Science.gov

Sample records for atmospheric sulfur behavior

  1. The sulfur cycle in the marine atmosphere

    NASA Technical Reports Server (NTRS)

    Toon, Owen B.; Kasting, James F.; Turco, Richard P.; Liu, May S.

    1987-01-01

    The simulation of the sulfur cycle in the marine atmosphere using a one-dimensional photochemical model is described and evaluated. Theoretical uncertainties concerning the operation of the marine sulfur cycle are examined, and measurements of sulfur gases in the marine atmosphere necessary for developing the model are derived. Previous modeling studies are reviewed, and the data from these studies are compared to the model simulations. Recommendations for improving the simulation of the sulfur cycle in the marine atmosphere are discussed.

  2. Accumulation of atmospheric sulfur in some Costa Rican soils

    USGS Publications Warehouse

    Bern, Carleton R.; Townsend, Alan R.

    2013-01-01

    Sulfur is one of the macronutrient elements whose sources to terrestrial ecosystems should shift from dominance by rock-weathering to atmospheric deposition as soils and underlying substrate undergo progressive weathering and leaching. However, the nature and timing of this transition is not well known. We investigated sources of sulfur to tropical rain forests growing on basalt-derived soils in the Osa Peninsula region of Costa Rica. Sulfur sources were examined using stable isotope ratios (δ34S) and compared to chemical indices of soil development. The most weathered soils, and the forests they supported, are dominated by atmospheric sulfur, while a less weathered soil type contains both rock-derived and atmospheric sulfur. Patterns of increasing δ34S with increasing soil sulfur concentration across the landscape suggest atmospheric sulfur is accumulating, and little rock-derived sulfur has been retained. Soil sulfur, minus adsorbed sulfate, is correlated with carbon and nitrogen, implying that sulfur accumulation occurs as plants and microbes incorporate sulfur into organic matter. Only the lower depth increments of the more weathered soils contained significant adsorbed sulfate. The evidence suggests a pattern of soil development in which sulfur-bearing minerals in rock, such as sulfides, weather early relative to other minerals, and the released sulfate is leached away. Sulfur added via atmospheric deposition is retained as organic matter accumulates in the soil profile. Adsorbed sulfate accumulates later, driven by changes in soil chemistry and mineralogy. These aspects of sulfur behavior during pedogenesis in this environment may hasten the transition to dominance by atmospheric sources.

  3. Gaseous sulfur in the Venusian atmosphere

    NASA Astrophysics Data System (ADS)

    San'ko, N. F.

    1980-07-01

    It is shown that the increased extinction of solar radiation scattered in the Venusian atmosphere, recorded by scanning spectrophotometers on board Venera 11 and 12, may be explained by the presence of gaseous sulfur in the lower atmosphere of the planet. A model of the vertical distribution of gaseous sulfur with respect to allotropic states is proposed.

  4. Behavior of sulfur during coal pyrolysis

    USGS Publications Warehouse

    Shao, D.; Hutchinson, E.J.; Heidbrink, J.; Pan, W.-P.; Chou, C.-L.

    1994-01-01

    The behavior of sulfur in Illinois coals during pyrolysis was evaluated by thermogravimetry/ Fourier transform-infrared spectroscopy (TG/FT-IR) techniques. SO2, COS, and H2S were major gaseous sulfur-containing products observed during coal pyrolysis. The release rates of the gaseous sulfur species showed several peaks within the temperature ranges, which were due to the emission of different forms of sulfur in coal. ?? 1994.

  5. Thermochemistry of substellar atmospheres: Water, oxygen, sulfur, and phosphorus

    NASA Astrophysics Data System (ADS)

    Visscher, Channon Wayne

    2006-09-01

    Thermochemical equilibrium and kinetic calculations are used to investigate atmospheric chemistry in substellar objects: giant planets, extrasolar giant planets (EGPs), and brown dwarfs. These studies include an assessment of the water and total oxygen inventories in the interiors of Jupiter and Saturn, and detailed modeling of sulfur and phosphorus chemistry in the atmospheres of substellar objects. In the first part of the dissertation, the water and total oxygen abundances in the deep atmospheres of Jupiter and Saturn are determined by considering the effects of H 2 O and O on the chemistry of CO, PH 3 , and SiH 4 . On Jupiter, the observed CO abundance indicates a water abundance of 0.4--1.4 times the protosolar H 2 O/H 2 ratio (8.96 × 10 -4 ). On Saturn, a combination of CO and PH 3 chemical constraints requires a water abundance of 1.9--6.1 times the protosolar abundance. Combining these results with Si mass balance considerations gives a total oxygen abundance of 0.7--1.7 and 3.2--6.4 times the protosolar O/H 2 ratio (1.16 × 10 -3 ) on Jupiter and Saturn, respectively. In both planets, oxygen is less enriched than other heavy elements (such as carbon) relative to hydrogen and the solar system composition. These results provide important constraints for giant planet formation mechanisms and models of tropospheric chemistry. The second part of the dissertation is a detailed study of sulfur and phosphorus chemistry in substellar atmospheres. The chemical behavior of individual S- and P-bearing gases and condensates is determined as a function of temperature, total pressure, and metallicity. Aside from minor amounts of sulfur removed by metal sulfide cloud formation, H 2 S is approximately representative of the sulfur inventory throughout substellar atmospheres. Silicon sulfide (SiS) is a potential tracer of weather in EGPs and L dwarfs. Phosphorus chemistry is considerably more complex than that of sulfur. Disequilibrium abundances of PH 3 approximately

  6. Pacific Atmospheric Sulfur Experiment (PASE): An Overview

    NASA Astrophysics Data System (ADS)

    Bandy, A. R.; Blomquist, B.; Huebert, B.; Howell, S.; Clarke, T.; Hudson, J.; Faloona, I.; Wang, Y.; Mauldin, R. L.; Heikes, B.; Merrill, J.; O'Sullivan, D.

    2008-12-01

    The Pacific Atmospheric Sulfur Experiment (PASE) was a study of the chemistry of sulfur in a cloud free region of the equatorial Pacific Ocean. The experiment was conducted aboard the NSF C130 just east of Christmas Island during August and early September of 2007 in the prevailing southeasterly trade wind flow. PASE is envisioned as the first of a series of experiments focused on developing an understanding of how the chemistry of sulfur affects climate in general but especially with respect to its impact on cloud chemistry and physics. Being the first of this series, PASE was focused on (but not limited to) clear air to narrow the scope of the science to control costs and to reflect the fact that most of the available instrumentation cannot make effective measurements in clouds. PASE is unique in that it brought together several instruments (SO2, DMS, O3 and H2O) that make measurements fast enough to permit the computation of vertical fluxes by eddy covariance allowing the flux terms in chemical budgets to be determined quantitatively. The PASE instrument payload also made a large suite of slower measurements including but not limited to OH, HO2, RO2, H2SO4, methane sulfonic acid (MSA), H2O2, CH3COOH, thermally resolved CN(>15nm), ultrafine CN (>3 nm), bulk aerosol composition, and cloud condensation nuclei (CCN). The high rate instruments enabled quantification of the vertical exchange that could be generalized to estimate the mixing of the slower analytes. One of the surprising results from PASE was the large and very steady levels of CCN observed throughout the experiment. Furthermore, the vertical gradient indicated that boundary layer venting via shallow convection was a persistent sink of the CCN. Taken in concert the unique data set renders a picture of marine air that has not been purged by precipitation in a long while, allowing it to build up large amounts of volatile sulfur in the condensed phase and providing a superb environment to investigate

  7. Sulfur accumulation and atmospherically deposited sulfate in the Lake States.

    Treesearch

    Mark B. David; George Z. Gernter; David F. Grigal; Lewis F. Ohmann

    1989-01-01

    Characterizes the mass of soil sulfur (adjusted for nitrogen), and atmospherically deposited sulfate along an acid precipitation gradient from Minnesota to Michigan. The relationship of these variables, presented graphically through contour mapping, suggests that patterns of atmospheric wet sulfate deposition are reflected in soil sulfur pools.

  8. Sulfur Chemistry in the Early and Present Atmosphere of Mars

    NASA Technical Reports Server (NTRS)

    Levine, Joel S.; Summers, M. E.

    2011-01-01

    Atmospheric sulfur species resulting from volcanic emissions impact the composition and chemistry of the atmosphere, impact the climate, and hence, the habitability of Mars and impact the mineralogy and composition of the surface of Mars. The geochemical/ photochemical cycling of sulfur species between the interior (via volcanism), the atmosphere (atmospheric photochemical and chemical processes) and the deposition of sulfuric acid on the surface of Mars is an important, but as yet poorly understood geochemical/ photochemical cycle on Mars. There is no observational evidence to indicate that Mars is volcanically active at the present time, however, there is strong evidence that volcanism was an important and widespread process on early Mars. The chemistry and photochemistry of sulfur species in the early and present atmosphere of Mars will be assessed using a one-dimensional photochemical model. Since it is generally assumed that the atmosphere of early Mars was significantly denser than the present 6-millibar atmosphere, photochemical calculations were performed for the present atmosphere and for the atmosphere of early Mars with assumed surface pressures of 60 and 350-millibars, where higher surface pressure resulted from enhanced atmospheric concentrations of carbon dioxide (CO2). The following sections include the results of earlier modeling studies, a summary of the one-dimensional photochemical model used in this study, a summary of the photochemistry and chemistry of sulfur species in the atmosphere of Mars and some of the results of the calculations.

  9. Sulfur dioxide contributions to the atmosphere by volcanoes.

    PubMed

    Stoiber, R E; Jepsen, A

    1973-11-09

    The first extensive measurements by remote-sensing correlation spectrometry of the sulfur dioxide emitted by volcanic plumes indicate that on the order of 10(3) metric tons of sulfur dioxide gas enter the atmosphere daily from Central American volcanoes. Extrapolation gives a minimum estimate of the annual amount of sulfur dioxide emitted from the world's volcanoes of about 10(7) metric tons.

  10. Atmospheric sulfur as related to acid precipitation and soil fertility

    SciTech Connect

    Suarez, E.L.; Jones, U.S.

    1982-09-01

    Conductivity, pH, and ionic components were determined in the rainfall and particulate matter at Clemson, S.C., Experiment, Ga., and Franklin, N.C., using a wet/dry collector. Sulfur in the air was collected at Clemson on a 30-d interval in a standard lead peroxide sampler. Soil samples were taken from 15 locations in South Carolina and analyzed for sulfur. It was observed that the average loading concentration of anions in rainwater increased during the spring-summer months and decreased during the fall-winter months. Sulfuric and nitric acids were found to be the major components of acid rainfall. Rainfall and air deposition contributed approximately 10.7 and 1.8 kg/ha of sulfur per year, respectively, at Clemson. Atmospheric deposition from the particulate matter contributed an estimated 3.0 kg/ha of sulfur during the year. Increases in corn grain and silage yields were obtained with the application of 18 kg/ha of sulfur at Darlington, S.C. A relationship between applied sulfur and crop response for the other crops considered could not be established. A need for reevaluating the findings and recommendations for sulfur fertilizers was apparent because of the contribution of atmospheric-deposited sulfur to the soil and plant sulfur supply.

  11. The transport of atmospheric sulfur over Cape Town

    NASA Astrophysics Data System (ADS)

    Jenner, Samantha L.; Abiodun, Babatunde J.

    2013-11-01

    Cape Town, renowned for its natural beauty, is troubled by an unpleasant brown haze pollution, in which atmospheric sulfur plays a major role. This study investigates whether Cape Town is a net producer or recipient of anthropogenic sulfur pollution. In the study, two atmospheric chemistry-transport models (RegCM and WRF) are used to simulate atmospheric flow and chemistry transport over South Africa for two years (2001 and 2002). Both models reproduce the observed seasonal variability in the atmospheric flow and SO2 concentration over Cape Town. The models simulations agree on the seasonal pattern of SO2 over South Africa but disagree on that of SO4. The simulations show that ambient sulfur in Cape Town may be linked with pollutant emissions from the Mpumalanga Highveld, South Africa's most industrialized region. While part of atmospheric SO2 from the Highveld is transported at 700 hPa level toward the Indian Ocean (confirming previous studies), part is transported at low level from the Highveld toward Cape Town. In April, a band of high concentration SO2 extends between the Highveld and Cape Town, following the south coast. Extreme sulfur pollution events in Cape Town are associated with weak flow convergence or stagnant conditions over the city, both of which encourage the accumulation of pollution. However the study suggests that atmospheric sulfur is being advected from Mpumalanga Highveld to Cape Town and this may contribute to atmospheric pollution problems in Cape Town.

  12. Sulfuric acid aerosols in the atmospheres of the terrestrial planets

    NASA Astrophysics Data System (ADS)

    McGouldrick, Kevin; Toon, Owen B.; Grinspoon, David H.

