction and their response to experimental temperature changes in coastal sediments of Qi'ao Island, Zhujiang River Estuary in China

Subtropical sediment cores （QA09-1 and QA12-9） from the coastal zone of Qi’ao Island in the Zhujiang River Estuary were used to determine the rates of sulfate reduction and their response to experimental tempera-ture changes. The depth distribution of the sulfate reduction rates was measured from whole-core incu-bations with radioactive tracer35SO42-, and peaks of 181.19 nmol/（cm3·d） and 107.49 nmol/（cm3·d） were exhibited at stations QA09-1 and QA12-9, respectively. The profiles of the pore water methane and sulfate concentrations demonstrated that anaerobic oxidation of methane occurred in the study area, which result-ed in an increase in the sulfate reduction rate at the base of the sulfate-reducing zone. Meanwhile, the sulfate concentration was not a major limiting factor for controlling the rates of sulfate reduction. In addition, the incubation of the sediment slurries in a block with a temperature gradient showed that the optimum tem-perature for the sulfate reduction reaction was 36°C. The Arrhenius plot was linear from the lowest tempera-ture to the optimum temperature, and the activation energy was at the lower end of the range of previously reported values. The results suggested that the ambient temperature regime of marine environments prob-ably selected for the microbial population with the best-suited physiology for the respective environment.

The First Report of Thermochemical Sulfate Reduction Reaction in the Upper Paleozoic Carbonate Rocks of Southeastern Ordos Basin

Thermochemical sulfate reduction （TSR） is the reaction between anhydrite and petroleum fluids at elevated temperatures to produce H2S and CO2. TSR has been studied in many sedimentary basins such as China＇s Sichuan and Tarim basins because it has a profound impact on the commercial viability of petroleum resources, with HzS typically being undesirable.

Sulfate reduction behavior in pressure-bearing leachate saturated zone

Attention should be paid to the sulfate reduction behavior in a pressure-bearing leachate saturated zone.In this study,within the relative pressure range of 0–0.6 MPa,the ambient temperature with the highest sulfate reduction rate of 50℃ was selected to explore the difference in sulfate reduction behavior in a pressure-bearing leachate saturated zone.The results showed that the sulfate reduction rate might further increase with an increase in pressure;however,owing to the effect of pressure increase,the generated hydrogen sulfide (H_(2)S) could not be released on time,thereby decreasing its highest concentration by approximately 85%,and the duration extended to about two times that of the atmospheric pressure.Microbial community structure and functional gene abundance analyses showed that the community distribution of sulfate-reducing bacteria was significantly affected by pressure conditions,and there was a negative correlation between disulfide reductase B(dsrB) gene abundance and H_(2)S release rate.Other sulfate reduction processes that do not require disulfide reductase A (dsrA) and dsrB genes may be the key pathways affecting the sulfate reduction rate in the pressure-bearing leachate saturated zone.This study improves the understanding of sulfate reduction in landfills as well as provides a theoretical basis for the operation and management of landfills.

PICRUSt2 functionally predicts organic compounds degradation and sulfate reduction pathways in an acidogenic bioreactor

For comprehensive insights into the influences of sulfate on performance,microbial community and metabolic pathways in the acidification phase of a two-phase anaerobic system,a laboratory-scale acidogenic bioreactor was continuously operated to treat wastewater with elevated sulfate concentrations from 2000 to 14000 mg/L.The results showed that the acidogenic bioreactor could achieve sulfate reduction efficiency of greater than 70%for influent sulfate content less than 12000 mg/L.Increased sulfate induced the accumulation of volatile fatty acids(VPAs),especially propionate and butyrate,which was the primary negative effects to system performance under the high-sulfate environment.High-throughput sequencing coupled with PICRUSt2 uncovered that the accumulation of VFAs was triggered by the decreasing of genes encoding short-chain acyl-CoA dehydrogenase(EC:1.3.8.1),regulating the transformation of propanoyl-CoA to propenoyl-CoA and butanoyl-CoA to crotonyl-CoA of propionate and butyrate oxidation pathways,which made these two process hardly proceed.Besides,genes encoding(EC:1.3.8.1)were mainly carried by order Clostridiales.Desulfovibrio was the most abundant sulfate-reducing bacteria and identified as the primary host of dissimilatory sulfate reduction ftinctional genes.Functional analysis indicated the dissimilatory sulfate reduction process predominated under a low sulfate environment,but was not favored under the circumstance of high-sulfate.With the increase of sulfate,the assimilatory sulfate reduction process finally overwhelmed dissimilatory as the dominant sulfate reduction pathway in acidogenic bioreactor.

