The low-temperature hydrolysis of carbonyl sulfide and carbon disulfide: a review

Rhodes, Colin; Riddel, Stewart; West, John; Williams, B. Peter; Hutchings, Graham J.

doi:10.1016/s0920-5861(00)00309-6

Cited by 203 publications

(123 citation statements)

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“…A number of hypotheses including the thermal degradation of soil organic matter or desorption of COS from soil surfaces have been proposed and are partially supported by the persistence of COS emissions after autoclaving (Kato et al, 2008;Whelan & Rhew, 2015;. Another abiotic process that could lead to 10 COS production is the chemical reaction that occurs in flue gas from molecules present during combustion such as CH4 + SO2  COS + H2O + H2 (Rhodes et al, 2000). Both sulphur dioxide (SO2) and methane (CH4) can be produced in soils, however CH4 is generally produced in anaerobic zones of submerged soils and tends not to accumulate at the soil surface (Le Mer and Roger, 2001).…”

Section: Drivers and Mechanisms Of Cos Production Across European Soimentioning

confidence: 99%

Disentangling the rates of carbonyl sulphide (COS) production and consumption and their dependency with soil properties across biomes and land use types

Kaisermann¹,

Ogée²,

Sauze³

et al. 2018

Preprint

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Abstract. Soils both emit and consume the trace gas carbonyl sulphide (COS) leading to a soil-air COS exchange rate that is the net result of two opposing fluxes. Partitioning these two gross fluxes and understanding their drivers are necessary to 10 estimate the contribution of soils to the current and future atmospheric budget of COS.Previous efforts to disentangle the gross COS fluxes from soils have used flux measurements on air-dried soils as a proxy for the COS emission rates of moist soils. However, this method implicitly assumes that COS uptake becomes negligible and COS emission remains steady while soils are drying. We tested this assumption by estimating simultaneously the soil COS sources and sinks and their temperature sensitivity (Q10) from soil-air COS flux measurements on fresh soils at different COS 15 concentrations and two soil temperatures. Measurements were performed on 27 European soils from different biomes and land use types in order to obtain a large range of physical-chemical properties and identify the drivers of COS consumption and production rates.We found that COS production rates from moist and air-dried soils were not significantly different for a given soil and that the COS production rates had Q10 values (3.96 ± 3.94) that were larger and more variable than the Q10 for COS consumption 20(1.17 ± 0.27). COS production generally contributed less to the net flux that was dominated by gross COS consumption but this contribution of COS production increased rapidly at higher temperature, lower soil moisture and lower COS concentrations. Consequently, measurements at higher COS concentrations (viz. 1000 ppt) always increased the robustness of COS consumption estimates. Across the range of biomes and land use types, COS production rates co-varied with total soil nitrogen (r = 0.68, P < 0.05) and the first-order COS uptake rate co-varied most with microbial N content (r = 0.64, P < 0.05) 25providing new insights on how to upscale the contribution of soils to the global COS atmospheric budget.Atmos. Chem. Phys. Discuss., https://doi

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Section: Drivers and Mechanisms Of Cos Production Across European Soimentioning

confidence: 99%

Disentangling the rates of carbonyl sulphide (COS) production and consumption and their dependency with soil properties across biomes and land use types

Kaisermann¹,

Ogée²,

Sauze³

et al. 2018

Preprint

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“…Processes for removing H 2 S are not normally effective in removing OCS, and these may even produce OCS through a reaction of H 2 S with CO 2 (Pessayre et al, 2007;Rhodes et al, 2000).…”

Section: Vehicles and Shipsmentioning

confidence: 99%

Anthropogenic contributions to global carbonyl sulfide, carbon disulfide and organosulfides fluxes

