ALBERT

Description / Table of Contents: Contents: Preface. - Workshop Participants and Contributors to this Volume. - 1 Sulphur Isotopes in Nature and the Environment: An Overview. - 1.1 Introduction. - 1.2 Theory and measurement of isotope effects. - 1.2.1 Equilibrium isotope effects. - 1.2.2 Kinetic isotope effects-isotope fractionation in unidirectional process. - 1.2.3 Fractionation factors. - 1.3 Sulphur isotope variations in nature. - 1.3.1 Biological sulphur cycle. - 1.3.1.1 Isotope fractionation by assimilatory reduction of sulphate. - 1.3.1.2 Isotope effects in the dissimilatory reduction of sulphate. - 1.3.1.3 Isotope fractionation during oxidation of sulphide. - 1.3.2 The marine sedimentary cycle. - 1.3 .3 Fossil fuels. - 1.4 Sulphur isotopes in the atmosphere. - 1.5 Rain water. - 1.5 .1 Ocean sulphate in rain water. - 1.6 Lakes and rivers. - 1.7 Vegetation. - 1.8 Applications. - 2 Oxygen Isotope Fractionation for Understanding the Sulphur Cycle. - 2.1 Introduction. - 2.2 Bases for the use of oxygen isotopy. - 2.2.1 Sulphate-water isotope exchange. - 2.2.2 SO2- water isotope exchange. - 2.2.2.1 Aqueous systems. - 2.2.2.2 Systems with no liquid water. - 2.2.3 [Delta]18O values of SO2 oxidants and of associated water. - 2.2.4 Rapid hydration of SO3. - 2.2.5 Sulphide oxidation. - 2.2.6 Bacterial SO4^-2. - 2.2. 7 Sulphate crystallization. - 2.3 Applications of 18^O studies to environmental sulphates. - 2.3.1 Atmosphere. - 2.3 .1.1 Precipitation sulphates. - 2.3 .1.2 Aerosol sulphates. - 2.3.1.3 Sulphur dioxide. - 2.3.2 Hydrosphere. - 2.3.2.1 Oceans. - 2.3.2.2 Streams and lakes. - 2.3.2.3 Ground waters. - 2.3.3 Lithosphere. - 2.4 Conclusions. - 3 The Isotopic Analysis of Sulphur and Oxygen. - 3.1 The isotopic analysis of sulphur. - 3.1.1 Introduction. - 3.1.2 The chemical pretreatment of sulphur samples. - 3.1.2.1 Introduction. - 3.1.2.2 The conversion of barium sulphate to silver sulphide. - 3.1.2.3 Sulphur in the atmosphere and in water. - 3.1.2.4 Sulphur in vegetation, soils, and sediments. - 3.1.2.5 Sulphur in petroleum, coal, and sulphurores. - 3.1.3 The preparation of sulphur samples for mass spectrometry. - 3.1.3.1 lntroduction. - 3.1.3.2 Combustion of sulphides in oxygen. - 3.1.3.3 Oxidation of sulphides using a solid oxygen donor. - 3.1.3.4 Direct conversion of barium sulphate to sulphur dioxide. - 3.1.3.5 The purification and storage of sulphur dioxide. - 3.1.3.6 The preparation of sulphur hexafluoride. - 3 .1.4 The mass spectrometric analysis of sulphur. - 3.2 Oxygen isotopes. - 3.2.1 lntroduction. - 3.2.2 Sampie collection. - 3.2.3 Sampie preparation. - 3.2.3.1 Introduction. - 3.2.3.2 Sulphate. - 3.2.3.3 Water. - 3.2.3.4 SO2 and O2. - 3.2.4 The mass spectrometric analysis of oxygen. - 4 Lithospheric Sources of Sulphur. - 4.1 Sulphur in the cosmos and the crust-mantle system. - 4.2 Sulphur and oxygen isotope composition of marine evaporite and barite strata. - 4.2.1 Introduction. - 4.2.2 Compilation of [Delta]^34S and [Delta]^18O data for marine evaporites. - 4.2.2.1 General remarks on the data. - 4.2.2.2 Description of the [Delta]^34S- and [Delta]^18O- age curves. - 4.2.2.3 Minima and abrupt rises in the [Delta]^34S-age curve. - 4.2.2.4 Non-marine evaporites. - 4.2.3 Data from marine barites. - 4.2.4 Reservoir of evaporite sulphur. - 4.3 Isotopic composition of sulphur in sulphide ores. - 4.4 Native eiemental sulphur deposits. - 4.5 Sulphur isotope composition of fossil fuels. - 4. 