Decreasing ruminal methane production through enhancing the sulfate reduction pathway

Methane(CH4)production from ruminants accounts for 16%of the global greenhouse gas emissions and represents 2%to 12%of feed energy.Mitigating CH_(4) production from ruminants is of great importance for sustainable development of the ruminant industry.H_(2) is the primary substrate for CH_(4) production in the processes of ruminal methanogenesis.Sulfate reducing bacteria are able to compete with methanogens for H_(2) in the rumen,and consequently inhibit the methanogenesis.Enhancing the ruminal sulfate reducing pathway is an important approach to mitigate CH_(4) emissions in ruminants.The review summarized the effects of sulfate and elemental S on ruminal methanogenesis,and clarified the related mechanisms through the impacts of sulfate and elemental S on major ruminal sulfate reducing bacteria.Enhancing the activities of the major ruminal sulfate reducing bacteria including Desulfovibrio,Desulfohalobium and Sulfolobus through dietary sulfate addition,elemental S and dried distillers grains with solubles can effectively decrease the ruminal CH_(4) emissions.Suitable levels of dietary addition with different S sources for reducing the ruminal CH_(4) production,as well as maintaining the performance and health of ruminants,need to be investigated in the future.

Experimental Investigation on Hydrothermal Reduction of Sulfates to H₂S and Organic Sulfides by Ethene

The kinetic characteristics of alkenes involved in thermochemical sulfate reduction (TSR) have been never reported in geological literature. In this study, TSR by ethene under hydrothermal conditions was performed in the constrained simulation experiments. Typical TSR products consisted of H2S, CO2, mercaptans, sulfides, thiophenes derivatives and benzothiophene. The apparent activation energy E and apparent frequency factor A for TSR by ethene were determined as 76.370 kJ/mol and 4.579 s-1, respectively. The lower activation energy for ethene involved in TSR relative to ethane suggested that the reactivity of ethene is much higher than that of ethane, in accordance with the thermodynamic analysis. Rate constants were determined experimentally using first-order kinetics extrapolate to MgSO4 half-lives of 67.329 years - 3.053 years in deep burial diagenetic settings (120°C - 180°C). These values demonstrate that the reaction rate for TSR by ethene is extraordinarily fast in high-temperature gas reservoirs (120°C - 180°C). Consequently, the newly formed ethene from thermal cracking and TSR alteration of natural gas and/or petroleum could not survive after TSR process and were rarely detected in natural TSR reservoirs.

Organic matter accumulation in lacustrine shale of the Permian Jimsar Sag,Junggar Basin,NW China