    2011-08-01

    Clouds and hazes composed of sulfuric acid are observed to exist or postulated to have once existed on each of the terrestrial planets with atmospheres in our solar system. Venus today maintains a global cover of clouds composed of a sulfuric acid/water solution that extends in altitude from roughly 50 km to roughly 80 km. Terrestrial polar stratospheric clouds (PSCs) form on stratospheric sulfuric acid aerosols, and both PSCs and stratospheric aerosols play a critical role in the formation of the ozone hole. Stratospheric aerosols can modify the climate when they are enhanced following volcanic eruptions, and are a current focus for geoengineering studies. Rain is made more acidic by sulfuric acid originating from sulfur dioxide generated by industry on Earth. Analysis of the sulfur content of Martian rocks has led to the hypothesis that an early Martian atmosphere, rich in SO 2 and H 2O, could support a sulfur-infused hydrological cycle. Here we consider the plausibility of frozen sulfuric acid in the upper clouds of Venus, which could lead to lightning generation, with implications for observations by the European Space Agency's Venus Express and the Japan Aerospace Exploration Agency's Venus Climate Orbiter (also known as Akatsuki). We also present simulations of a sulfur-rich early Martian atmosphere. We find that about 40 cm/yr of precipitation having a pH of about 2.0 could fall in an early Martian atmosphere, assuming a surface temperature of 273 K, and SO 2 generation rates consistent with the formation of Tharsis. This modeled acid rain is a powerful sink for SO 2, quickly removing it and preventing it from having a significant greenhouse effect.

  13. Sulfur Mass Independent Fractionation in the Oxidizing Atmosphere?

    NASA Astrophysics Data System (ADS)

    Mills, M. J.; Pavlov, A. A.; Toon, O. B.

    2004-12-01

    The discovery of mass-independent fractionation (MIF) in sulfur isotopes in Archean sediments and a lack of MIF in sulfur in the younger rocks (Farquhar, 2000) places a strict upper constraint on the amount of oxidants and oxygen in the ancient atmosphere prior to 2.3 Gyr ago (Pavlov and Kasting, 2002). However recent Antarctic ice core measurements show a small, but non-zero, MIF in sulfate correlated with the large volcanic eruptions (Savarino et al., 2003). Moreover, recent measurements of isotopic compositions in present-day sulfate aerosols also exhibit non-zero MIF (Romero and Thiemens, 2003). MIF must be produced by UV photolysis in the stratosphere or mesosphere, but sulfur re-entering the troposphere takes only one chemical form (sulfate), making preservation of any sulfur MIF signature difficult to explain. We added sulfur isotopes to the Garcia-Solomon 2D dynamical/chemical model with aerosol microphysics and looked at how strong the initial atmospheric fractionation has to be in order to be preserved upon descent to the troposphere. Our calculations can quantitatively constrain the oxidative capacity of the atmosphere over the period of the ice core record. We will discuss two possibilities to preserve small sulfur MIF in the present atmosphere: 1) Preservation through stratospheric and mesospheric sulfate aerosols 2) Preservation through the alternative pathway of SO2 oxidation (Savarino et al., 2003).

  14. Quantum Chemical Studies of Reactions Involving Sulfur and Sulfur-Chlorine Compounds for Venus Atmospheric Modeling Networks

    NASA Astrophysics Data System (ADS)

    Woon, D. E.; Maffucci, D. M.; Herbst, E.

    2017-05-01

    We are characterizing reactions involving sulfur and sulfur-chlorine compounds thought to be relevant to Venus using high level quantum chemical theory and reaction rate theory in order to improve atmospheric modeling studies.

  15. Connection of sulfuric acid to atmospheric nucleation in boreal forest.

    PubMed

    Nieminen, T; Manninen, H E; Sihto, S L; Yli-Juuti, T; Mauldin, R L; Petäjä, T; Riipinen, I; Kerminen, V M; Kulmala, M

    2009-07-01

    Gas to particle conversion in the boundary layer occurs worldwide. Sulfuric acid is considered to be one of the key components in these new particle formation events. In this study we explore the connection between measured sulfuric acid and observed formation rate of both charged 2 nm as well as neutral clusters in a boreal forest environment A very short time delay of the order of ten minutes between these two parameters was detected. On average the event days were clearly associated with higher sulfuric acid concentrations and lower condensation sink (CS) values than the nonevent days. Although there was not a clear sharp boundary between the nucleation and no-nucleation days in sulfuric acid-CS plane, at our measurement site a typical threshold concentration of 3.10(5) molecules cm(-3) of sulfuric acid was needed to initiate the new particle formation. Two proposed nucleation mechanisms were tested. Our results are somewhat more in favor of activation type nucleation than of kinetic type nucleation, even though our data set is too limited to omit either of these two mechanisms. In line with earlier studies, the atmospheric nucleation seems to start from sizes very close to 2 nm.

  16. One. Phase transformations and the spectral reflectance of solid sulfur: Possible metastable sulfur allotropes on Io's surface. 2. Photochemistry and aerosol formation in Neptune's atmosphere

    NASA Astrophysics Data System (ADS)

    Moses, Julianne Ives

    Two papers are presented, and in the first one the spectral reflectance of elemental sulfur is examined in a set of laboratory experiments to determine the factors that affect the transformation rate of monoclinic (beta) sulfur and various other sulfur allotropes into orthorhombic (alpha) sulfur. The laboratory data have implications for the spectral variation and physical behavior of freshly solidified sulfur, if any exists, on Jupiter's satellite Io. Depending on its thermal history, molten sulfur on Io would initially solidify into a glassy solid or a monoclinic crystalline lattice; these forms might contain polymeric sulfur molecules as well as the more abundant S8 molecules. If freshly frozen sulfur on Io could lose heat rapidly and approach ambient dayside Io temperatures within several hours, then some of the metastable sulfur allotropes could be maintained on Io virtually indefinitely. Small droplets of sulfur ejected during plume eruptions might cool quickly enough to preserve these allotropes, but sulfur in large volcanic flows or lakes would probably remain warm long enough for phase transformations to proceed at a visible rate. The second paper involves the photodissociation of methane at high levels in Neptune's atmosphere leads to the production of more complex hydrocarbon species such as ethane, acetylene, methylacetylene, propane, diacetylene, ethylacetylene, and butane. These gases diffuse to the lower stratosphere where temperatures are low enough to allow all seven of the aforementioned species to condense. Particle formation may not occur readily, however, as the vapor species become supersaturated. We present a theoretical analysis of particle formation mechanisms at conditions relevant to Neptune's troposphere and stratosphere and show that hydrocarbon nucleation is very inefficient under Neptunian conditions: saturation ratios much greater than unity are required for aerosol formation by either heterogeneous, ion-induced, or homogeneous

  17. Composition and oxidation state of sulfur in atmospheric particulate matter

    NASA Astrophysics Data System (ADS)

    Longo, Amelia F.; Vine, David J.; King, Laura E.; Oakes, Michelle; Weber, Rodney J.; Huey, Lewis Gregory; Russell, Armistead G.; Ingall, Ellery D.

    2016-10-01

    The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS) and X-ray fluorescence (XRF) microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm) analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

  18. Sulfur and Sulfuric Acid Microphysics in the Venus Atmosphere: Implications for the Unknown UV Absorber

    NASA Astrophysics Data System (ADS)

    Gao, P.; Carlson, R. W.; Robinson, T. D.; Crisp, D.; Lyons, J. R.; Yung, Y. L.

    2016-12-01

    A mystery that has continued to plague our sister planet, Venus, for nearly a century is the nature of the brightness contrasts observed crisscrossing its disk in near-ultraviolet wavelength images. These contrasts - specifically the dark regions - have been attributed to the actions of an unknown UV absorber, knowing the identity of which is integral to understanding the Venus atmosphere due to the high rates of mesospheric heating attributed to the absorption of solar UV. One possible candidate for the UV absorber is polysulfur, which form from polymerization of elemental sulfur arising from SO2 photolysis at the Venus cloud tops under low O2 conditions. In this work we investigate the microphysics of condensed polysulfur and its interaction with the sulfuric acid clouds. We consider the "gumdrop model", where sulfur is allowed to condense onto sulfuric acid cloud particles. We explore the possibility that S2 vapor may condense faster than its loss to gas phase reactions that produce higher allotropes, leading to solid state polymerization to S8. This process may explain the ephemeral and variable nature of the UV absorption.

  19. Sulfur during the Transition from Anoxic to Oxic Atmospheres

    NASA Technical Reports Server (NTRS)

    Zahnle, Kevin; Catling, David; Claire, Mark

    2006-01-01

    The invention of oxygenic photosynthesis was likely accompanied by the introduction of large amounts of O2 and complementary reduced gases (chiefly CH4) into the atmosphere. To first approximation the venting of O2 and CH4 are stochiometrically linked. We therefore present a suite of numerical photochemical models that address the anoxic-oxic transition in an atmosphere driven by large linked inputs of biogenic 02 and CH4. We find in general that, in steady state, there are two solutions, one oxic and the other anoxic. The anoxic solution appears to be linearly stable. If volcanic SO2 fluxes are large, S disproportionates into oxidized (H2S04) and reduced (S8) exit channels. As elemental sulfur is insoluble it provides a means of preserving photochemical mass-independent fractionation (MIF). On the other hand, if the source of volcanic SO2 is smaller than today, all S can leave the atmosphere as S8. Under these conditions there would be no MIF signal. The oxic solution appears to be linearly unstable. In the oxic solutions S is invariably oxidized to sulfate, and the MIF signal would be absent. The transitional atmosphere is relatively unstable and is also the most photochemically active. Consequently it is the transitional atmosphere, not the oxic or anoxic atmospheres, that has the lowest CH4 levels and weakest greenhouse warming. As a practical matter we expect the transitional atmospheres to vary strongly in response to diurnal and seasonal biological forcing.

  20. Sulfur during the Transition from Anoxic to Oxic Atmospheres

    NASA Technical Reports Server (NTRS)

    Zahnle, Kevin; Catling, David; Claire, Mark

    2006-01-01

    The invention of oxygenic photosynthesis was likely accompanied by the introduction of large amounts of O2 and complementary reduced gases (chiefly CH4) into the atmosphere. To first approximation the venting of O2 and CH4 are stochiometrically linked. We therefore present a suite of numerical photochemical models that address the anoxic-oxic transition in an atmosphere driven by large linked inputs of biogenic 02 and CH4. We find in general that, in steady state, there are two solutions, one oxic and the other anoxic. The anoxic solution appears to be linearly stable. If volcanic SO2 fluxes are large, S disproportionates into oxidized (H2S04) and reduced (S8) exit channels. As elemental sulfur is insoluble it provides a means of preserving photochemical mass-independent fractionation (MIF). On the other hand, if the source of volcanic SO2 is smaller than today, all S can leave the atmosphere as S8. Under these conditions there would be no MIF signal. The oxic solution appears to be linearly unstable. In the oxic solutions S is invariably oxidized to sulfate, and the MIF signal would be absent. The transitional atmosphere is relatively unstable and is also the most photochemically active. Consequently it is the transitional atmosphere, not the oxic or anoxic atmospheres, that has the lowest CH4 levels and weakest greenhouse warming. As a practical matter we expect the transitional atmospheres to vary strongly in response to diurnal and seasonal biological forcing.

  1. Total Sulfur Deposition (wet+dry) from the Atmosphere

    EPA Pesticide Factsheets

    Sulfur Dioxide (SO2) is emitted primarily as a by-product of coal combustion from power plants. Sulfur Dioxide reacts in the atmosphere to form other chemical such as Sulfuric Acid and Amonium Sulfate. These compounds and their secondarily formed constituents deposit to the surface either in a dry form as gas or particulate or in a wet form along with rain and other forms for precipitation. Sulfate deposition can cause acidification of surface waters. The first, https://edg.epa.gov/dataORD/NERL/ReVA/ReVA_Data.zip, contains the variables used in this study and is freely available to the public. The second, www.waratah.com/region3edt is available to the general public to learn more about the ReVA program within EPA Region 3. The third, http://www.waratah.com/revanew/Welcome.asp, provides additional information about the tools and variables used in this program, but users must first obtain a user name and password to access it. A user name and password may be obtained from Vasu Kilaru at kilaru.vasu@epa.gov.

  2. Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

    NASA Technical Reports Server (NTRS)

    Baldwin, A. C.; Golden, D. M.

    1979-01-01

    The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

  3. Electrochemical behavior of silver in concentrated sulfuric acid solutions

    SciTech Connect

    Gordeeva, T.V.; Krasikov, B.S.

    1985-04-20

    The authors use stationary and rotating silver disk electrodes for studying the electrochemical behavior of silver in sulfuric acid solutions. Charts present data gathered on potential of the silver electrode in absence of current in sulfate solutions; on calculated curves and experimental points for anodic dissolution of a rotating silver disk electrode in sulfuric acid solution; and on influence of the average activity of sulfuric acid on the equilibrium potential of the silver electrode. The authors conclude that the rates of electrodeposition and dissolution of silver in concentrated sulfuric acid solutions, whether containing silver ions or not, are determined only by the rates of diffusion of silver ions and their sulfate complexes.

  4. Atmospheric Sulfur Hexafluoride: Measurements and Emission Estimates from 1970 - 2008

    NASA Astrophysics Data System (ADS)

    Rigby, M. L.; Prinn, R. G.; Muhle, J.; Miller, B. R.; Dlugokencky, E. J.; Krummel, P. B.; Steele, L. P.; Fraser, P. J.; Leist, M.; Weiss, R. F.; Harth, C. M.; O'Doherty, S. J.; Greally, B. R.; Simmonds, P. G.; Derek, N.; Vollmer, M. K.; Kim, J.; Kim, K.; Porter, L. W.

