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At least 37 records · Page 2

Process sensitivity studies of the Westinghouse sulfur cycle for hydrogen generation

The effect of variations of acid concentration, pressure, and temperature on the thermal process efficiency of the Westinghouse sulfur cycle was examined using the HYDRGN program. Modifications to the original program were made to duplicate the process flowsheet and take into account combined cycle heat-to-work efficiencies for electrochemical work requirements, aqueous solutions, and heat-of-mixing effects. A total of 125 process variations were considered (acid concentration: 50-90 w/o; pressure: 15-750 psia; temperature: 922K - 1366K). The methods of analysis, results, and conclusions are presented.

Carty, R. H.↗

Process sensitivity studies of the Westinghouse Sulfur Cycle for hydrogen generation

The effect of variations of acid concentration, pressure, and temperature on the thermal process efficiency of the Westinghouse Sulfur Cycle was examined using the University of Kentucky's HYDRGN program. Modifications to the original program were made to duplicate the process flow sheet and take into account combined-cycle heat-to-work efficiencies for electrochemical work requirements, aqueous solutions, and heat-of-mixing effects. A total of 125 process variations were considered (acid concentration: 50-90 w/o; pressure: 15-750 psia; temperature: 922-1366 K (2000 F)). The methods of analysis, results, and conclusions are presented.

Carty, R.↗

Sulfur cycling in freshwater sediments

Organic sulfur containing compounds represent greater than 80% of the total sulfur in sediments of eutrophic freshwater lakes. Although sedimentary sulfur is predominantly in the form of organic compounds, more sulfur is transformed by sulfate reduction than by any other process. Rates of sulfate reduction in these sediments average 7 mmol/sq m/day. This rate is 19 times greater than the net rate of production of inorganic sulfur from organic compounds on an annual basis.

Klug, M. J.↗

Global Studies of the Sulfur Cycle Including the Influence of DMS and Fossil Fuel Sulfur on Climate and Climate Change

The indirect effect of anthropogenic aerosols, wherein aerosol particles are thought to increase cloud droplet concentrations and cloud lifetime, is the most uncertain component of climate forcing over the past 100 years. Here, for the first time, we use a mechanistic treatment of droplet nucleation and a prognostic treatment of the number of cloud droplets to study the indirect aerosol effect from changes in carbonaceous and sulfate aerosols. Cloud droplet nucleation is parameterized as a function of total aerosol number concentration, updraft velocity and a shape parameter, which takes into account the mechanism, of sulfate aerosol formation, while cloud droplet number depends on the nucleation as well as on droplet sinks. Whereas previous treatments have predicted annual average indirect effects between -1 and -2 W/sq m, we obtain an indirect aerosol effect between -0.14 W/sq m and -0.42 W/sq m in the global mean.

Penner, Joyce E.↗

Sulfur Cycle

Among the general categories of tropospheric sulfur sources, anthropogenic sources have been quantified the most accurately. Research on fluxes of sulfur compounds from volcanic sources is now in progress. Natural sources of reduced sulfur compounds are highly variable in both space and time. Variables, such as soil temperature, hydrology (tidal and water table), and organic flux into the soil, all interact to determine microbial production and subsequent emissions of reduced sulfur compounds from anaerobic soils and sediments. Available information on sources of COS, CS2, DMS, and H2S to the troposphere in the following paragraphs are summarized; these are the major biogenic sulfur species with a clearly identified role in tropospheric chemistry. The oxidation of SO2 to H2SO4 can often have a significant impact on the acidity of precipitation. A schematic representation of some important transformations and sinks for selected sulfur species is illustrated.

Hariss, R.↗

Possible roles of manganese redox chemistry in the sulfur cycle

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

Nealson, K. H.↗

Microbial Diversity and Sulfur Cycling in an Early Earth Analogue: From Ancient Novelty to Modern Commonality

Life emerged and diversified in the absence of molecular oxygen. The prevailing anoxia and unique sulfur chemistry in the Paleo-, Meso-, and Neoarchean and early Proterozoic eras may have supported microbial communities that differ from those currently thriving on the earth’s surface. Zodletone spring in southwestern Oklahoma represents a unique habitat where spatial sampling could substitute for geological eras namely, from the anoxic, surficial light-exposed sediments simulating a preoxygenated earth to overlaid water column where air exposure simulates oxygen intrusion during the Neoproterozoic era. We document a remarkably diverse microbial community in the anoxic spring sediments, with 340/516 (65.89%) of genomes recovered in a metagenomic survey belonging to 200 bacterial and archaeal families that were either previously undescribed or that exhibit an extremely rare distribution on the current earth. Such diversity is underpinned by the widespread occurrence of sulfite, thiosulfate, tetrathionate, and sulfur reduction and the paucity of sulfate reduction machineries in these taxa.