The lacustrine organic-rich shale in the Permian Lucaogou(LCG)Formation of the Jimsar Sag,Junggar Basin,is one of the main shale oil plays in China.In this paper,geological and geochemical research techniques were employed to evaluate the geochemical variability of the lacustrine shale and the pro-duction of organic matter and its preservation conditions.The LcG Formation is characterized by its complex mineral compositions and a wide range of organic matter richness and quality.The presence of high proportions ofβ-carotane and C2g steranes,indicates that the organic matter mainly originated from phytoplankton and aquatic algal-bacterial organisms,especially cyanobacteria.This study found that the productivity of the Lower LCG Member(P2li)was highest,and the Middle LCG Member(P_(2)l_(2))was the lowest.During the deposition of the Lower LCG Member,the lake's bottom water was predominantly a reducing environment,and the degradation of organic matter was largely a result of bacterial sulfate reduction.During the deposition of the Middle and Upper LCG members,the lake's bottom water was mainly oxidizing,and the degradation of organic matter was likely to be caused by aerobic processes.Based on a comprehensive analysis of the origin and production of organic matter,as well as its depo-sitional environment and preservation conditions,two organic matter accumulation models were pro-posed to explain the distribution of the organic-rich shale.In model A,the high influx of volcanic ash released nutrients and brought abundant sulfate into the water,the accumulation of organic matter was mainly controlled by the preservation of organic matter,which was mainly controlled by BsR.In the model B,the influx of volcanic ash was small,organic matter was mainly degraded by oxygen and the accumulation of organic matter is mainly determined by the production of organic matter.

Diverse transformations of sulfur in seabird-affected sediments revealed by microbial and stable isotope analyses

Microbial communities,sulfur isotope of sulfides(δ^(34)S_(AVS)and δ^(34)S_(CRS)),and sulfur and oxygen isotopes of sulfate(δ^(34)S_(SO_(4))and δ^(18)O_(SO_(4)))in sediments were analyzed to reveal the biogeochemical transformations of sulfur in a seabird-affected lake Y2 and a se abird-free YO from Fildes Peninsula,Antarctic Peninsula.The microbial communities in Y2 were mainly associated with penguin activities,while those in YO were limited by nutrients.The much enriched δ^(34)S_(SO_(4))recorded at depth of 30,41,and 52 cm in Y2indicates very strong sulfate reduction therein.The sulfur-degrading bacteria Pseudomonas in 0-23 cm of Y2 was 3.5 time s as abundant as that of sulfur oxidizing bacteria(SOB),indicating remarkable remineralization of organic sulfur.The abundant SOB and ^(34)S-depleted sulfate indicate considerable sulfur oxidation in 34-56-cm layer in Y2.In YO sediments,the highest abundance of Desulfotalea and the most enriched δ^(34)S_(SO_(4))(35.2‰)and δ^(34)S_(CRS)(2.5‰)indicate the strongest sulfate reduction in 28-cm layer.High abundance of Pseudomonas indicates active remineralization of organic sulfur in 3-5-cm layer in YO.The medium δ^(34)S_(SO_(4))and considerable abundance of SOB and sulfate-reducing bacteria(SRB)indicate concurrence of sulfur oxidation and sulfate reduction in other layers in YO.Therefore,a high level of organic matter input from penguin populations supported the diverse microbial community and transformations of sulfur in aquatic ecosystems in Antarctica.

Origins of High H_2S-bearing Natural Gas in China

Natural gas containing hydrogen sulphide （H2S） has been found in several petroliferous basins in China, such as the Sichuan Basin, Bohai Bay Basin, Ordos Basin, Tarim Basin, etc. Natural gas with higher HES contents （HES 〉5 % mol.） is mostly distributed in both the gas reservoirs of Dukouhe, Luojiazhai, Puguang and Tieshanpo, which belong to the Triassic Feixianguan Formation in the northeastern Sichuan Basin and those of the Kongdian-Shahejie formations in the northeastern Jinxian Sag of the Jizhong Depression, Bohai Bay Basin. In the Sichuan Basin, the HES contents of natural gas average over 9% and some can be 17 %, while those of the Bohai Bay Basin range from 40 % to 92 %, being then one of the gas reservoirs with the highest H2S contents in the world. Based on detailed observation and sample analysis results of a total 5000 m of core from over 70 wells in the above-mentioned two basins, especially sulfur isotopic analysis of gypsum, brimstone, pyrite and natural gas, also with integrated study of the geochemical characteristics of hydrocarbons, it is thought that the natural gas with high HES contents resulted from thermochemical sulfate reduction （TSR） reactions. Among them, the natural gas in the Feixianguan Formation resulted from TSR reactions participated by hydrocarbon gas, while that in the Zhaolanzhuang of the Jinxian Sag being the product of TSR participated by crude oil. During the consumption process of hydrocarbons due to TSR, the heavy hydrocarbons were apt to react with sulfate, which accordingly resulted in the dry coefficient of natural gas increasing and the carbon isotopes becoming heavier.