    2009-12-01

    We present an air history of atmospheric sulfur hexafluoride (SF6) from the early 1970s through 2008. During this period, concentrations of this extremely potent and long-lived greenhouse gas have increased by more than an order of magnitude, and its growth has accelerated in recent years. In this study, historical concentrations are determined from archived air samples measured on the Advanced Global Atmospheric Gases Experiment (AGAGE) ‘Medusa’ gas chromatography/mass spectrometry system. These data are combined with modern high-frequency measurements from the AGAGE and National Oceanic and Atmospheric Administration (NOAA) in situ networks and ˜weekly samples from the NOAA flask network, to produce a unique time series with increasing global coverage spanning almost four decades. Using the three-dimensional chemical transport Model for Ozone and Related Tracers (MOZART v4.5) and a discrete Kalman filter, we derive estimates of the annual emission strength of SF6 on hemispheric scales from 1970 - 2004 and on continental scales from 2004 - 2008. Our emission estimates are compared to the recently compiled Emissions Database for Global Atmospheric Research (EDGAR v4), and emissions reported under the United Nations Framework Convention on Climate Change (UNFCCC). The cause of the recent growth rate increase is also investigated, indicating that the origin of the required emissions rise is likely to be South-East Asia.

  5. Atmospheric sulfur deposition and streamwater quality in Finland

    NASA Astrophysics Data System (ADS)

    Lahermo, P. W.; Tarvainen, T.; Tuovinen, J.-P.

    1994-10-01

    The correlation between sulfate concentrations in Finnish headwater streams and atmospheric sulfate deposition has been studied by using data from the streamwater chemistry in August September 1990 and computed S deposition from the anthropogenic emissions. The sulfate concentrations and acidity in water are interpolated and smoothed into a deposition model grid. These data are compared with geological and pedogeochemical (glacial till) background information. The areas where the streamwater SO4 concentrations are mainly controlled by either anthropogenic S deposition or sulfur in till is estimated by applying the fuzzy Gustafsson-Kessel algorithm, which provides a soft clustering suitable for overlapping control factors. Residual areas can be well explained by the SO4-rich Littorina clay deposits. The higher overall background SO4 concentrations in streams in south Finland compared with central and northern Finland are an indisputable consequence of the heavier S deposition load in the south. However, anthropogenic sulfur deposition has a clear correlation with the sulfates in streamwaters only in northeastern Lapland impacted by the large industrial emissions in the Kola Peninsula. The secondary sulfide and sulfate minerals of marine Littorina sediments are dominating sources in the broad coastal belts, as are the primary sulfide minerals locally in the Pori-Vammala area, at the eastern end of the main sulfide ore belt between Lake Ladoga and the Gulf of Bothnia, in the Outokumpu area, and in the Peräpohja and central Lapland schist belts. Consequently, in addition to the anthropogenic deposition, there are natural sources of sulfur which cause acidity of streamwaters.

  6. A descriptive model for sulfur capture in bubbling atmospheric pressure fluidized bed combustors

    SciTech Connect

    Walsh, P.M.

    1995-12-31

    A model of sorbent behavior is proposed for interpretation of measurements of sulfur capture in large-scale bubbling atmospheric pressure fluidized bad combustors (AFBC). The objective is to account for effects of the stone feed size distribution, attrition, recycle ratio, sulfation capacity, and sulfation rate on sulfur capture in practical systems. The parameters used in the simulation are limited to those whose values can be estimated from measurements in full-scale plants. Fines introduced with the limestone feed or formed on calcination, fines generated by attrition of bed particles, sulfur capture in the freeboard, and fines recycle were included in the description of the system. The sorbent was characterized by its sulfation capacity, fines content, attrition coefficient, and a first-order rate coefficient for reaction with SO{sub 2}. The model was compared with measurements by the Tennessee Valley Authority (TVA) and Electric Power Research Institute (EPRI) in the TVA 20 MW AFBC (TVA and EPRI, 1984), Measurements of sulfur capture over the range of recycle ratios from 0 to 4 kg recycle/kg coal, and calcium-to-sulfur ratios from 1.5 to 5 kmol Ca/kmol S, were reproduced with an average error of 5% sulfur capture. The principal source of error is thought to be neglect of fines formation during calcination of the stone. With further refinement the approach may be useful for characterization of sorbents in pilot and industrial-scale systems, and for evaluation of the effects of changes in operating conditions on sorbent performance in existing units.

  7. Environmental behavior and analysis of agricultural sulfur.

    PubMed

    Griffith, Corey M; Woodrow, James E; Seiber, James N

    2015-11-01

    Sulfur has been widely used for centuries as a staple for pest and disease management in agriculture. Presently, it is the largest-volume pesticide in use worldwide. This review describes the sources and recovery methods for sulfur, its allotropic forms and properties and its agricultural uses, including development and potential advantages of nanosulfur as a fungicide. Chemical and microbial reactivity, interactions in soil and water and analytical methods for determination in environmental samples and foodstuffs, including inexpensive analytical methods for sulfur residues in wine, beer and other food/beverage substrates, will be reviewed. The toxicology of sulfur towards humans and agriculturally important fungi is included, with some restrictions on use to promote safety. The review concludes with areas for which more research is warranted. © 2015 Society of Chemical Industry.

  8. Isotopic evidence in tree rings for historical changes in atmospheric sulfur sources.

    PubMed

    Kawamura, Hidehisa; Matsuoka, Nobuaki; Momoshima, Noriyuki; Koike, Masami; Takashima, Yoshimasa

    2006-09-15

    Little is understood about the usefulness of sulfur isotopic ratios (sigma 34S) in tree rings because the sulfur content in rings is generally insufficient for analysis using conventional methods. We present sigma 34S values of the water-soluble and the organically bound sulfur fractions in rings of coniferous trees grown in Japan, analyzed using a large-volume oxygen bomb. Comparing the sigma 34S values of the organically bound fraction in tree rings with past atmospheric sulfur concentrations and with those of their sources, we find clear evidence that the sigma 34S values of the organically bound fraction in the rings are dependent upon the values of the atmospheric sulfur sources. The evidence suggests that the sigma 34S values in tree rings are a useful chronological proxy for evaluating possible causes of past atmospheric sulfur pollution.

  9. Atmospheric Sulfur Hexafluoride: Sources, Sinks and Greenhouse Warming

    NASA Technical Reports Server (NTRS)

    Sze, Nien Dak; Wang, Wei-Chyung; Shia, George; Goldman, Aaron; Murcray, Frank J.; Murcray, David G.; Rinsland, Curtis P.

    1993-01-01

    Model calculations using estimated reaction rates of sulfur hexafluoride (SF6) with OH and 0('D) indicate that the atmospheric lifetime due to these processes may be very long (25,000 years). An upper limit for the UV cross section would suggest a photolysis lifetime much longer than 1000 years. The possibility of other removal mechanisms are discussed. The estimated lifetimes are consistent with other estimated values based on recent laboratory measurements. There appears to be no known natural source of SF6. An estimate of the current production rate of SF6 is about 5 kt/yr. Based on historical emission rates, we calculated a present-day atmospheric concentrations for SF6 of about 2.5 parts per trillion by volume (pptv) and compared the results with available atmospheric measurements. It is difficult to estimate the atmospheric lifetime of SF6 based on mass balance of the emission rate and observed abundance. There are large uncertainties concerning what portion of the SF6 is released to the atmosphere. Even if the emission rate were precisely known, it would be difficult to distinguish among lifetimes longer than 100 years since the current abundance of SF6 is due to emission in the past three decades. More information on the measured trends over the past decade and observed vertical and latitudinal distributions of SF6 in the lower stratosphere will help to narrow the uncertainty in the lifetime. Based on laboratory-measured IR absorption cross section for SF6, we showed that SF6 is about 3 times more effective as a greenhouse gas compared to CFC 11 on a per molecule basis. However, its effect on atmospheric warming will be minimal because of its very small concentration. We estimated the future concentration of SF6 at 2010 to be 8 and 10 pptv based on two projected emission scenarios. The corresponding equilibrium warming of 0.0035 C and 0.0043 C is to be compared with the estimated warming due to CO2 increase of about 0.8 C in the same period.

  10. Atmospheric DMS and Biogenic Sulfur aerosol measurements in the Arctic

    NASA Astrophysics Data System (ADS)

    Ghahremaninezhadgharelar, R.; Norman, A. L.; Wentworth, G.; Burkart, J.; Leaitch, W. R.; Abbatt, J.; Sharma, S.; Desiree, T. S.

    2014-12-01

    Dimethyl Sulfide (DMS) and its oxidation products were measured on the board of the Canadian Coast Guard Ship (CCGS) Amundsen and above melt ponds in the Arctic during July 2014 in the context of the NETCARE study which seeks to understand the effect of DMS and its oxidation products with respect to aerosol nucleation, as well as its effect on cloud and precipitation properties. The objective of this study is to quantify the role of DMS in aerosol growth and activation in the Arctic atmosphere. Atmospheric DMS samples were collected from different altitudes, from 200 to 9500 feet, aboard the POLAR6 aircraft expedition to determine variations in the DMS concentration and a comparison was made to shipboard DMS measurements and its effects on aerosol size fractions. The chemical and isotopic composition of sulfate aerosol size fractions was studied. Sulfur isotope ratios (34S/32S) offer a way to determine the oceanic DMS contribution to aerosol growth. The results are expected to address the contribution of anthropogenic as well as biogenic sources of aerosols to the growth of the different aerosol size fractions. In addition, aerosol sulfate concentrations were measured at the same time within precipitation and fogs to compare with the characteristics of aerosols in each size fraction with the characteristics of the sulfate in each medium. This measurement is expected to explain the contribution of DMS oxidation in aerosol activation in the Arctic summer. Preliminary results from the measurement campaign for DMS and its oxidation products in air, fog and precipitation will be presented.

  11. Decreased atmospheric sulfur deposition across the southeastern U.S.: When will watersheds release stored sulfate?

    Treesearch

    Karen C. Rice; Todd M. Scanlon; Jason A. Lynch; Bernard J. Cosby

    2014-01-01

    Emissions of sulfur dioxide (SO2) to the atmosphere lead to atmospheric deposition of sulfate (SO42-), which is the dominant strong acid anion causing acidification of surface waters and soils in the eastern United States. Since passage of the Clean Air Act and its Amendments, atmospheric deposition...

  12. Sulfur isotopic signatures in rainwater and moss Haplocladium microphyllum indicating atmospheric sulfur sources in Nanchang City (SE China).

    PubMed

    Xiao, Hua-Yun; Zhu, Ren-Guo; Lin, Bi-Na; Liu, Cong-Qiang

    2011-05-01

    Sulfur source identification previously reported has been based on sulfur isotopic ratios in either rainwater or mosses. The δ(34)S values of rainwater sulfate and the epilithic moss Haplocladium microphyllum in Nanchang region (China) were determined for comparisons and used to delineate atmospheric sulfur sources. At the urban and rural sites, similar mean δ(34)S values were observed between rainwater sulfate (+1.6‰ and -0.2‰, respectively) and epilithic mosses (+1.7‰ and +0.6‰, respectively), suggesting that mosses acquire δ(34)S values similar to those found for rainwater sulfate. This has further demonstrated that moss δ(34)S signatures hold valuable source-specific information as rainwater δ(34)S values do. The δ(34)S values of both rainwater sulfate and epilithic mosses indicated that atmospheric sulfur in Nanchang region was mainly associated with coal combustion. The lower δ(34)S values at the rural site can be explained by higher contribution of local coals (lower δ(34)S values relative to those of north Chinese coals) and biogenic sulfur.

  13. Kinetics of Thermochemical Reactions Important in the Venus Atmospheric Sulfur Cycle

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr.

    1997-01-01

    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.

