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http://dzumenvis.nic.in/Microbes%20and%20Metals%20Interaction/pdf/Bacterial%20and%20thermochemical%20sulfate%20reduction.pdf

Bacterial and thermochemical sulfate reduction in diagenetic settings — old and new insights

Preface 1 Carbon, the Earth and life: 11 Carbon and the basic requirements of life12 Chemical elements, simple compounds and their origins13 The origin of life14 Evolution of life and the atmosphere15 Major contributors to sedimentary organic matter 2 Chemical composition of biogenic matter: 21 Structure of natural products22 Carbohydrates23 Amino acids and proteins24 Lipids25 Lignins, tannins and related compounds26 Nucleotides and nucleic acids27 Geochemical implicatiions of compositional variation 3 Production, preservation and degradation of organic matter: 31 How and why organic-rich deposits form32 Controls on primary production33 Preservation and degradation of organic matter34 Depositional environments associated with accumulation of organic matter 4 Long-term fate of organic matter in the geosphere: 41 Diagenesis42 Humic material43 Coal44 Kerogen45 Catagenesis and metagenesis46 Temporal and geographical distribution of fossil organic carbon 5 Chemical stratigraphy 51 Biologically mediated transformations52 Examples of source indicators in recent sediments53 Diagenesis at the molecular level54 Source and environment indicators in ancient sediments and oil55 Thermal maturity and molecular transformations56 Palaeotemperature and age measurement57 Maturity of ancient sedimentary organic matter58 Isotopic palaeontology 6 The carbon cycle and climate 61 Global carbon cycle62 Changes in carbon reservoirs over geological time63 Palaeoclimatic variations64 Isotopic excursions at period boundaries65 Human influence on the carbon cycle 7 Anthropogenic carbon and the environment 71 Introduction72 Halocarbons73 Hydrocarbon pollution in aquatic environments74 Endocrine disrupting chemicals75 Environmental behaviour of selected xenobiotic compounds76 Factors affecting the rate of anthropogenic components Appendix 1: SI units usedAppendix 2: SI unit prefixesAppendix 3: Geological timescaleReferencesIndex

An introduction to organic geochemistry

The association of dissolved sulfate and hydrocarbons is thermodynamically unstable in virtually all diagenetic environments. Hence, redox-reactions occur, whereby sulfate is reduced by hydrocarbons either bacterially (bacterial sulfate reductiona BSR) or inorganically (thermochemical sulphate reductiona TSR). Their geologically and economically significant products are similar. Based on empirical evidence, BSR and TSR occur in two mutually exclusive thermal regimes, i.e. low-temperature and hightemperature diagenetic environments, respectively. BSR is common in diagenetic settings from 0 up to about 60‐808C. Above this temperature range, almost all sulfate-reducing microbes cease to metabolize. Those few types of hyperthermophilic microbes that can form H2S at higher temperatures appear to be very rare and do not normally occur and/or metabolize in geologic settings that are otherwise conducive to BSR. TSR appears to be common in geologic settings with temperatures of about 100‐1408C, but in some settings temperatures of 160‐1808C appear to be necessary. TSR does not have a sharply defined, generally valid minimum temperature because the onset and rate of TSR are governed by several factors that vary from place to place, i.e. the composition of the available organic reactants, kinetic inhibitors and/or catalysts, anhydrite dissolution rates, wettability, as well as migration and diffusion rates of the major reactants toward one another. BSR is geologically instantaneous in most geologic settings. Rates of TSR are much lower, but still geologically significant. TSR may form sour gas reservoirs and/or MVT deposits in several tens of thousands to a few million years in the temperature range of 100‐1408C. BSR and TSR may be exothermic or endothermic, depending mainly on the presence or absence of specific organic reactants. However, if the reactions are exothermic, the amount of heat liberated is very small, and this heat usually dissipates quickly. Hence, heat anomalies found in association with TSR settings are normally not generated by TSR. The main organic reactants for BSR are organic acids and other products of aerobic or fermentative biodegradation. The main organic reactants for TSR are branched and n-alkanes, followed by cyclic and mono-aromatic species, in the gasoline range. Sulfate is derived almost invariably from the dissolution of gypsum and/or anhydrite, which may be primary or secondary deposits at or near the redox-reaction site(s). The products of BSR and TSR are similar, but their relative amounts vary widely and are determined by a number of locally variable factors, including availability of reactants, formation water chemistry, and wettability. The primary inorganic reaction products in both thermal regimes are H2S(HS 2 ) and HCO3 (CO2). The presence of alkali earth metals often results in the formation of carbonates, particularly calcite and dolomite. Other carbonates, i.e. ankerite, siderite, witherite, strontianite, may form if the respective metal cations are available. Iron sulfides, galena, and sphalerite form as by-products of hydrogen sulfide generation, if the respective transition or base metals are present or transported to a BSR/TSR reaction site. Elemental sulfur may accumulate as a volumetrically significant

Bacterial and Thermochemical Sulfate Reduction in Diagenetic Settings - Old and New Insights

Products and distinguishing criteria of bacterial and thermochemical sulfate reduction

Large H2S accumulations in deep carbonate reservoirs have been attributed to thermochemical sulphate reduction. Although organic matter has been invoked as the reducing agent, individual reactants in specific environments have hitherto not been identified. Carbon isotope data reveal that light hydrocarbon gases have been effective reducing agents in some Palaeozoic foothill reservoirs of western Canada.