Isotopic Compositions of Sulfur in the Jinshachang Lead–Zinc Deposit, Yunnan, China, and its Implication on the Formation of Sulfur-Bearing Minerals

The Jinshachang lead-zinc deposit is mainly hosted in the Upper Neoproterozoic carbonate rocks of the Dengying Group and located in the Sichuan-Yunnan-Guizhou （SYG） Pb-Zn-Ag multi- metal mineralization area in China. Sulfides minerals including sphalerite, galena and pyrite postdate or coprecipitate with gangue mainly consisting of fluorite, quartz, and barite, making this deposit distinct from most lead-zinc deposits in the SYG. This deposit is controlled by tectonic structures, and most mineralization is located along or near faults zones. Emeishan basalts near the ore district might have contributed to the formation of orebodies. The j34S values of sphalerite, galena, pyrite and barite were estimated to be 3.6‰-13.4‰, 3.7‰-9.0‰, -6.4‰ to 29.2‰ and 32.1‰34.7‰, respectively. In view of the similar δ34S values of barite and sulfates being from the Cambrian strata, the sulfur of barite was likely derived from the Cambrian strata. The homogenization temperatures （T ≈ 134--383℃） of fluid inclusions were not suitable for reducing bacteria, therefore, the bacterial sulfate reduction could not have been an efficient path to generate reduced sulfur in this district. Although thermochemical sulfate reduction process had contributed to the production of reduced sulfur, it was not the main mechanism. Considering other aspects, it can be suggested that sulfur of sulfides should have been derived from magmatic activities. The δ34S values of sphalerite were found to be higher than those of coexisting galena. The equilibrium temperatures calculated by using the sulfur isotopic composition of mineral pairs matched well with the homogenization temperature of fluid inclusions, suggesting that the sulfur isotopic composition in ore-forming fluids had reached a partial equilibrium.

Geochemical Characterization and Origin of High-Sulfur,Heavy Oils in Jiyang Sub-Basin,East China

High-sulfur,heavy petroleum is widely occurring in the Tertiary lacustrine Jiyang sub-basin, Bohai Bay Basin.They are differentiated into two families based on the bulk properties and biomarker compositions.Family 1 is characterized by high resins（40%-71%）and sulfur（2%-4%）,and low wax （l%-6%）,with n-alkanes removed by biodegradation,whereas family 2 is characterized by extremely abundant sulfur（3%-10%）,and high asphaltenes（7%-31%）and wax（2%-19%）,with no evidence of microbial attack.The oils of family 1 are distributed in the reservoir,lower than 1500 m throughout the sub-basin.Biomarker assemblages,such as low pristane/phytane ratios（1 Pr/Ph）and a high abundance of carotane,gammacerane,and dinosterane,suggest that they are derived from the calcareous mudstones and shales among the stratified,saline Es_4~u unit,in addition to the in situ biodegradation-concentrated sulfur content.However,the oils of family 2 are identified only in the western Zhanhua and eastern Chezhen depressions,with a depth deeper than 1700 m.Physical properties,together with biomarker ratios,including even-numbered n-alkanes,1 Pr/Ph,trace diasteranes,higher C35 homohopanes,and abundant dibenzothiophene series,with1 dibenzothiophene/phenanthrene,indicate an origin from carbonate source rocks.The X-ray diffraction analysis showed that the carbonate source rock is limited in the Es_4~u unit of the Bonan sag,which is different from most other source rocks in the same horizon.It is suggested that the high-sulfur,heavy oils are generated at the early stage of the oil window.Bacterial sulfate reduction might be responsible for the occurrence of sulfur species in the high-sulfur,heavy oils,while heavy biodegradation will enhance sulfur concentrations.