5.1 Peat and Iignite. - 4.5.2 Coal. - 4.5.3 Oil. - 4.5.3.1 Introduction. - 4.5.3.2 Summary of [Delta]^34S data for oil. - 4.5.3.3 Estimate of the mean [Delta]^34S value of oil. - 4.5.3.4 Use of sulphur isotope analyses to determine petroleum contamination in sediments. - 4.5.4 H2S in hydrocarbon deposits. - 4.6 Flux of volcanogenic sulphur to the atmosphere and isotopic composition of total sulphur. - 4.6.1 Volcanogenic sulphur flux to the atmosphere. - 4.6.2 Isotopic composition of volcanogenic sulphur. - 4.6.2.1 Isotopic composition of gases emitted to the atmosphere during eruption. - 4.6.2.2 Isotopic composition of ash emitted to the atmosphere during eruptions. - 4.6.2.3 The sulphur isotope composition of gaseous emissions from fumaroles and solfataras. - 4.6.3 The isotopic composition of total volcanic sulphur entering the atmosphere. - 5 Sulphur Isotope Variations in the Atmosphere. - 5.1 Introduction. - 5.2 Sulphur species in the atmosphere. - 5.2.1 Atmospheric S compounds and their concentrations. - 5.2.2 The atmospheric chemistry of sulphur. - 5.2.2.1 H2S oxidation . - 5.2.2.2 S^O dust. - 5.2.2.3 SO2 chemistry. - 5.3 Analytical techniques. - 5.3.1 Sampling of atmospheric S compounds. - 5.3.2 Further characterization of atmospheric compounds for sulphur isotope analyses. - 5.3.2.1 Wind direction. - 5.3.2.2 Particle size. - 5.3.2.3 Photographic examination of particles. - 5.3.2.4 Endogenous versus adsorbed sulphur. - 5.3.3 The use of sulphur isotope data from vegetation and soils. - 5.4 Sulphur isotope abundance variations in atmospheric compounds. - 5.4.1 Fractionation of sulphur isotopes during transformations of atmospheric sulphur compounds. - 5.4.2 Natural sources. - 5.4.2.1 Sea spray and marine aerosols. - 5.4.2.2 Biogenic emissions. - 5.4.2.3 Volcanic activity. - 5.4.3 Anthropogenic sources. - 5.4.3.1 Combustion of coal. - 5.4.3.2 Combustion and refining of oil and gas. - 5.4.3.3 Sulphide ores. - 5.4.3.4 Gypsum mining and processing. - 5.4.4 Summary. - 5.5 Delineation of anthropogenic and natural fluxes of atmospheric S compounds. - 5.5.1 Use of [Delta]^34S and concentration data to identify sources of atmospheric gases. - 5.5.2 Use of [Delta]^34S and concentration data to identify sources of SO4^2- in precipitation. - 5.5.3 Use of [Delta]^18O and concentration data to identify sources of So4^2- in precipitation. - 5.5.4 lsotopic delineation of sources of sulphur emissions in local situations. - 5.5.5 Construction of regional balances of atmospheric sulphur. - 5.5.6 Estimate of the isotopic composition of biogenic sulphur in the atmosphere. - 5.6 Potential of using enriched sulphur isotopes for studying transport, transformations, and removal of atmospheric sulphur. - 5.6.1 Introduction. - 5.6.2 Background fluctuations. - 5.6.3 Dispersion and dilution. - 5.6.4 Economic evaluation. - 6 Hydrosphere. - 6.1 Introduction. - 6.2 Oceans. - 6.2.1 Dissolved sulphate. - 6.2.2 Sulphur of aquatic organisms. - 6.3 Modern world sediments. - 6.3.1 Intensity of sulphate reduction. - 6.3.2 Rate of bacterial sulphate reduction and other factors influencing the distribution of sulphur compounds and their [Delta]^34S values in recent sediments. - 6.3.3 Mass and isotopic balance of sulphur in recent sediments. - 6.3.4 Inftuence of the rate of sulphate reduction on sulphide mineral formation. - 6.4 Lakes. - 6.4.1 Lakes: water column. - 6.4.1.1 Isotopic changes due to Iake pollution. - 6.4.1.2 Oligotrophic lakes. - 6.4.1.3 Eutrophic lakes. - 6.4.1.4 Meromictic lakes. - 6.4.2 Lakes: sediments. - 6.4.2.1 Anthropogenic inftuence on the isotopic composition of sulphur in Iake sediments of eastern North America. - 6.5 Isotopic composition of sulphur in continental seas. - 6.5.1 The Black Sea. - 6.5.2 The Azov Sea. - 6.5.3 The Caspian Sea. - 6.5.4 The Baltic Sea. - 6.5.5 The Red Sea . - 6.5 .6 Conclusion. - 6.6 Rivers. - 6.7 Ground water. - 6. 