59 BASIC BIOLOGICAL SCIENCES↗

Kinetics of Thermochemical Reactions Important in the Venus Atmospheric Sulfur Cycle

The purpose of this project was to experimentally measure the rates of several thermochemical gas-solid reactions between sulfur gases in the Venus atmosphere and reactive minerals on the hot Venus surface. Despite the great importance of these reactions for the maintenance of significant amounts of sulfur gases (and thus for the maintenance of the global cloud cover) in the atmosphere of Venus, essentially no kinetic data are currently available for them.

Fegley, Bruce, Jr.↗

Some thoughts on GAIA and the sulfur cycle

The data hypothesis states that the composition, oxidation reduction state, and temperature of the troposphere are actively regulated by the biota for the biota. One of the early predictions of the Gaia hypothesis was that there should be a sulfur compound made by the biota in the oceans. It would need to be stable enough against oxidation in water to allow its transfer to the air. Either the sulfur compound itself or its atmospheric oxidation product would have to return sulfur from the sea to the land surfaces. The most likely candidate for this role was dimethyl sulfide. Another sulfur compound of interest from a Gaian viewpoint CS2 (carbon disulfide) is discussed. Theories on the production of dimethyl sulfide and carbon disulfide related to the Gaian hypothesis are examined.

Lovelock, J. E.↗

Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle

The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.

Fegley, Bruce, Jr.↗

A study on the electrolysis of sulfur dioxide and water for the sulfur cycle hydrogen production process

Experimental electrolysis cells using various platinum catalyzed carbon electrodes were tested. When operated at 200 mA/sq cm current density using 50 w/o acid at 50 C and 1 atm, a reference cell required 1.22 volts and degraded rapidly. After several improvements were incorporated into electrodes and the test cell configuration, a later cell required only 0.77 volts under identical operating conditions. At a lower current density, 100 mA/sq cm, the cell required only 0.63 volts. Kinetic studies on metal electrodes, measurements of temperature effects on electrode kinetics, investigations of electrocatalytic activities of metal electrodes over a wide range of acid concentrations, cyclic voltametric studies and evaluation of alternate catalysts were also conducted. From diffusivity experiments, a cation exchange membrane material, P-4010, exhibited an excellent diffusion coefficient, more than two orders of magnitude lower than that of rubber. Ionic resistivity measurements of eight materials showed that microporous rubber had the lowest resistivity.

Source record↗

Carbon and sulfur cycling through geologic time

Mathematical models of the coupled global systems of sedimentary reservoirs and fluxes are used to infer variations in reservoir sizes and rates of sedimentation over periods of hundreds of millions of years. Perhaps most interesting is the coupled sulfide/sulfate carbon/carbonate system that controls global oxygen and carbon dioxide production and consumption is discussed.

Garrels, R. M.↗

A 3-D Model Analysis of The Impact of Asian Anthropogenic Emissions on the Sulfur Cycle Over the Pacific Ocean

The impact of anthropogenic activities on the SO2 and sulfate aerosol levels over the Pacific region is examined in the Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model. We focus on the analysis of the data from the NASA Pacific Exploratory Missions (PEM) over the western North Pacific and the tropical Pacific. These missions include PEM-West A in September-October 1991, when the Asian outflow was at the minimum but the upper atmosphere was heavily influenced by the Pinatubo volcanic eruption, and PEM-West B in March-April 1994 when the Asian outflow was at the maximum, and PEM-Tropics A in August-September at a region relatively free of direct anthropogenic influences. Specifically, we will examine the relative importance of anthropogenic, volcanic and biogenic sources to the SO2 and sulfate concentrations over the Pacific, and quantify the processes controlling the distributions of SO2 and sulfate in both the boundary layer and the free troposphere. We will also assess the global impact of SO2 emission in Asia on the sulfate aerosol loading.

Chin, Mian↗

Sulfur Cycling Mediates Calcium Carbonate Geochemistry in Modern Marine Stromatolites

Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.

Visscher, P. T.↗