Simulation Experiments on the Reaction of CH_4-CaSO_4 and Its Carbon Kinetic Isotope Fractionation

Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H2S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carried out using an autoclave at high temperatures and high pressures. The products were characterized with analytical methods including carbon isotope analysis. It is found that the reaction can proceed to produce H2S, H2O and CaCO3 as the main products. Based on the experimental results, the carbon kinetic isotope fractionation was investigated, and the value of Ki (kinetic isotope effect) was calculated. The results obtained in this paper can provide useful information to explain the occurrence of H2S in deep carbonate gas reservoirs.

Diagenesis and Restructuring Mechanism of Oil and Gas Reservoir in the Marine Carbonate Formation,Northeastern Sichuan:A Case Study of the Puguang Gas Reservoir

Based on the technology of balanced cross-section and physical simulation experiments associated with natural gas geochemical characteristic analyses, core and thin section observations, it has been proven that the Puguang gas reservoir has experienced two periods of diagenesis and restructuring since the Late Indo-Chinese epoch. One is the fluid transfer controlled by the tectonic movement and the other is geochemical reconstruction controlled by thermochemical sulfate reduction （TSR）. The middle Yanshan epoch was the main period that the Puguang gas reservoir experienced the geochemical reaction of TSR. TSR can recreate the fluid in the gas reservoir, which makes the gas drying index higher and carbon isotope heavier because C2＋ （ethane and heavy hydrocarbon） and 12C （carbon 12 isotope） is first consumed relative to CH4 and 13C （carbon 13 isotope）. However, the reciprocity between fluid regarding TSR （hydrocarbon, sulfureted hydrogen （H2S）, and water） and reservoir rock results in reservoir rock erosion and anhydrite alteration, which increases porosity in reservoir, thereby improving the petrophysical properties. Superimposed by later tectonic movement, the fluid in Puguang reservoir has twice experienced adjustment, one in the late Yanshan epoch to the early Himalayan epoch and the other time in late Himalayan epoch, after which Puguang gas reservoir is finally developed.

Evaluation Methods and Indexes for Ultra-deep Petroleum Reservoir Preservation with Case Studies

Following consideration of the characteristics of high temperature,high pressure and high in-situ stress in ultradeep sedimentary basins,together with the existence of hydrocarbon phase state transformation,hydrocarbon-water-rock interaction and rock mechanical property transition at those depths,the evaluation index system for hydrocarbon preservation was established.The physical leakage evaluation indexes can be divided into three categories:the dynamic efficiency indexes of micro-sealing,caprock integrity and natural gas diffusion.The chemical loss evaluation indexes can be divided into two categories:the thermochemical sulfate reduction(TSR)index in marine gypsum-bearing carbonate strata and the thermochemical oxidation of hydrocarbons(TOH)index in clastic strata.The slippage angle and overconsolidation ratio(OCR)are the key evaluation indexes in the evaluation of the integrity of shale caprocks.TSR intensity can be quantitatively calculated by use of the Zn PVT state parameter method.The TOH strength can be used to estimate the degree of hydrocarbon chemical loss,based on the TOH-related authigenic calcite cement content or the degree of negativeδ^(13)C of authigenic calcite.For the evaluation of ultra-deep preservation in specific areas,key indexes can be selected according to the local geological conditions,instead of all indexes needing to be evaluated for every scenario.