  14. Atmospheric sulfur loading by the ongoing Nornahraun eruption, North Iceland

    NASA Astrophysics Data System (ADS)

    Thordarson, Thorvaldur; Hartley, Margaret

    2015-04-01

    The ongoing Nornahraun fissure eruption has maintained a 1-4 km-high, gas-charged and sulfur-rich eruption plume since the onset of eruption on 31 August 2014 and had discharged ~1 km3 of lava at the end of 2014. During this time (i.e. September through December 2014), the SO2 emissions have produced significant volcanic pollution across Iceland with several short-lived events where the SO2 concentrations have exceeded toxic levels [1]. Although measurements of SO2 concentrations and fluxes is relatively straightforward at specific sites or localities within Iceland, it has been challenging to obtain good ground- or satellite-based time series measurements of the SO2 flux released by the magma upon venting. These difficulties arise because: (i) the eruption site is remote and nested in the centre of the Icelandic highland, thus these measurements are hampered by access and by weather conditions, (ii) the plume is confined to the lower troposphere where the conversion rate of SO2 to H2SO4 aerosols is very rapid, or hours (?) to days [2] and (iii) the plume is commonly obscured by clouds due of its low rise heights. The empirical sulphur emission method of Thordarson et al (2003) is an alternative way to obtain estimates on the total as well as temporal atmospheric SO2-loading by the Nornahraun eruption. We use the TiO2/FeO value of 0.156, obtained via microprobe analyses of groundmass glass in tephra grains, to calculate initial (1420 ppm) and degassed (435 ppm) S values for the Nornahraun magma. These values compare well with measured groundmass values (425 ppm = degassed S content) and melt inclusion values (~1400 ppm = initial S content of the magma). The difference in the above listed values represents the amount of S released into the atmosphere at the vents and indicates a 5.3 kg SO2-loading by each cubic meter of erupted magma. This implies a total atmospheric SO2-mass-loading of 5 million tons (= 5 terragrams) by the Nornahraun event during the first 4

  15. Consistency Between Measurements and Theory for Sulfur Gases and Oxidants During the Pacific Atmospheric Sulfur Experiment

    NASA Astrophysics Data System (ADS)

    Heikes, B. G.; Higbie, A.; O'Sullivan, D. W.; Bandy, A. R.; Mauldin, L.; Cantrell, C.; Anderson, R. S.; Campos, T.; Huebert, B.; Bloomquist, B.; Wang, Y.; Heizer, C. G.; Pollack, I. B.; Weinheimer, A. J.

    2008-12-01

    Airborne gas phase measurements of sulfur dioxide, dimethylsulfide, dimethylsulfoxide, methane sulfonic acid, sulfuric acid, hydroxyl, perhydroxyl, hydrogen peroxide, methylhydroperoxide, ozone, and carbon monoxide together with aerosol microphysical properties and bulk and size-dependent aerosol composition are examined for consistency with photochemical theory. The observations come from 14 research flights using the NCAR C-130 flown mostly southeast of Kiritimati in relatively cloud-free marine boundary layer air. This region was chosen because of its extremely low nitrogen oxide mixing ratios and minimal horizontal gradients in composition. A size-dependent gas-particle mass-transfer model is used to calculate the exchange rates of dimethylsulfoxide, methanesulfonic acid and sulfuric acid between the gas and aerosol. Gas kinetic reactions, aqueous reactions, and heterogeneous processes are used in the evaluation. Mass accommodation coefficients, Henry's Law solubilities, and the effective yields of methanesulfonic acid, sulfur dioxide, sulfuric acid and dimethylsulfoxide from dimethylsulfide are estimated and consistent with the literature. Gas phase hydroxyl chemistry alone is sufficient to explain observed methanesulfonic acid and sulfuric acid vapor concentrations.

  16. Identifying the change in atmospheric sulfur sources in China using isotopic ratios in mosses

    NASA Astrophysics Data System (ADS)

    Xiao, Hua-Yun; Tang, Cong-Guo; Xiao, Hong-Wei; Liu, Xue-Yan; Liu, Cong-Qiang

    2009-08-01

    A considerable number of studies on rainwater sulfur isotopic ratios (δ34Srain) have been conducted to trace sulfur sources at a large number of sites in the past. If longitudinal studies on the isotope composition of precipitation sulfate were conducted, it is possible to relate that to changes in sulfur emissions. But direct measurement needs considerable labor and time. So, in this study, sulfur isotopic ratios in rainwater and mosses were analyzed at Guiyang and Nanchang to evaluate the possibility of using mosses as a substitute for rainwater. We found that present moss sulfur isotopic ratios were comparable to those of present rainwater. Additionally, we investigated the changes of atmospheric sulfur sources and sulfur concentrations using an isotopic graphic analysis at five industrial cities, two forested areas, and two remote areas in China. Mosses in industrial cities show a wide range of δ34S values, with the highest occurring at Chongqing (+3.9‰) and the lowest at Guiyang (-3.1‰). But as compared to those in forested and remote areas, δ34S values of mosses in all the five industrial cities are lower. On the basis of isotopic comparisons between past rainwater (reported in the literature) and present mosses, in the plot of δ34Smoss versus δ34Srain, six zones indicating different atmospheric sulfur change are separated by the 1:1 line and δ34S values of potential sulfur sources. Our results indicate that atmospheric sulfur pollution in most of the industrial cities decreased, while at the two forested areas, no significant changes were observed, and a new anxiousness coming from new energy sources (e.g., oil) appeared in some cities. Studies on the change of ambient SO2 concentrations support these results.

  17. Atmospheric dry deposition of sulfur and nitrogen in the Athabasca Oil Sands Region, Alberta, Canada

    Treesearch

    Yu-Mei Hsu; Andrzej Bytnerowicz; Mark E. Fenn; Kevin E. Percy

    2016-01-01

    Due to the potential ecological effects on terrestrial and aquatic ecosystems from atmospheric deposition in the Athabasca Oil Sands Region (AOSR), Alberta, Canada, this study was implemented to estimate atmospheric nitrogen (N) and sulfur (S) inputs. Passive samplers were used to measure ambient concentrations of ammonia (NH3), nitrogen dioxide...

  18. Sulfur

    USGS Publications Warehouse

    Apodaca, L.E.

    2012-01-01

    In 2011, elemental sulfur and the byproduct sulfuric acid were produced at 109 operations in 29 states and the U.S. Virgin Islands. Total shipments were valued at about $1.6 billion. Elemental sulfur production was 8.2 Mt (9 million st); Louisiana and Texas accounted for about 53 percent of domestic production.

  19. Atmospheric Chemistry in Giant Planets, Brown Dwarfs, and Low-Mass Dwarf Stars. II. Sulfur and Phosphorus

    NASA Astrophysics Data System (ADS)

    Visscher, Channon; Lodders, Katharina; Fegley, Bruce, Jr.

    2006-09-01

    Thermochemical equilibrium and kinetic calculations are used to model sulfur and phosphorus chemistry in giant planets, brown dwarfs, and extrasolar giant planets (EGPs). The chemical behavior of individual S- and P-bearing gases and condensates is determined as a function of pressure, temperature, and metallicity. The results are independent of particular model atmospheres, and in principle, the equilibrium composition along the pressure-temperature profile of any object can be determined. Hydrogen sulfide (H2S) is the dominant S-bearing gas throughout substellar atmospheres and approximately represents the atmospheric sulfur inventory. Silicon sulfide (SiS) is a potential tracer of weather in substellar atmospheres. Disequilibrium abundances of phosphine (PH3) approximately representative of the total atmospheric phosphorus inventory are expected to be mixed upward into the observable atmospheres of giant planets and T dwarfs. In hotter objects, several P-bearing gases (e.g., P2, PH3, PH 2, PH, and HCP) become increasingly important at high temperatures.

  20. Atmospheric Sulfur Cycle Effects of Carbonyl Sulfide (OCS)

    NASA Technical Reports Server (NTRS)

    McBee, Joshua

    1996-01-01

    Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

  1. Atmospheric Sulfur Cycle Effects of Carbonyl Sulfide (OCS)

    NASA Technical Reports Server (NTRS)

    McBee, Joshua

    1996-01-01

    Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

  2. Photon and Water Mediated Sulfur Oxide and Acid Chemistry in the Atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Kroll, Jay A.; Vaida, Veronica

    2014-06-01

    Sulfur compounds have been observed in the atmospheres of a number of planetary bodies in our solar system including Venus, Earth, Mars, Io, Europa, and Callisto. The global cloud cover on Venus located at an altitude between 50 and 80 kilometers is composed primarily of sulfuric acid (H_2SO_4) and water. Planetary photochemical models have attempted to explain observations of sulfuric acid and sulfur oxides with significant discrepancies remaining between models and observation. In particular, high SO_2 mixing ratios are observed above 90 km which exceed model predictions by orders of magnitude. Work recently done in the Vaida lab has shown red light can drive photochemistry through overtone pumping for acids like H_2SO_4 and has been successful in explaining much of the sulfur chemistry in Earth's atmosphere. Water can have a number of interesting effects such as catalysis, suppression, and anti-catalysis of thermal and photochemical processes. We investigate the role of water complexes in the hydration of sulfur oxides and dehydration of sulfur acids and present spectroscopic studies to document such effects. We investigate these reactions using FTIR and UV/Vis spectroscopy and will report on our findings.

  3. Sulfurization behavior of thorium dioxide with carbon disulfide

    NASA Astrophysics Data System (ADS)

    Sato, N.; Kirishima, A.

    2011-07-01

    A novel reprocessing process based on sulfide chemistry has been proposed for the recovery of nuclear materials from spent fuel. To apply the sulfide process in the thorium fuel cycle, the sulfurization behavior of thorium dioxide (ThO 2) with CS 2 was examined as a basic study. When thorium dioxide powder reacted with a mixture gas of Ar and CS 2 at different temperatures in a quartz reaction tube, the phases after the reaction were identified by the X-ray diffraction method. At temperatures lower than 673 K, ThO 2 was found to be stable because the lattice parameter of the ThO 2 phases does not change with increasing sulfurization temperatures. However, the weight gradually increased, suggesting that a small amount of sulfur was trapped in the lattice from the sulfurization. The formation of the intermediate phase ThOS was observed at 973 K. At 1073 K, both the ThOS and ThS 2 phases were observed. Finally, a single phase of ThS 2 was obtained at temperatures higher than 1173 K. The obtained results were compared with the thermodynamic consideration by using the potential diagram of the Th-S 2-O 2 system and the experimental results were in good agreement with the thermodynamic considerations.

  4. Low level atmospheric sulfur dioxide pollution and childhood asthma

    SciTech Connect

    Tseng, R.Y.; Li, C.K. )

    1990-11-01

    Quarterly analysis (1983-1987) of childhood asthma in Hong Kong from 13,620 hospitalization episodes in relation to levels of pollutants (SO{sub 2}, NO{sub 2}, NO, O{sub 3}, TSP, and RSP) revealed a seasonal pattern of attack rates that correlates inversely with exposure to sulfur dioxide (r = -.52, P less than .05). The same cannot be found with other pollutants. Many factors may contribute to the seasonal variation of asthma attacks. We speculate that prolonged exposure (in terms of months) to low level SO{sub 2} is one factor that might induce airway inflammation and bronchial hyperreactivity and predispose to episodes of asthma.

  5. Laboratory measurements and modeling of molecular photoabsorption in the ultraviolet for planetary atmospheres applications: diatomic sulfur and sulfur monoxide

    NASA Astrophysics Data System (ADS)

    Stark, Glenn

    2016-07-01

    Our research program comprises the measurement and modeling of ultraviolet molecular photoabsorption cross sections with the highest practical resolution. It supports efforts to interpret and model observations of planetary atmospheres. Measurement and modeling efforts on diatomic sulfur (S _{2}) and sulfur monoxide (SO) are in progress. S _{2}: Interpretations of atmospheric (Io, Jupiter, cometary comae) S _{2} absorption features are hindered by a complete lack of laboratory cross section data in the ultraviolet. We are working to quantify the photoabsorption spectrum of S _{2} from 240 to 300 nm based on laboratory measurements and theoretical calculations. We have constructed an experimental apparatus to produce a stable column of S _{2} vapor at a temperature of 800 K. High-resolution measurements of the absorption spectrum of the strong B - X system of S _{2} were completed using the NIST VUV-FTS at Gaithersburg, Maryland. These measurements are currently being incorporated into a coupled-channel model of the absorption spectrum of S _{2} to quantify the contributions from individual band features and to establish the mechanisms responsible for the strong predissociation signature of the B - X system. A successful coupled channels model can then be used to calculate the B - X absorption spectrum at any temperature. SO: There has been a long-standing need for high-resolution cross sections of sulfur monoxide radicals in the ultraviolet and vacuum ultraviolet regions, where the molecule strongly predissociates, for modeling the atmospheres of Io and Venus, and most recently for understanding sulfur isotope effects in the ancient (pre-O _{2}) atmosphere of Earth. We have produced a measurable column of SO in a continuous-flow DC discharge cell, using SO _{2} as a parent molecule. Photoabsorption measurements were recently recorded on the DESIRS beamline of the SOLEIL synchrotron, taking advantage of the high-resolution VUV-FTS on that beamline. A number of

  6. Effects of sulfur loading on the corrosion behaviors of metal lithium anode in lithium–sulfur batteries

    SciTech Connect

    Han, Yamiao; Duan, Xiaobo; Li, Yanbing; Huang, Liwu; Zhu, Ding; Chen, Yungui

    2015-08-15

    Highlights: • The effects of sulfur loading on the corrosion behaviors were investigated systematically. • The corrosion became severer with increasing sulfur loading or cycle times. • The corrosion films are porous and loose and cannot prevent further reaction between lithium and polysulfides. - Abstract: The corrosion behaviors in rechargeable lithium–sulfur batteries come from the reactions between polysulfides and metal lithium anode, and they are significantly influenced by the sulfur loading. While there are limited papers reported on the effects of sulfur loading on the corrosion behaviors. In this paper, the effects have been investigated systematically. The corrosion films consisted of insulating lithium ion conductors are loose and porous, so that the corrosive reactions cannot be hindered. The thickness of the corrosion layers, consequently, increased along with increasing sulfur loading or cycle times. For instance, the thickness of corrosion layers after 50 cycles was 98 μm in the cell with 5 mg sulfur while it reached up to 518 μm when the loading increased to 15 mg. The continuous deposition of corrosion products gave rise to low active materials utilization and poor cycling performance.