Chemical and isotopic evidence of thermochemical sulphate reduction by light hydrocarbon gases in deep carbonate reservoirs

Automatic δD and δ18O analyses of multi-water samples using H2- and CO2-water equilibration methods with a common equilibration set-up

34S-enriched sulphate in the Belcher Group, N.W.T., Canada: evidence for dissimilatory sulphate reduction in the early Proterozoic ocean

The chemical and isotopic compositions were determined for fumarolic gas samples collected between May 1988 and January 1991 from the summit (“A” terrace) and from the south caldera rim of Izu-Oshima volcano, Japan. The contribution of meteoric water and/or seawater to the “A” terrace fumarolic discharges increased as the fumarole temperature decreased. A large contribution of seawater to the fumarolic gas was inferred during the period from December 1988 to May 1989. The fumaroles which first appeared in June 1989 on the south caldera rim discharge the water vapor derived from local meteoric water. The isotopic compositions of water vapor followed a Rayleigh fractionation process; a part of vapor condensed during ascent in a gas conduit. A scenario for the changes in the discharge system of fumarolic gases at Izu-Oshima volcano is proposed as follows: The proportion of groundwater to the “A” terrace fumarolic gas increased with time as the magma head subsided. The fracture network which formed beneath the caldera during 1986 eruption may have allowed seawater incursion from the coast to the central part of the island. Loss of a large amount of groundwater in the form of vapor from the summit crater may have accelerated infiltration of seawater. The discharge system developed over a wider area as the deeper magma head subsided.

Discharge model of fumarolic gases during post-eruptive degassing of Izu-Oshima volcano, Japan.

大気降下物の起源を明らかにするため湿性降下物とエアロゾルに含まれている非海塩性硫酸イオンの硫黄同位体比 (δ34Snss) を検討した.湿性降下物は山形県の酒田市と山形市で1991年から1999年まで, また, エアロゾルは山形県の鶴岡市と山形市で1993年から1999年まで採取した.(1) 湿性降下物酒田における非海塩性硫酸イオンの硫黄同位体比は冬季に+12～+14‰と高く, 夏季に+1～+6‰と低くなった.冬季に非海塩性硫酸イオンの硫黄同位体比が高くなるのは, アジア大陸北部で使用されている石炭が燃焼される際に発生する人為起源のイオウ酸化物 (SOX) が, 北西季節風によって日本まで輸送されてきているためと考えられる.一方, 山形における非海塩性硫酸イオンの硫黄同位体比は冬季に+6～+10‰, と高く, 夏季に+0～+2‰と低くなった.山形では非海塩性硫酸イオンの硫黄同位体比の季節変動が明瞭な年と不明瞭な年が存在する.これは, 大陸起源の汚染物質の流入の影響が大きい年と小さい年があることを示すものであろう.(2) エアロゾル鶴岡におけるエアロゾルに含まれる非海塩性硫酸イオンの硫黄同位体比は秋季から春季に+5～+14‰と高く, 夏季に+1～+6‰と低くなった.非海塩性硫酸イオンの硫黄同位体比が秋季から春季に高くなるのは, アジア大陸内陸の砂漠起源の硫酸塩を含んだ粒子が日本に長距離輸送されてきているためと考えられる.一方, 山形における非海塩性硫酸イオンの硫黄同位体比は+1～+8‰の範囲で変動しているが, 明瞭な季節変化を示していない.このことは, 内陸である山形では, アジア大陸からもたらされる粒子状物質の影響が小さいことを意味すると考えられる.

https://www.jstage.jst.go.jp/article/seppyo1941/62/3/62_3_215/_pdf

Akira Ueda

Papers

Chemical and isotopic evidence of thermochemical sulphate reduction by light hydrocarbon gases in deep carbonate reservoirs

Automatic δD and δ18O analyses of multi-water samples using H2- and CO2-water equilibration methods with a common equilibration set-up

34S-enriched sulphate in the Belcher Group, N.W.T., Canada: evidence for dissimilatory sulphate reduction in the early Proterozoic ocean

Discharge model of fumarolic gases during post-eruptive degassing of Izu-Oshima volcano, Japan.

Sulfur Isotope Ratio of Non Sea Salt Sulfate in Aerosol and Wet Deposition in Yamagata, Japan