Lee

Brimblecombe

2016

Earth-Science Reviews

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Previous studies of the global sulfur cycle have focused almost exclusively on oxidized species and just a few sulfides. This focus is expanded here to include a wider range of reduced sulfur compounds. Inorganic sulfides tend to be bound into sediments, and sulfates are present both in sediments and the oceans. Sulfur can adopt polymeric forms that include S-S bonds. This review examines the global anthropogenic sources of reduced sulfur, updating emission inventories and widening the consideration of industrial sources. It estimates the anthropogenic fluxes of key sulfides to the atmosphere (units Gg S

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“…It is widely known that S is detrimental to the Fischer-Tropsch reaction in particular (LIU et al, 1994;RHODES et al, 2000). Thus, the applicability of this type of synthesis to S-rich natural hydrothermal systems is still a matter of debate.…”

Section: Ch 3 Oh and Ch 4 Formationmentioning

confidence: 99%

Laboratory and field-based investigations of subsurface geochemical processes in seafloor hydrothermal systems

Reeves¹

2010

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This thesis presents the results of four discrete investigations into processes governing the organic and inorganic chemical composition of seafloor hydrothermal fluids in a variety of geologic settings. Though Chapters 2 through 5 of this thesis are disparate in focus, each represents a novel investigation aimed at furthering our understanding of subsurface geochemical processes affecting hydrothermal fluid compositions. Chapters 2 and 3 concern the abiotic (nonbiological) formation of organic compounds in high temperature vent fluids, a process which has direct implications for the emergence of life in early Earth settings and sustainment of present day microbial populations in hydrothermal environments. Chapter 2 represents an experimental investigation of methane (CH 4 ) formation under hydrothermal conditions. The overall reduction of carbon dioxide (CO 2 ) to CH 4 , previously assumed to be kinetically inhibited in the absence of mineral catalysts, is shown to proceed on timescales pertinent to crustal residence times of hydrothermal fluids. In Chapter 3, the abundance of methanethiol (CH 3 SH), considered to be a crucial precursor for the emergence of primitive chemoautotrophic life, is characterized in vent fluids from ultramafic-, basalt-and sediment-hosted hydrothermal systems. Previous assumptions that CH 3 SH forms by reduction of CO 2 are not supported by the observed distribution in natural systems. Chapter 4 investigates factors regulating the hydrogen isotope composition of hydrocarbons under hydrothermal conditions. Isotopic exchange between low molecular weight n-alkanes and water is shown to be facilitated by metastable equilibrium reactions between alkanes and their corresponding alkenes, which are feasible in natural systems. In Chapter 5, the controls on vent fluid composition in a backarc hydrothermal system are investigated. A comprehensive survey of the inorganic geochemistry of fluids from sites of hydrothermal activity in the eastern Manus Basin indicates that fluids there are influenced by input of acidic magmatic solutions at depth, and subsequently modified by variable extents of seawater entrainment and mixing-related secondary acidity production. CHAPTER 1 IntroductionSeafloor hydrothermal systems associated with the generation of oceanic crust represent a dramatic expression of heat and mass transfer from the interior of the Earth. In addition to profound effects on ocean chemistry, convective circulation of seawater through volcanically active oceanic crust leads to the formation of metal sulfide deposits. In addition, seafloor hot springs are often invoked as ideal settings from which early microbial life could have emerged.Since the initial discovery of low temperature venting at the Galápagos Spreading Center in 1977 (CORLISS et al., 1979), our understanding of the composition and diversity of hydrothermal solutions has expanded greatly. During convection through oceanic crust of basaltic composition, O 2 -replete seawater reacts with crustal rock, typically producin...

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The low-temperature hydrolysis of carbonyl sulfide and carbon disulfide: a review

Cited by 203 publications

References 55 publications

Disentangling the rates of carbonyl sulphide (COS) production and consumption and their dependency with soil properties across biomes and land use types

Disentangling the rates of carbonyl sulphide (COS) production and consumption and their dependency with soil properties across biomes and land use types

Anthropogenic contributions to global carbonyl sulfide, carbon disulfide and organosulfides fluxes

Laboratory and field-based investigations of subsurface geochemical processes in seafloor hydrothermal systems

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