  7. Reevaluating the contribution of sulfuric acid and the origin of organic compounds in atmospheric nanoparticle growth

    NASA Astrophysics Data System (ADS)

    Vakkari, Ville; Tiitta, Petri; Jaars, Kerneels; Croteau, Philip; Beukes, Johan Paul; Josipovic, Miroslav; Kerminen, Veli-Matti; Kulmala, Markku; Venter, Andrew D.; Zyl, Pieter G.; Worsnop, Douglas R.; Laakso, Lauri

    2015-12-01

    Aerosol particles formed in the atmosphere are important to the Earth's climate system due to their ability to affect cloud properties. At present, little is known about the atmospheric chemistry responsible for the growth of newly formed aerosol particles to climate-relevant sizes. Here combining detailed aerosol measurements with a theoretical framework we found that depending on the gaseous precursors and size of the newly formed particles, the growth was dominated by either sulfuric acid accompanied by ammonium or organic compounds originating in either biogenic emissions or savannah fires. The contribution of sulfuric acid was larger during the early phases of the growth, but in clean conditions organic compounds dominated the growth from 1.5 nm up to climatically relevant sizes. Furthermore, our analysis indicates that in polluted environments the contribution of sulfuric acid to the growth may have been underestimated by up to a factor of 10.

  8. Strong Hydrogen Bonded Molecular Interactions between Atmospheric Diamines and Sulfuric Acid.

    PubMed

    Elm, Jonas; Jen, Coty N; Kurtén, Theo; Vehkamäki, Hanna

    2016-05-26

    We investigate the molecular interaction between methyl-substituted N,N,N',N'-ethylenediamines, propane-1,3-diamine, butane-1,4-diamine, and sulfuric acid using computational methods. Molecular structure of the diamines and their dimer clusters with sulfuric acid is studied using three density functional theory methods (PW91, M06-2X, and ωB97X-D) with the 6-31++G(d,p) basis set. A high level explicitly correlated CCSD(T)-F12a/VDZ-F12 method is used to obtain accurate binding energies. The reaction Gibbs free energies are evaluated and compared with values for reactions involving ammonia and atmospherically relevant monoamines (methylamine, dimethylamine, and trimethylamine). We find that the complex formation between sulfuric acid and the studied diamines provides similar or more favorable reaction free energies than dimethylamine. Diamines that contain one or more secondary amino groups are found to stabilize sulfuric acid complexes more efficiently. Elongating the carbon backbone from ethylenediamine to propane-1,3-diamine or butane-1,4-diamine further stabilizes the complex formation with sulfuric acid by up to 4.3 kcal/mol. Dimethyl-substituted butane-1,4-diamine yields a staggering formation free energy of -19.1 kcal/mol for the clustering with sulfuric acid, indicating that such diamines could potentially be a key species in the initial step in the formation of new particles. For studying larger clusters consisting of a diamine molecule with up to four sulfuric acid molecules, we benchmark and utilize a domain local pair natural orbital coupled cluster (DLPNO-CCSD(T)) method. We find that a single diamine is capable of efficiently stabilizing sulfuric acid clusters with up to four acid molecules, whereas monoamines such as dimethylamine are capable of stabilizing at most 2-3 sulfuric acid molecules.

  9. Sulfur Isotopes in Swaziland System Barites and the Evolution of the Earth's Atmosphere.

    PubMed

    Perry, E C; Monster, J; Reimer, T

    1971-03-12

    Sedimentary barites from the Swaziland System of South Africa (more than 3000 million years old) have sulfur-34 ratios that are enriched by only 2.5 per mil with respect to contemporary sulfides. To explain this small fractionation, it is proposed that oxygen pressure in the earth's atmosphere was very low and that local oxidation occurred in a photosynthetic layer of the ocean.

  10. Sulfur dioxide in the Venus atmosphere: I. Vertical distribution and variability

    NASA Astrophysics Data System (ADS)

    Vandaele, A. C.; Korablev, O.; Belyaev, D.; Chamberlain, S.; Evdokimova, D.; Encrenaz, Th.; Esposito, L.; Jessup, K. L.; Lefèvre, F.; Limaye, S.; Mahieux, A.; Marcq, E.; Mills, F. P.; Montmessin, F.; Parkinson, C. D.; Robert, S.; Roman, T.; Sandor, B.; Stolzenbach, A.; Wilson, C.; Wilquet, V.

    2017-10-01

    Recent observations of sulfur containing species (SO2, SO, OCS, and H2SO4) in Venus' mesosphere have generated controversy and great interest in the scientific community. These observations revealed unexpected spatial patterns and spatial/temporal variability that have not been satisfactorily explained by models. Sulfur oxide chemistry on Venus is closely linked to the global-scale cloud and haze layers, which are composed primarily of concentrated sulfuric acid. Sulfur oxide observations provide therefore important insight into the on-going chemical evolution of Venus' atmosphere, atmospheric dynamics, and possible volcanism. This paper is the first of a series of two investigating the SO2 and SO variability in the Venus atmosphere. This first part of the study will focus on the vertical distribution of SO2, considering mostly observations performed by instruments and techniques providing accurate vertical information. This comprises instruments in space (SPICAV/SOIR suite on board Venus Express) and Earth-based instruments (JCMT). The most noticeable feature of the vertical profile of the SO2 abundance in the Venus atmosphere is the presence of an inversion layer located at about 70-75 km, with VMRs increasing above. The observations presented in this compilation indicate that at least one other significant sulfur reservoir (in addition to SO2 and SO) must be present throughout the 70-100 km altitude region to explain the inversion in the SO2 vertical profile. No photochemical model has an explanation for this behaviour. GCM modelling indicates that dynamics may play an important role in generating an inflection point at 75 km altitude but does not provide a definitive explanation of the source of the inflection at all local times or latitudes The current study has been carried out within the frame of the International Space Science Institute (ISSI) International Team entitled 'SO2 variability in the Venus atmosphere'.

  11. Modeling the signature of sulfur mass-independent fractionation produced in the Archean atmosphere

    NASA Astrophysics Data System (ADS)

    Claire, Mark W.; Kasting, James F.; Domagal-Goldman, Shawn D.; Stüeken, Eva E.; Buick, Roger; Meadows, Victoria S.

    2014-09-01

    Minor sulfur isotope anomalies indicate the absence of O2 from the Archean atmosphere. A rich dataset showing large variations in magnitude and sign of Δ33S and Δ36S, preserved in both sulfates and sulfides, suggests that further constraints on Archean atmospheric chemistry are possible. We review previous quantitative constraints on atmospheric Δ33S production, and suggest that a new approach is needed. We added sulfur species containing 33S and 34S to a 1-D photochemical model and describe the numerical methodology needed to ensure accurate prediction of the magnitude and sign of Δ33S produced by and deposited from the Archean atmosphere. This methodology can test multiple MIF-S formation mechanisms subject to a variety of proposed atmospheric compositions, yielding Δ33S predictions that can be compared to the rock record. We systematically test SO2 isotopologue absorption effects in SO2 photolysis (Danielache et al., 2008), one of the primary proposed mechanisms for Δ33S formation. We find that differential absorption through the Danielache et al. (2008) cross sections is capable of altering predicted Δ33S as a function of multiple atmospheric variables, including trace O2 concentration, total sulfur flux, CO2 content, and the presence of hydrocarbons, but find a limited role for OCS and H2S. Under all realistic conditions, the Danielache et al. (2008) cross sections yield Δ33S predictions at odds with the geologic record, implying that additional pathways for sulfur MIF formation exist and/or the cross sections have significant errors. The methodology presented here will allow for quantitative constraints on the Archean atmosphere beyond the absence of O2, as soon as additional experimental measurements of MIF-S producing processes become available.

  12. Chemistry in the Venus clouds: Sulfuric acid reactions and freezing behavior of aqueous liquid droplets

    NASA Astrophysics Data System (ADS)

    Delitsky, M. L.; Baines, K. H.

    2015-11-01

    Venus has a thick cloud deck at 40-70 km altitude consisting of liquid droplets and solid particles surrounded by atmospheric gases. The liquid droplets are highly concentrated aqueous solutions of sulfuric acid ranging in concentration from 70-99 wt%. Weight percent drops off with altitude (Imamura and Hashimoto 2001). There will be uptake of atmospheric gases into the droplet solutions and the ratios of gas-phase to liquid-phase species will depend on the Henry’s Law constant for those solutions. Reactions of sulfuric acid with these gases will form products with differing solubilities. For example, uptake of HCl by H2SO4/H2O droplets yields chlorosulfonic acid, ClSO3H (Robinson et al 1998) in solution. This may eventually decompose to thionyl- or sulfuryl chlorides, which have UV absorbances. HF will also uptake, creating fluorosulfonic acid, FSO3H, which has a greater solubility than the chloro- acid. As uptake continues, there will be many dissolved species in the cloudwaters. Baines and Delitsky (2013) showed that uptake will have a maximum at ~62 km and this is very close to the reported altitude for the mystery UV absorber in the Venus atmosphere. In addition, at very strong concentrations in lower altitude clouds, sulfuric acid will form hydrates such as H2SO4.H2O and H2SO4.4H2O which will have very different freezing behavior than sulfuric acid, with much higher freezing temperatures (Carslaw et al, 1997). Using temperature data from Venus Express from Tellmann et al (2009), and changes in H2SO4 concentrations as a function of altitude (James et al 1997), we calculate that freezing out of sulfuric acid hydrates can be significant down to as low as 56 km altitude. As a result, balloons, aircraft or other probes in the Venus atmosphere may be limited to flying below certain altitudes. Any craft flying at altitudes above ~55 km may suffer icing on the wings, propellers, balloons and instruments which could cause possible detrimental effects (thermal

  13. Homogenous nucleation of sulfuric acid and water at close to atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Brus, D.; Neitola, K.; Hyvärinen, A.-P.; Petäjä, T.; Vanhanen, J.; Sipilä, M.; Paasonen, P.; Kulmala, M.; Lihavainen, H.

    2011-06-01

    In this study the homogeneous nucleation rates in the system of sulfuric acid and water were measured by using a flow tube technique. The goal was to directly compare particle formation rates obtained from atmospheric measurements with nucleation rates of freshly nucleated particles measured with particle size magnifier (PSM) which has detection efficiency of unity for particles having mobility diameter of 1.5 nm. The gas phase sulfuric acid concentration in this study was measured with the chemical ionization mass spectrometer (CIMS), commonly used in field measurements. The wall losses of sulfuric acid were estimated from measured concentration profiles along the flow tube. The initial concentrations of sulfuric acid estimated from loss measurements ranged from 108 to 3 × 109 molecules cm-3. The nucleation rates obtained in this study cover about three orders of magnitude from 10-1 to 102 cm-3 s-1 for commercial ultrafine condensation particle counter (UCPC) TSI model 3025A and from 101 to 104 cm-3 s-1 for PSM. The nucleation rates and the slopes (dlnJ/dln [H2SO4]) show satisfactory agreement when compared to empirical kinetic and activation models and the latest atmospheric nucleation data. To the best of our knowledge, this is the first experimental work providing temperature dependent nucleation rate measurements using a high efficiency particle counter with a cut-off-size of 1.5 nm together with direct measurements of gas phase sulfuric acid concentration.

  14. [Research on determination of total volatile organic sulfur compounds in the atmosphere].

    PubMed

    Wang, Yan-Jun; Zheng, Xiao-Ling; He, Ying; Zhang, Dong; Wang, Bao-Dong

    2011-12-01

    A detection technology was established comprising trap, desorption, oxidation and UV fluorescence determination process, and used for the test of total concentration of trace volatile sulfur compounds (VSCs) in the atmosphere. A cryogenic trap-thermal desorption device was developed, integrating the advantages of solid retention method and cryogenic condensation method, which was applied to capture and enrich trace volatile organic sulfur compounds. Under high temperature and combustion-supporting gas, the VSCs were completely oxidized into sulfur dioxide. By analyzing the content of sulfur dioxide through ultraviolet fluorescence method indirectly calculated to gain the total concentration of volatile organic sulfur compounds. The trapping temperature, desorption temperature and the oxidation temperature were 5 degrees C, 150 degrees C and 1 000 degrees C, and the precision and recovery of the method were 5.46% and 99.6%-109.2%, respectively. The content of trace amounts of atmospheric VSCs determined from February to April at Qingdao was 42-195 ng x m(-3).

  15. The atmospheric sulfur cycle over the Amazon Basin. 2. Wet season

    SciTech Connect

    Andreae, M.O.; Berresheim, H.; Lewis, B.L.; Li, S. ); Jacob, D.J. ); Talbot, R.W. ); Bingemer, H.