Isotopic Composition of Dissolved Carbonates Meromictic Soda Lake Doroninskoe(Eastern Transbaikalia,Russia)

1 Introduction Meromictic soda Lake Doroninskoe localized in the intermountain area,filled with continental sediments of the Mesozoic,in the upper basin of the river Amur.Coordinates of its location are N51°14’42"E112°14’40",

Hydrochemistry of Salt Lakes in Southeastern Transbaikalia(Russia) in the Time of Arid Phase of Climate Change at the Beginning of the XXI Century

1 Introduction In the south of Eastern Transbaikalia in the border area with China and Mongolia,there are at least 300 saline without outlet lakes.They are confined to the semi-arid zone Daurian steppes with pronounced continental salinization processes and are mostly located on the bottoms of the intermountain basins.Their origin is related to evaporative concentration of fresh waters lakes filling.

Microbial Processes in Stratified Lake Doroninskoe(Transbaikal Region)

In recent decades,meromictic ponds attract the attention of researchers in different directions,because here the character of the physical,chemical and biological processes differ from those of typical mixing waters(Kuznetsov,1970;Hutchinson,1969).In Transbaikalia widely distributed soda and salt lakes with different salinity.Notable among them is Lake Doroninskoye,which has a pronounced stratification for a

The crucial role of deep-sourced methane in maintaining the subseafloor sulfate budget

Methane(CH4)is a powerful greenhouse gas and its largest reservoir on Earth is held in marine sediments.CH4 in marine sediments is mainly stored in gas-hydrate reservoirs and deep sedimentary strata along continental margins,where large amounts of deep-sourced CH4 ascend to different degrees toward the seafloor.However,the amount of deep-sourced CH4 and its role in subseafloor carbon and sulfur cycling remains poorly constrained.We analyzed sulfate(SO_(4)^(2-))profiles of 157 sites along with previous published 85 sites to determine the regional distribution and amount of SO_(4)^(2-) reduction for an area of 1.23×10^(5) km^(2) of the northern South China Sea.Then we compared these obtained results with estimates based on sedimentation rates from the same area.Significantly higher regional SO_(4)^(2-) flux estimates based on SO_(4)^(2-) profiles(4.26×10^(-3)Tmol a^(-1)),compared to lower estimates based on sedimentation rates(1.23×10^(-3)Tmol a^(-1)),reflect abundant ascending deep-sourced CH4.The difference of the regional SO_(4)^(2-) flux estimates(3.03×10^(-3)Tmol a^(-1))represents the amount of SO_(4)^(2-) reduced by CH_(4) through the anaerobic oxidation of CH_(4)(AOM).Deep-sourced CH_(4) contributes 71%to total SO_(4)^(2-) consumption in the study area,largely exceeding SO_(4)^(2-) consumption by organoclastic sulfate reduction.Our findings substantiate that deep-sourced CH4 governs subseafloor carbon and sulfur cycling to a previously underrated extent,fueling extensive chemosynthesis-based ecosystems along continental slope and rise.

Effect of Sodium Sulfate on Direct Reduction of Beach Titanomagnetite for Separation of Iron and Titanium

The effect of sodium sulfate on direct reduction of beach titanomagnetite,followed by magnetic separation,to separate iron and titanium was investigated. Direct reduced iron（ DRI） with a high Fe content,low TiO_2 content and low iron recovery was obtained after adding sodium sulfate. When the sodium sulfate dosage was increased from 0 to 10 mass%,the Fe content of the DRI increased from 90. 00 mass% to 93. 55 mass% and the TiO_2 content decreased from 1. 27 mass% to 0. 70 mass%. The reduction mechanism of sodium sulfate was investigated by X-ray diffraction（ XRD） and scanning electron microscopy（ SEM） with energy dispersive spectrometer（ EDS）. Results revealed that the metallic iron grains in the reduced ore with sodium sulfate were larger than those in the ore without sodium sulfate. Sodium sulfate promoted the migration of iron as well as the accumulation and growth of metallic iron grains by low-melting-point carnegieite and troilite formed in the redox system. Low-melting-point carnegieite decreased the melting point of the system and then promoted liquefaction. Troilite could decrease the surface tension and melting point of metallic iron grains.