7.1 Introduction. - 6.7.2 The recharge environment. - 6.7.3 Ground water. - 6.8 Isotopic composition of sulphate in gas- and oilfield formation waters. - 6.9 Geothermal areas. - 6.10 Warm and cold springs. - 6.10.1 Introduction. - 6.10.2 Springs containing primarily dissolved sulphate. - 6.10.3 Springs containing primarily dissolved sulphide. - 6.10.4 Sulphur geochemistry of springs in relation to anthropogenic sulphur. - 6.11 Summary and key areas for further research. - 7 Pedosphere and Biosphere. - 7.1 Pedosphere. - 7.1.1 Forms of sulphur in soil. - 7.1.1.1 Inorganic sulphur. - 7.1.1.2 Organic sulphur. - 7.1.1.3 Transformations of sulphur in soils. - 7 .1.2 Sources of sulphur compounds in soil. - 7.1.3 Sulphur and oxygen isotope variations in soil. - 7.1.4 Relationships among [Delta]^34S values of different soil extracts.- 7.1.5 Transfer of sulphur into the soil as revealed by sulphur isotope data. - 7.2 Vegetation. - 7.2.1 Forms of sulphur in vegetation. - 7 .2.2 Sulphur isotope distribution in vegetation. - 7.2.3 Assimilation of sulphate by plants and algae. - 7.2.4 Uptake of sulphide by plants and algae. - 7.2.5 Relative incorporation of soil and atmospheric sulphur by vegetation. - 7.2.6 The influence of biological parameters on the sulphur isotope composition of plants. - 7.2.7 Emission of reduced sulphur compounds by vegetation. - 7.3 Food webs and higher animals. - 8 Case Studies and Potential Applications. - 8.1 Introduction. - 8.2 Sulphur isotope tracing of the fate of emissions from sour gas processing in Alberta, Canada. - 8.2.1 Overview. - 8.2.2 The sour gas industry of Alberta. - 8.2.3 Sulphur isotope composition of the atmosphere in Alberta. - 8.2.3.1 Regional pattern. - 8.2.3.2 Relationship of [Delta]^34S to concentrations of atmospheric S compounds. - 8.2.3.3 Dependence of [Delta]^34S values of atmospheric S on wind direction. - 8.2.3.4 Isotopic composition of atmospheric particulate matter. - 8.2.4 Sulphur isotope composition of surface waters. - 8.2.5 Sulphur isotope abundances in soils and vegetation of Alberta. - 8.2.6 Isotopic modelling of uptake of industrial S by the environment near sour gas processing plants in Alberta. - 8.2.7 Discussion and recommendations. - 8.3 The isotopic composition and content of sulphur in soils of Kansk-Achinsk fuel power generation complex. - 8.3.1 lntroduction. - 8.3.2 Results. - 8.3.3 Conclusion. - 8.4 Sulphur isotope measurements relevant to power plant emissions in the northeastern United States. - 8.4.1 Introduction. - 8.4.2 Fuels in use. - 8.4.3 Sulphur isotope compositions of ambient ground-level SO2 and sulphate. - 8.4.4 Available fuels and other sources. - 8.4.5 Conclusions. - 8.5 Environmental sulphur isotope studies in Japan. - 8.5 .1 Introduction. - 8.5.2 The quantity and sulphur isotopic composition of hydrogen sulphide released from tidal flats. - 8.5.2.1 Sampling. - 8.5.2.2 Observations and discussion. - 8.5.3 Secondary production in sulphuric acid from volcanic ash in surface water after a volcanic eruption. - 8.5.3.1 Introduction. - 8.5.3.2 Results and discussion. - 8.5.4 Sources of atmospheric sulphur compounds based on the sulphur isotopic composition of SO4^2- in precipitation in Japan, 1960-79. - 8.5.4.1 