    1990-09-20

    The authors determined the fluxes and concentrations of atmospheric sulfur species at ground level and from aircraft over the Amazon Basin during the 1987 wet season, providing a comprehensive description of the sulfur cycle over a remote tropical region. The vertical profile of dimethylsulfide (DMS) during the wet season was found to be very similar to that measured during the dry season. The concentrations of hydrogen sulfide (H{sub 2}S) were almost an order of magnitude higher than those of DMS, which makes H{sub 2}S the most important biogenic source species in the atmospheric sulfur cycle over the Amazon Basin. Using the gradient-flux approach, estimated the flux of DMS at the top of the tree canopy. The canopy was a source of DMS during the day, and a weak sink during the night. Measurements of sulfur gas emissions from soils, using the chamber method, showed very small fluxes, consistent with the hypothesis that the forest canopy is the major source of sulfur gases. The observed soil and canopy emission fluxes are similar to those measured in temperate regions. The concentrations of SO{sub 2} and sulfate aerosol in the wet season atmosphere were similar to dry season values. The sulfate concentration in rainwater, on the other hand, was lower by about a factor of 5 during the wet season. Due to the higher precipitation rate, however, the wet deposition flux of sulfate was not significantly different between the seasons. The measured fluxes and concentrations of DMS, H{sub 2}S, and SO{sub 2} were consistent with a model describing transport and chemistry of these sulfur species in the boundary layer. The concentrations of aerosol and the sulfate deposition rate, on the other hand, could only be explained by import of significant amounts of marine and anthropogenic sulfate aerosol into the Amazon Basin.

  16. Sulfur isotopic zoning in apatite crystals: A new record of dynamic sulfur behavior in magmas

    NASA Astrophysics Data System (ADS)

    Economos, Rita; Boehnke, Patrick; Burgisser, Alain

    2017-10-01

    The mobility and geochemical behavior of sulfur in magmas is complex due to its multi-phase (solid, immiscible liquid, gaseous, dissolved ions) and multi-valent (from S2- to S6+) nature. Sulfur behavior is closely linked with the evolution of oxygen fugacity (fO2) in magmas; the record of fO2 evolution is often enigmatic to extract from rock records, particularly for intrusive systems. We apply a novel method of measuring S isotopic ratios in zoned apatite crystals that we interpret as a record of open-system magmatic processes. We interrogate the S concentration and isotopic variations preserved in multiple apatite crystals from single hand specimens from the Cadiz Valley Batholith, CA via electron microprobe and ion microprobe. Isotopic variations in single apatite crystals ranged from 0 to 3.8‰ δ34S and total variation within a single hand sample was 6.1‰ δ34S. High S concentration cores yielded high isotopic ratios while low S concentration rims yielded low isotopic ratios. We discuss a range of possible natural scenarios and favor an explanation of a combination of magma mixing and open-system, ascent-driven degassing under moderately reduced conditions: fO2 at or below NNO+1, although the synchronous crystallization of apatite and anhydrite is also a viable scenario. Our conclusions have implications for the coupled S and fO2 evolution of granitic plutons and suggest that in-situ apatite S isotopic measurements could be a powerful new tool for evaluating redox and S systematics in magmatic systems.

  17. Manganese-catalysed autoxidation of dissolved sulfur dioxide in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Berglund, Johan; Elding, Lars I.

    Autoxidation of SO 2(aq) in the presence of manganese(II) is one of the important pathways for sulfuric acid formation in atmospheric clouds and fogs. Recent experimental results indicating that the catalyzed reaction takes place via a complex free-radical mechanism are discussed. Previous literature is reviewed in the light of this mechanism. Under atmospheric conditions of low total concentrations of manganese(II) ( < 2 × 10 -5 M) and sulfur(IV) ( ≤ 10 -5 M) and 2.5 < pH < 5, the rate law for conversion of SO 2(aq) to SO 3(aq) is reduced to d[S(IV)]/d t = k[Mn(II)][S(IV)], where [S(IV)] denotes the total concentration. A value of the overall rate constant k of 1.4 × 10 3 M -1s -1 is recommended for use in atmospheric model calculations.

  18. Atmospheric sulfur hexafluoride - Sources, sinks and greenhouse warming

    NASA Technical Reports Server (NTRS)

    Ko, Malcolm K. W.; Sze, Nien D.; Wang, Wei-Chyung; Shia, George; Goldman, Aaron; Murcray, Frank J.; Murcray, David G.; Rinsland, Curtis P.

    1993-01-01

    An estimate is obtained of worldwide production of SF6, from which a global emission rate is derived and extrapolated for the next 20 years. The atmospheric lifetime of SF6 is then estimated based on a known mechanism (e.g., photolysis and atmospheric oxidation) and/or on the mass balance method. Finally, the radiative forcing of SF6 is calculated based on recent laboratory IR absorption data, and the expected warming over the time period 1950-2010 is computed for several emission scenarios. Calculations showed that SF6 is 3 times more effective as a greenhouse gas compared to CFC 11 on a per-molecule basis. However, based on projected emission scenarios, the expected warming from SF6 through 2010 is small (0.004 C), compared to the warming from CO2 and other trace gases (0.8 C).

  19. Chlorine, fluorine, and sulfur emissions from Mount Erebus, Antarctica and estimated contributions to the Antarctic atmosphere

    NASA Astrophysics Data System (ADS)

    Zreda-Gostynska, Grazyna; Kyle, Philip R.; Finnegan, David L.

    1993-09-01

    The discharge rates of halogens in aerosols and gases emitted from Mount Erebus between December 1986 and January 1991 were estimated by combining element-to-sulfur ratios on filter samples with SO2 output measured by COSPEC. The halogen and sulfur content of the gas vary in a quasi-cyclical pattern possibly because of a heterogeneous distribution of volatiles in the Erebus magmatic system. The emission rates of HF and HCl have increased twofold since 1986 reaching 6 and 13.3 Gg/yr, respectively, in 1991, making Erebus an important contributor of halogens to the Antarctic atmosphere.

  20. Attribution of atmospheric sulfur dioxide over the English Channel to dimethyl sulfide and changing ship emissions

    NASA Astrophysics Data System (ADS)

    Yang, Mingxi; Bell, Thomas G.; Hopkins, Frances E.; Smyth, Timothy J.

    2016-04-01

    Atmospheric sulfur dioxide (SO2) was measured continuously from the Penlee Point Atmospheric Observatory (PPAO) near Plymouth, United Kingdom, between May 2014 and November 2015. This coastal site is exposed to marine air across a wide wind sector. The predominant southwesterly winds carry relatively clean background Atlantic air. In contrast, air from the southeast is heavily influenced by exhaust plumes from ships in the English Channel as well as near Plymouth Sound. A new International Maritime Organization (IMO) regulation came into force in January 2015 to reduce the maximum allowed sulfur content in ships' fuel 10-fold in sulfur emission control areas such as the English Channel. Our observations suggest a 3-fold reduction in ship-emitted SO2 from 2014 to 2015. Apparent fuel sulfur content calculated from coincidental SO2 and carbon dioxide (CO2) peaks from local ship plumes show a high level of compliance to the IMO regulation (> 95 %) in both years (˜ 70 % of ships in 2014 were already emitting at levels below the 2015 cap). Dimethyl sulfide (DMS) is an important source of atmospheric SO2 even in this semi-polluted region. The relative contribution of DMS oxidation to the SO2 burden over the English Channel increased from about one-third in 2014 to about one-half in 2015 due to the reduction in ship sulfur emissions. Our diel analysis suggests that SO2 is removed from the marine atmospheric boundary layer in about half a day, with dry deposition to the ocean accounting for a quarter of the total loss.

  1. Role of chromium and vanadium in the atmospheric oxidation of sulfur(IV)

    NASA Astrophysics Data System (ADS)

    Brandt, Christian; Elding, Lars I.

    Oxidation of HSO 3- in aqueous solution has been studied in the presence of vanadium(V), chromium(III) and chromium(VI). Based on spectrophotometric kinetics data and product analysis it is concluded that the autoxidation rate of sulfur(IV) in slightly acidic solution is unaffected by the presence of vanadium(V) and chromium(III). Chromate(VI), on the other hand, oxidizes sulfur(IV) in a direct redox process in acidic solution. The overall rate of this reaction decreases with increasing pH and it becomes relatively slow in the atmospherically relevant pH range 4-6. Moreover, chromium(III) dominates strongly over chromium(VI) in the atmospheric aqueous phase. Hence, it is concluded that cations of vanadium and chromium have no significant influence on the atmospheric aqueous-phase oxidation of sulfur(IV) under most ambient atmospheric conditions. Only in very acidic droplets, direct redox between chromium(VI) and sulfite might be of some importance.

  2. High-Southern Latitudes Sulfur Cycle in an Atmospheric General Circulation Model

    NASA Astrophysics Data System (ADS)

    Cosme, E.; Genthon, C.; Martinerie, P.; Boucher, O.; Pham, M.

    2002-05-01

    This modeling study (Cosme et al., Sulfur cycle in the high southern latitudes in the LMD-ZT General Circulation Model, submitted to JGR) was motivated by the recent publication of annual time-scale records of dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) in Antarctica, completing the available series of sulfate and methanesulfonic acid (MSA). Sulfur chemistry has been incorporated in the Laboratoire de Météorologie Dynamique Atmospheric General Circulation Model (AGCM), LMD-ZT, with high resolution and improved physics in the high-southern latitudes. The model predicts the concentration of 6 major sulfur species through emissions, transport, wet and dry deposition and chemistry in both gaseous and aqueous phases. Model results are broadly realistic when compared with measurements in air and snow or ice, and to results of other modeling studies, at high- and mid- southern latitudes. Although not corrected in this work, defects are identified and discussed: Atmospheric MSA concentrations are underestimated and DMSO concentrations are overestimated in summer, reflecting the lack of a DMSO sink leading to MSA; the deposition scheme used in the model may not be adapted to polar regions; DMS concentrations are underestimated in winter, and the model does not adequately reproduces interannual variability. Oceanic DMS sources appear deciding for the description of the sulfur cycle in these regions. The model suggests that ground atmospheric DMS concentrations are higher in winter than in summer, in a large part of central Antarctica. In the high-southern latitudes, high loads of DMS and DMSO are found and the main chemical sink of sulfur dioxide (SO2) is aqueous oxidation by ozone (O3), whereas oxidation by hydrogen peroxide (H2O2) dominates at the global scale.

  3. The role of cluster energy nonaccommodation in atmospheric sulfuric acid nucleation

    SciTech Connect

    Kurten, T.; Kuang, C.; Gomez, P.; McMurry, P. H.; Vehkamaki, H.; Ortega, I.; Noppel, M.; Kulmala, M.

    2010-01-11

    We discuss the possible role of energy nonaccommodation (monomer-cluster collisions that do not result in stable product formation due to liberated excess energy) in atmospheric nucleation processes involving sulfuric acid. Qualitative estimates of the role of nonaccommodation are computed using quantum Rice-Ramsberger-Kassel theory together with quantum chemically calculated vibrational frequencies and anharmonic coupling constants for small sulfuric acid-containing clusters. We find that energy nonaccommodation effects may, at most, decrease the net formation rate of sulfuric acid dimers by up to a factor of 10 with respect to the hard-sphere collision rate. A decrease in energy nonaccommodation due to an increasing number of internal degrees of freedom may kinetically slightly favor the participation of amines rather than ammonia as stabilizing agents in sulfuric acid nucleation, though the kinetic enhancement factor is likely to be less than three. However, hydration of the clusters (which always occurs in ambient conditions) is likely to increase the energy accommodation factor, reducing the role that energy nonaccommodation plays in atmospheric nucleation.

  4. Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere

    PubMed Central

    Shaheen, Robina; Abaunza, Mariana M.; Jackson, Teresa L.; McCabe, Justin; Savarino, Joël; Thiemens, Mark H.

    2014-01-01

    Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984–2001) showed the highest S-isotopic anomalies (Δ33S = +1.66‰ and Δ36S = +2‰) in a nonvolcanic (1998–1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997–1998)-induced changes in troposphere–stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ36S = −0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere. PMID:25092338

  5. Homogenous nucleation of sulfuric acid and water at atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Brus, D.; Neitola, K.; Petäjä, T.; Vanhanen, J.; Hyvärinen, A.-P.; Sipilä, M.; Paasonen, P.; Lihavainen, H.; Kulmala, M.

    2010-11-01

    In this study the homogeneous nucleation rates of sulfuric acid and water were measured by using a flow tube technique. The goal was to directly compare particle formation rates obtained from atmospheric measurements with nucleation rates of freshly nucleated particles measured with particle size magnifier (PSM) which has detection efficiency of unity for particles having mobility diameter of 1.5 nm. The gas phase sulfuric acid concentration in this study was measured with the chemical ionization mass spectrometer (CIMS), commonly used in field measurements. The wall losses of sulfuric acid were estimated from measured concentration profiles along the flow tube. The initial concentrations of sulfuric acid estimated from loss measurements ranged from 108 to 3×109 molecules cm-3. The nucleation rates obtained in this study cover about three orders of magnitude from 10-1 to 102 cm3 s-1 for commercial ultrafine condensation particle counter (UCPC) TSI model 3025A and from 101 to 104 cm3 s-1 for PSM. The nucleation rates and the slopes (dlnJ/dln[H2SO4]) show satisfactory agreement when compared to empirical kinetic and activation models and the latest atmospheric nucleation data.

