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.

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.

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.

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.

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.

Study of Thermodynamics and Kinetics of CH_4-CaSO_4 and H_2S-Fe_2O_3 Systems

The destruction of hydrocarbon in deep carbonate diagenetic environment is one of problems on the formation of oil and gas. Organic-inorganic reactions in the process of TSR(Thermochemical Sulfate Reduction) are the main reason to make disappearance of the hydrocarbons. The work in this field has often been the subject of much research work in recent years. In this paper, the thermodynamics of CH4-CaSO4 and H2S-Fe2O3 systems is discussed to investigate the possibility of reactions. It is found that these two reactions can proceed spontaneously.Increasing temperature is favorite for CH4-CaSO4 system but disfavorite for H2S-Fe2O3 system. Thermal simulation experiments were carried out using autoclave at high temperature and high pressure. The properties of the products were characterized by microcoulometry, FT-IR and XRD methods. On the basis of the experimental data, a reaction kinetic model is developed and kinetic parameters are determined.

The Role of Saturated Hydrocarbon in Enrichment of Cu, Pb, Zn in Kupferschiefer, Southwestern Poland

In order to clarify the role of organic matter in the enrichment of base metal, 10 samples of the Permian Kupferschiefer from southwestern Poland were analyzed by using microscopic and geochemical methods. The results indicate that the solvent extracts have been depleted in the samples with high Cu, Pb, Zn contents. This depletion occurred preferably in saturated hydrocarbons. Saturated hydrocarbons served as hydrogen donor for thermochemical sulfate reduction (TSR). The GC traces of saturated hydrocarbon show that the depletion occurred mainly in long chain n alkanes.

Chemical, carbon and sulfur isotopic compositions constrain the origin of Upper Carboniferous-Lower Triassic gases in eastern Sichuan Basin, SW China

Methane dominated gas is one of the cleanest energy resources;however, there is no direct method to determine its source rock. Natural gases produced from the eastern Sichuan Basin together with seismic data were studied for their sources and secondary alteration by thermochemical sulfate reduction(TSR). Our results demonstrate that Upper Permian to Lower Triassic(P_(3)ch-T_(1)f) gases in the surrounding of the Kaijiang-Liangping area show volatile organic sulfur compounds(VOSCs) δ^(34)S values close to those of the associated H_(2)S, and may have been altered by methane-dominated TSR, resulting in positive shift in methane δ^(13)C_(1)values with increasing TSR extents. Other(or group 2) gases produced from the P_(3)ch-T_(1)f reservoirs from the southern area and the Upper Carboniferous to Middle Permian(C_(2)h-P_(2)q) from the eastern Sichuan Basin are not significantly changed by TSR, show similar δ^(34)S values between the kerogens and some VOSCs, and may have been derived from the Lower Silurian and Middle Permian source rocks. This study demonstrates a case for the first time showing the δ^(34)S values of VOSCs can be used as a tool for direct correlation between non-TSR altered gas and source rocks. Methane-dominated gas pools can be found using gas and source rock geochemistry combined with seismic data.

Characteristics and geochemical implications of light hydrocarbons from ultra-deep Ordovician oils in the North Shuntuoguole area, Tarim Basin

The ultra-deep Ordovician reservoirs in North Shuntuoguole Oilfield(or Shunbei Oilfield)of Sinopec have achieved annual production of one million ton,and the oil&gas in different faults show different physical properties and fluid phases.In this study,the 28 oil samples from the ultra-deep Ordovician were analyzed using whole oil chromatography.The heptane and isoheptane values of the oil samples were in the range of 29.79%‒46.86%and 1.01%-3.06%,respectively,indicating the oils are high mature.The maturity that calculated based on light hydrocarbon values was higher than which calculated by using aromatic hydrocarbon parameters,suggesting the light hydrocarbon maturity mostly reflects the maturity of the late charged hydrocarbon.The 2M-/3M-C5 and 2M-/3M-C_(6) ratios varied in the ranges of 1.41‒1.81 and 0.79-1.09,respectively,and the iC_(5)/nC_(5) and 3M-C_(5)/nC_(6) ratios were 0.31‒0.90 and 0.16-0.37,respectively,indicating that ultra-deep Ordovician reservoirs have not experienced biodegradation.The Mango parameter K_(1) of the oil samples ranges 0.96‒1.01 except for the oil from Well SB4,which suggests that most of the reservoirs have not suffered thermochemical sulfur reduction(TSR).Meanwhile,the oils have not experienced evaporative fractionation since the toluene/nC_(7) and nC_(7)/MCC_(6) ratios range from 0.10-0.38 and 1.50‒1.80,respectively.The close correlation between P_(3) and P_(2)+N_(2) and between P_(2) and N_(2)/P_(3) indicates that the oils from different faults have the same origin.According to the characteristics of LHs rich in n-alkane,as well as other biomarkers,such as aryl isoprenoids,and aromatic hydrocarbon parameters,the oil originated from the source rock of Lower Cambrian Yu’ertusi Formation.Meanwhile,the source rocks in different fault zones slightly differed in organic facies.