Introduction. - 8.5.4.2 Atmospheric SO2 and H2S and pH of precipitation in Japan. - 8.5.4.3 Sulphur isotopic composition of SO4^2- in rain and snow in Japan. - 8.5 .5 Estimation of the contribution of anthropogenic sulphur to the atmosphere in Japan. - 8.6 The use of sulphur and other stable isotopes in environmental studies of regional groundwater flow and sulphate mineral formation in Kuwait. - 8.6.1 Introduction. - 8.6.2 Geological setting. - 8.6.3 Sampling and analytical techniques. - 8.6.4 Isotopic composition of the waters. - 8.6.5 Isotopic composition of the sulphate. - 8.6.6 Conclusions. - 8.7 Natural sulphur isotope distributions for sulphate and sulphides in semi-arid, marginal marine environments in Australia. - 8.7.1 Introduction. - 8.7.2 Study sites. - 8.7.2.1 Spencer Gulf, South Australia. - 8.7.2.2 Shark Bay, Western Australia. - 8. 7.3 Isotope data for water and sulphates. - 8.7.3.1 Continental waters, Spencer Gulf. - 8.7.3.2 Pertidal waters, Spencer Gulf. - 8.7.3.3 Shark Bay. - 8.7.4 Isotope distribution in peritidal sulphides. - 8.7.5 Summary. - 8.8 Contributions to sulphur to the atmosphere from utilization of fossil fuels, Australia. - 8.8.1 Coals. - 8.8.2 Crudes and condensates. - 8.8.3 Natural gases. - 8.8.4 Oil shales. - 8.8.5 Isotopic composition and fate of sulphur mined in Australia with copper, Iead, zinc, and nickel ores. - 8.9 Sulphur isotope studies of atmospheric S and the corrosion of monuments in Prague, Czechoslovakia. - 8.9.1 Introduction. - 8.9.2 Analytical. - 8.9.3 Results and discussion. - 8.9.3.1 Atmospheric studies. - 8.9.3.2 Stone monuments. - 8.10 Determination of total sulphur [Delta]^34S values in ore deposits of the Precambrian of India. - 8.10.1 Overview. - 8.10.2 Introduction. - 8.10.3 Sulphur isotope data and estimation of ore solution parameters. - 8.10.4 Trace elements in the evaluation of [Delta]^34Stotal. - 8.10.5 Conclusions. - 8.11 Potential research areas for sulphur isotope geochemistry in Nigeria. - 8.11.1 Introduction. - 8.11.2 Research areas in Nigeria. - 8.11. 3 Stable sulphur isotopes in basic geochemical research. - 8.11.3.1 Basement complex rocks. - 8.11.3.2 Lead-zinc mineralization and salt deposits. - 8.11.3.3 Agulu-Nanka gully complex sulphur deposits. - 8.11.4 Fossil fuel deposits. - 8.11.4.1 Coal and mine drainage. - 8.11.4.2 Petroleum and natural gas. - 8.11.4.3 Oil shales and tar sands. - 8.11.5 Emission of sulphur. - 8.11.6 Other research areas. - Appendix. - 9 Summary. - Index.

Description / Table of Contents: This book addresses the important question of differentiating natural and anthropogenic sulphur in the environment. International experts explain how stable isotopes of sulphur and oxygen have been used to study the origin and transformations of sulphur in ecosystems. The topic is treated in logical sequence with the first two chapters providing an overview of the basic principles of sulphur and oxygen isotope research. The third chapter reviews experimental techniques. Subsequent chapters are devoted to the lithosphere, atmosphere, hydrosphere, pedosphere, and biosphere. In the final chapter, investigators relate how they have successfully applied, or plan to apply, stable isotope techniques to study sulphur in a variety of ecological systems throughout the world. Therefore this SCOPE report provides comprehensive coverage of both basic concepts and first hand experiences of practising scientists. The book is the outcome of a workshop of the Sulphur Unit of the United Nations Environmental Program.