  6. Apparatus for measurements of transport properties of thin films under sulfur atmosphere at moderate temperatures

    NASA Astrophysics Data System (ADS)

    Clamagirand, J. M.; Ares, J. R.; Diaz-Chao, P.; Pascual, A.; Ferrer, I. J.; Sánchez, C.

    2015-04-01

    An experimental system able to simultaneously measure the electrical resistance and the thermopower of metallic and semiconducting thin films (with thicknesses from ~nm to ~µm) under sulfur atmosphere from room temperature up to 400 °C and total pressures >0.5-1 mbar is designed and implemented. Calibration tests of the system were performed with palladium foils and films as well as p-type and n-type sulfide semiconducting films: iron disulfide and palladium monosulfide. Uncertainties of measured thermopower and resistance values are less than 10% and 5%, respectively. To check the capability of the system under sulfur atmosphere, in situ measurements of transport properties during sulfuration of palladium films were carried out. During the process, sulfur partial pressure and film temperature are accurately controlled. Apparatus may be used to determine the evolution of transport properties of different metal sulfides during their formation/decomposition processes, opening new pathways to investigate the thermoelectric properties of more complex thin film sulfides.

  7. Sulfur-containing particles emitted by concealed sulfide ore deposits: an unknown source of sulfur-containing particles in the atmosphere

    NASA Astrophysics Data System (ADS)

    Cao, J. J.; Li, Y. K.; Jiang, T.; Hu, G.

    2015-06-01

    Sources of sulfur dioxide, sulfates, and organic sulfur compounds, such as fossil fuels, volcanic eruptions, and animal feeding operations, have attracted considerable attention. In this study, we collected particles carried by geogas flows ascending through soil, geogas flows above the soil that had passed through the soil, and geogas flows ascending through deep faults of concealed sulfide ore deposits, and analysed them using transmission electron microscopy. Numerous crystalline and amorphous sulfur-containing particles or particle aggregations were found in the ascending geogas flows. In addition to S, the particles contained O, Ca, K, Mg, Fe, Na, Pb, Hg, Cu, Zn, As, Ti, Sr, Ba, Si, etc. Such particles are usually a few to several hundred nanometres in diameter with either regular or irregular morphology. The sulfur-containing particles originated from deep-seated weathering or faulting products of concealed sulfide ore deposits. The particles suspended in the ascending geogas flow migrated through faults from deep-seated sources to the atmosphere. This is a previously unknown source of the atmospheric particles. This paper reports, for the first time, the emission of sulfur-containing particles into the atmosphere from concealed sulfide ore deposits. The climatic and ecological influences of these sulfur-containing particles and particle aggregations should be assessed.

  8. Sulfur-containing particles emitted by concealed sulfide ore deposits: an unknown source of sulfur-containing particles in the atmosphere

    NASA Astrophysics Data System (ADS)

    Cao, J.; Li, Y.; Jiang, T.; Hu, G.

    2014-11-01

    Sources of sulfur dioxide, sulfates, and organic sulfur compounds, such as fossil fuels, volcanic eruptions, and animal feeding operations, have attracted considerable attention. In this study, we collected particles carried by geogas flows ascending through soil, geogas flows above the soil that had passed through the soil, and geogas flows ascending through deep faults of concealed sulfide ore deposits and analyzed them using transmission electron microscopy. Numerous crystalline and amorphous sulfur-containing particles or particle aggregations were found in the ascending geogas flows. In addition to S, the particles contained O, Ca, K, Mg, Fe, Na, Pb, Hg, Cu, Zn, As, Ti, Sr, Ba, Si, etc. Such particles are usually a few to several hundred nanometers in diameter with either regular or irregular morphology. The sulfur-containing particles originated from deep-seated weathering or faulting products of concealed sulfide ore deposits. The particles suspended in the ascending geogas flow migrated through faults from deep-seated sources to the atmosphere. This is a previously unknown source of the atmospheric particles. This paper reports, for the first time, the emission of sulfur-containing particles into the atmosphere from concealed sulfide ore deposits. The climatic and ecological influences of these sulfur-containing particles and particle aggregations should to be assessed.

  9. Erosion and landscape development decouple strontium and sulfur in the transition to dominance by atmospheric inputs

    USGS Publications Warehouse

    Bern, C.R.; Porder, S.; Townsend, A.R.

    2007-01-01

    Weathering and leaching can progressively deplete the pools of soluble, rock-derived elements in soils and ecosystems over millennial time-scales, such that productivity increasingly relies on inputs from atmospheric deposition. This transition has been explored using strontium isotopes, which have been widely assumed to be a proxy for the provenance of other rock-derived elements. We compared rock versus atmospheric proportions of strontium to those for sulfur, a plant macronutrient, at several tropical forest sites in Hawaii and Costa Rica. Isotopic analyses reveal that sulfur is often decoupled from strontium in the transition to atmospheric dependence. Decoupling is likely the result of differences in chemical factors such as atmospheric input rates, mobility in the soil environment, and mineral weathering susceptibility. Strontium and sulfur decoupling appears to be accentuated by the physical process of erosion. Erosion rates are presumed to be high on the Osa Peninsula of Costa Rica, where the recent onset of rapid tectonic uplift has placed the landscape in a transient state. Decoupling is strong there, as erosion has rejuvenated the supply of rock-derived strontium but not sulfur. The landscape response to changes in tectonic uplift on the Osa Peninsula has produced decoupling at the landscape scale. Decoupling is more variable along a Hawaiian catena, presumably due to smaller scale variations in erosion rates and their influence on rejuvenation of rock-strontium inputs. These results illustrate how chemical and physical processes can interact to produce contrasting origins for different nutrient elements in soils and the ecosystems they support. ?? 2007 Elsevier B.V. All rights reserved.

  10. Sulfur Hazes in Giant Exoplanet Atmospheres: Impacts on Reflected Light Spectra

    NASA Astrophysics Data System (ADS)

    Gao, Peter; Marley, Mark S.; Zahnle, Kevin; Robinson, Tyler D.; Lewis, Nikole K.

    2017-03-01

    Recent work has shown that sulfur hazes may arise in the atmospheres of some giant exoplanets, due to the photolysis of H2S. We investigate the impact such a haze would have on an exoplanet’s geometric albedo spectrum and how it may affect the direct imaging results of the Wide Field Infrared Survey Telescope (WFIRST), a planned NASA space telescope. For temperate (250 K < T eq < 700 K) Jupiter-mass planets, photochemical destruction of H2S results in the production of ∼1 ppmv of S8 between 100 and 0.1 mbar, which, if cool enough, will condense to form a haze. Nominal haze masses are found to drastically alter a planet’s geometric albedo spectrum: whereas a clear atmosphere is dark at wavelengths between 0.5 and 1 μm, due to molecular absorption, the addition of a sulfur haze boosts the albedo there to ∼0.7, due to scattering. Strong absorption by the haze shortward of 0.4 μm results in albedos <0.1, in contrast to the high albedos produced by Rayleigh scattering in a clear atmosphere. As a result, the color of the planet shifts from blue to orange. The existence of a sulfur haze masks the molecular signatures of methane and water, thereby complicating the characterization of atmospheric composition. Detection of such a haze by WFIRST is possible, though discriminating between a sulfur haze and any other highly reflective, high-altitude scatterer will require observations shortward of 0.4 μm, which is currently beyond WFIRST’s design.

  11. Formic Sulfuric Anhydride: a New Chemical Species with Possible Implications for Atmospheric Aerosol

    NASA Astrophysics Data System (ADS)

    Mackenzie, Becca; Dewberry, Chris; Leopold, Ken

    2015-06-01

    Aerosols are important players in the Earth's atmosphere, affecting climate, cloud formation, and human health. In this work, we report the discovery of a previously unknown molecule, formic sulfuric anhydride (FSA), that may influence the formation and composition of atmospheric aerosol particles. Five isotopologues of FSA have been observed by microwave spectroscopy and further characterized using DFT calculations. The system has dipole moment components along all three inertial axes, and indeed a, b, and c-type transitions have been observed. A π2 + π2 + σ2 cycloaddition reaction between SO3 and HCOOH is proposed as a possible mechanism for the formation of FSA and calculations indicate that the transformation is effectively barrierless. Facile formation of the anhydride followed by hydrolysis in small water-containing clusters or liquid droplets may provide a mechanism of incorporating volatile organics into atmospheric aerosol. We suggest that FSA and its derivatives be considered in future atmospheric and climate models.

  12. Atmospheric sulfur rearrangement 2.7 billion years ago: Evidence for oxygenic photosynthesis

    NASA Astrophysics Data System (ADS)

    Kurzweil, Florian; Claire, Mark; Thomazo, Christophe; Peters, Marc; Hannington, Mark; Strauss, Harald

    2013-03-01

    Mass-independently fractionated sulfur isotopes (MIF-S) provide strong evidence for an anoxic atmosphere during the Archean. Moreover, the temporal evolution of MIF-S shows increasing magnitudes between 2.7 and 2.5 Ga until the start of the Great Oxidation Event (G.O.E.) at around 2.4 Ga. The conclusion of a completely anoxic atmosphere up to the G.O.E. is in contrast to recent studies on redox-sensitive elements, which suggest slightly oxidizing conditions during continental weathering already several hundred million years prior to the G.O.E. In order to investigate this apparent inconsistency, we present multiple sulfur isotopes for 2.71 Ga pyritic black shales derived from the Kidd Creek area, Ontario, Canada. These samples display high positive Δ33S values up to 3.8‰ and the typical late Archean slope in Δ36S/Δ33S of -0.9. In contrast, the time period before (3.2-2.73 Ga) is characterized by greatly attenuated MIF-S magnitudes and a slope in Δ36S/Δ33S of -1.5. We attribute the increase in Δ33S magnitude as well as the contemporaneous change in the slope of Δ36S/Δ33S to changes in the relative reaction rate of different MIF-S source reactions and changes in atmospheric sulfur exit channels. Both of these are dependent on atmospheric CH4:CO2 and O2 mixing ratios. We propose a distinct change in atmospheric composition at 2.7 Ga resulting from increased fluxes of oxygen and methane as the best explanation for the observed Neoarchean MIF-S record. Our data and modeling results suggest that oxygenic photosynthesis was a major contributor to primary productivity 2.7 billion years ago.

  13. Sulfur species behavior in soil organic matter during decomposition

    USGS Publications Warehouse

    Schroth, A.W.; Bostick, B.C.; Graham, M.; Kaste, J.M.; Mitchell, M.J.; Friedland, A.J.

    2007-01-01

    Soil organic matter (SOM) is a primary re??servoir of terrestrial sulfur (S), but its role in the global S cycle remains poorly understood. We examine S speciation by X-ray absorption near-edge structure (XANES) spectroscopy to describe S species behavior during SOM decomposition. Sulfur species in SOM were best represented by organic sulfide, sulfoxide, sulfonate, and sulfate. The highest fraction of S in litter was organic sulfide, but as decomposition progressed, relative fractions of sulfonate and sulfate generally increased. Over 6-month laboratory incubations, organic sulfide was most reactive, suggesting that a fraction of this species was associated with a highly labile pool of SOM. During humification, relative concentrations of sulfoxide consistently decreased, demonstrating the importance of sulfoxide as a reactive S phase in soil. Sulfonate fractional abundance increased during humification irrespective of litter type, illustrating its relative stability in soils. The proportion of S species did not differ systematically by litter type, but organic sulfide became less abundant in conifer SOM during decomposition, while sulfate fractional abundance increased. Conversely, deciduous SOM exhibited lesser or nonexistent shifts in organic sulfide and sulfate fractions during decomposition, possibly suggesting that S reactivity in deciduous litter is coupled to rapid C mineralization and independent of S speciation. All trends were consistent in soils across study sites. We conclude that S reactivity is related to spqciation in SOM, particularly in conifer forests, and S species fractions in SOM change, during decomposition. Our data highlight the importance of intermediate valence species (sulfoxide and sulfonate) in the pedochemical cycling of organic bound S. Copyright 2007 by the American Geophysical Union.

  14. Minor Sulfur Isotope Constraints on the composition of Earth's Archean atmosphere

    NASA Astrophysics Data System (ADS)

    Claire, M.

    2016-12-01

    Minor sulfur isotope anomalies in the sedimentary record are direct recorders of ancient chemical reactions that occurred in the atmosphere, and therefore form the most direct proxy for Archean atmospheric composition. The mere presence of mass-independently fractionated sulfur isotopes (MIF-S) in the rock record has resolved nearly a century's worth of debate by constraining atmospheric oxygen to trace levels prior to 2.4 billion years ago, and indirectly indicates the presence of a dominant reducing gas, likely H2 or CH4. The MIF-S database has grown substantially in the past decade, and reveals complex time- and facies-dependent changes in MIF-S magnitudes. The structure within the sedimentary MIF-S record suggests that constraints beyond this simple "on-off" switch for atmospheric O2 are possible once we understand the mechanisms that generate and preserve the signal in the rock record. Recently, I proposed an initial quantitative framework for predictions of atmospheric MIF-S [1], but concluded that new measurements of MIF-S generation mechanisms were needed to provide robust constraints. Since then, identification of MIF-S arising from SO2 photoexcitation [2], and updated absorption cross-sections for SO2 and SO [3-4] provide critical new ground-truth on all 4 isotopes of sulfur. Furthermore, breakthroughs in coupled photochemical-climate modeling have enabled better predictions of UV transparency within hazy atmospheres [5] such as those that might have dominated in the Archean [6-8]. I will present 1-D photochemical modeling results based on these new fundamental constraints, in comparison with MIF-S data from the Archean, to interpret the steady-state composition of the Archean atmosphere and time-dependent perturbations to it. In particular, Δ36S/Δ33S resulting from perturbations to atmospheric species will be discussed as a key tool for constraining the composition of the reducing atmosphere. [1] Claire et al. (2014) GCA; [2] Whitehill et al., PNAS

  15. The molecular physics of photolytic fractionation of sulfur and oxygen isotopes in planetary atmospheres (Invited)

    NASA Astrophysics Data System (ADS)

    Johnson, M. S.; Schmidt, J. A.; Hattori, S.; Danielache, S.; Meusinger, C.; Schinke, R.; Ueno, Y.; Nanbu, S.; Kjaergaard, H. G.; Yoshida, N.

    2013-12-01

    Atmospheric photochemistry is able to produce large mass independent anomalies in atmospheric trace gases that can be found in geological and cryospheric records. This talk will present theoretical and experimental investigations of the molecular mechanisms producing photolytic fractionation of isotopes with special attention to sulfur and oxygen. The zero point vibrational energy (ZPE) shift and reflection principle theories are starting points for estimating isotopic fractionation, but these models ignore effects arising from isotope-dependent changes in couplings between surfaces, excited state dynamics, line densities and hot band populations. The isotope-dependent absorption spectra of the isotopologues of HCl, N2O, OCS, CO2 and SO2 have been examined in a series of papers and these results are compared with experiment and ZPE/reflection principle models. Isotopic fractionation in planetary atmospheres has many interesting applications. The UV absorption of CO2 is the basis of photochemistry in the CO2-rich atmospheres of the ancient Earth, and of Mars and Venus. For the first time we present accurate temperature and isotope dependent CO2 absorption cross sections with important implications for photolysis rates of SO2 and H2O, and the production of a mass independent anomaly in the Ox reservoir. Experimental and theoretical results for OCS have implications for the modern stratospheric sulfur budget. The absorption bands of SO2 are complex with rich structure producing isotopic fractionation in photolysis and photoexcitation.

  16. Stability of mechanical properties of vanadium catalysts for sulfuric acid manufacture in a humid atmosphere

    SciTech Connect

    Manaeva, L.N.; Malikman, V.I.; Dobkina, E.I.; Mukhlenov, I.P.

    1982-01-10

    Experience of the industrial use of catalysts in sulfuric acid manufacture shows that as the result of saturation with moisture the catalyst grains may lose strength and disintegrate during use. However, this question has not been examined experimentally and the mechanism of the effect has not been studied. Fresh catalyst may come into contact with atmospheric moisture during storage, and used catalyst as the result of uncontrolled leakages during stoppages and recharging of the catalytic converters. In the course of normal operation water vapor enters the catalytic converters together with sulfuric acid mist with the gas stream if the latter has not been adequately dried. The purpose of the present work was to study the mechanical stability, in a humid atmosphere, of industrial sulfuric acid catalysts: granulated SVD (5 mm in diameter) and SVS rings (8 x 8 x 2.5 mm). The catalysts were studied both in the fresh state and after use in a laboratory catalytic apparatus of the flow type.

  17. Sulfur behavior in the Sasol-Lurgi fixed-bed dry-bottom gasification process

    SciTech Connect

    M. Pat Skhonde; R. Henry Matjie; J. Reginald Bunt; A. Christien Strydom; H. Schobert

    2009-01-15

    This article reports on the findings of a study regarding the sulfur behavior across a Sasol-Lurgi gasifier. This was undertaken to understand the behavior of the various sulfur-bearing components in the coal, as they are exposed to the conditions in the gasifier. In this study, conventional characterization techniques were employed to monitor the behavior of sulfur-bearing mineral matter across the gasifier. It was observed from the study that the sulfur-bearing mineral (pyrite) in the coal structure undergoes various changes with pyrite being transformed to pyrrhotite and then to various oxides of iron with the subsequent loss of sulfur to form H{sub 2}S. A low proportion of the sulfur species including the organically associated sulfur was encapsulated by a melt that was formed by the interaction between kaolinite and fluxing minerals (pyrite, calcite, and dolomite/ankerite) present in the coal at elevated temperatures and pressure, thereby ending up in the ash. The remaining small proportions of sulfur-bearing mineral matter including pyrite and organically bound sulfur in the unburned carbon in the carbonaceous shales also report to the ash. 18 refs., 8 figs., 2 tabs.

  18. Recovery of elemental sulfur from zinc concentrate direct leaching residue using atmospheric distillation: a pilot-scale experimental study.

    PubMed

    Li, Hailong; Yao, Xiaolong; Wang, Mingxia; Wu, Shaokang; Ma, Weiwu; Wei, Wenwu; Li, Liqing

    2014-01-01

    Recovery of elemental sulfur from zinc concentrate direct leaching residue (DLR) using atmospheric distillation was systematically investigated on a pilot-scale system for the first time. Batch operating mode was suggested for recovery of elemental sulfur from water-rich DLR using atmospheric distillation. Elemental sulfur with purity higher than 99% was obtained under certain conditions in batch operating mode. With an appropriate feed amount of 1,200 kg, batch experiment conducted at 460 degrees C resulted in sulfur purity of 96.22% and a recovery rate higher than 85%. Only 0.59 and 1.24 kWh power was needed to handle 1.0 kg DLR and produce 1.0 kg elemental sulfur, respectively. The results suggest that recovery of elemental sulfur from zinc concentrate DLR using atmospheric distillation is technologically and economically feasible. Moreover, other metal elements such as zinc were enriched in the distillation concentrate, which could be used for metal refining. Technologies could effectively lower the moisture content of DLR, and lowering the distillation temperature would be of great value for recovery of elemental sulfur from DLR using a distillation method. Distillation is a promising solution for recovery of elemental sulfur from DLRs. This work revealed the possibility of separation of elemental sulfur from zinc concentrate DLR using atmospheric distillation. Such knowledge is of fundamental importance in developing field-scale separation and purification technologies and devices in which simultaneous sulfur recovery and precious metal enrichment are possible. Important tasks for follow-up research are also suggested.

  19. Sulfur Confined in Sub-Nanometer-Sized 2 D Graphene Interlayers and Its Electrochemical Behavior in Lithium-Sulfur Batteries.

    PubMed

    Du, Wen-Cheng; Zhang, Juan; Yin, Ya-Xia; Guo, Yu-Guo; Wan, Li-Jun

    2016-10-06

    Microspace-confined sulfur molecules as cathodes for lithium-sulfur (Li-S) batteries have shown great significance in both scientific and technical aspects. A study of different microspace-confined sulfur will not only promote the advancement of Li-S batteries but also arouse a wide interest in sulfur chemistry and related applications. Herein, we choose two-dimensional (2D) graphene interlayer as host and construct 2D space-confined sulfur model systems by simple intercalation chemistry of graphite oxide. Two routes, including solvothermal method and interlamellar reaction approach, are developed, and sulfur can be easily intercalated into sub-nanometer-sized graphene interlayers, forming a graphene confined sulfur structure. The 2D space-confined sulfur can work well in a carbonate-based electrolyte and show similar electrochemical behaviors of small sulfur molecules, indicating the special molecular form of sulfur in graphene layers. The 2D space-confined sulfur concept will be helpful for further understanding the electrochemical character of confined sulfur molecules and designing a high-performance sulfur cathode. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Mass-independent fractionation of sulfur isotopes in Archean sediments: strong evidence for an anoxic Archean atmosphere.

    PubMed

    Pavlov, A A; Kasting, J F

    2002-01-01

    Mass-independent fractionation (MIF) of sulfur isotopes has been reported in sediments of Archean and Early Proterozoic Age (> 2.3 Ga) but not in younger rocks. The only fractionation mechanism that is consistent with the data on all four sulfur isotopes involves atmospheric photochemical reactions such as SO2 photolysis. We have used a one-dimensional photochemical model to investigate how the isotopic fractionation produced during SO2 photolysis would have been transferred to other gaseous and particulate sulfur-bearing species in both low-O2 and high-O2 atmospheres. We show that in atmospheres with O2 concentrations < 10(-5) times the present atmospheric level (PAL), sulfur would have been removed from the atmosphere in a variety of different oxidation states, each of which would have had its own distinct isotopic signature. By contrast, in atmospheres with O2 concentrations > or = 10(-5) PAL, all sulfur-bearing species would have passed through the oceanic sulfate reservoir before being incorporated into sediments, so any signature of MIF would have been lost. We conclude that the atmospheric O2 concentration must have been < 10(-5) PAL prior to 2.3 Ga.

  1. Sulfuric acid vapor and other cloud-related gases in the Venus atmosphere - Abundances inferred from observed radio opacity

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.; Eshleman, V. R.

    1982-01-01

    It is suggested that the absorbing characteristics of sulfuric acid vapor appear to reconcile what had been thought to be an inconsistency among measurements and deductions regarding the constituents of the Venus atmosphere and radio occultation, radar reflection, and radio emission measurements of its opacity. Laboratory measurements of sulfuric acid, sulfur dioxide, water vapor, and carbon dioxide are used to model relative contributions to opacity as a function of height in a way that is consistent with observations of the constituents and absorbing properties of the atmosphere. It is concluded that sulfuric acid vapor is likely to be the principal microwave absorber in the 30-50 km altitude range of the middle atmosphere of Venus.

  2. Observation of dipropenyldisulfide and other organic sulfur compounds in the atmosphere of a beech forest with Allium ursinum ground cover

    NASA Astrophysics Data System (ADS)

    Puxbaum, H.; König, G.

    Dipropenyldisulfide, methylpropenyldisulfide, cis-propenylpropyldisulfide, diallylsulfide, dimethyldisulfide and 3-methylthiopropene were detected in the atmosphere of a beech forest with Allium ursinum (broad-leaved garlic) ground cover plants. Furthermore, it was shown that the Allium plants were the source of the organic sulfur compounds. The atmospheric concentrations of the organic sulfur observed on one day in May 1994 in a suburban forest in Vienna ranged from 0.3 to 7.8 ppb S with an average level of 2.9 ppb S. The atmospheric emission rate of organic sulfur species from A. ursinum determined with an enclosure box was the highest ever reported for terrestrial continental plants. The total organic sulfur flux on the average was at least 1 jug g-1h-1 (plant dry weight) or 60 gmgm-2 h-1 (per unit of ground area).

  3. Organic reactions increasing the absorption index of atmospheric sulfuric acid aerosols

    NASA Astrophysics Data System (ADS)

    Nozière, B.; Esteve, W.

    2005-02-01

    Unlike most environments present at Earth's surface atmospheric aerosols can be favorable to organic reactions. Among them, the acid-catalyzed aldol condensation of aldehydes and ketones produces light-absorbing compounds. In this work the increase of the absorption index of sulfuric acid solutions 50-96 wt. % resulting from the uptake of gas-phase acetaldehyde, acetone, and 2-butanone (methyl ethyl ketone), has been measured in the near UV and visible range. Our results indicate that the absorption index between 200 and 500 nm for stratospheric sulfuric aerosols exposed to 100 pptV of acetaldehyde (1 pptV = 10-12 v/v) would increase by four orders of magnitude over a two-year lifetime. Rough estimates based on previous radiative calculations suggest that this reaction could result in an increase of the radiative forcing of sulfate aerosols of the order of 0.01 W m-2, and that these processes are worth further investigation.

  4. Sulfur isotope dynamics in two central european watersheds affected by high atmospheric deposition of SO x

    NASA Astrophysics Data System (ADS)

    Novák, Martin; Kirchner, James W.; Groscheová, Hana; Havel, Miroslav; Černý, Jiří; Krejčí, Radovan; Buzek, František

    2000-02-01

    Sulfur fluxes and δ34S values were determined in two acidified small watersheds located near the Czech-German border, Central Europe. Sulfur of sulfate aerosol in the broader region (mean δ 34S of 7.5‰ CDT) was isotopically heavier than sulfur of airborne SO 2 (mean δ 34S of 4.7‰). The annual atmospheric S deposition to the Jezeřı´ watershed decreased markedly in 1993, 1994, and 1995 (40, 33, and 29 kg/ ha · yr), reflecting reductions in industrial S emissions. Sulfur export from Jezeří via surface discharge was twice atmospheric inputs, and increased from 52 to 58 to 85 kg/ha · yr over the same three-year period. The δ 34S value of Jezeřı´ streamflow was 4.5 ± 0.3‰, intermediate between the average atmospheric deposition (5.4 ± 0.2‰) and soil S (4.0 ± 0.5‰), suggesting that the excess sulfate in runoff comes from release of S from the soil. Bedrock is not a plausible source of the excess S, because its S concentration is very low (<0.003 wt.%) and because its δ 34S value is too high (5.8‰) to be consistent with the δ 34S of runoff. A sulfur isotope mixing model indicated that release of soil S accounted for 64 ± 33% of sulfate S in Jezeřı´ discharge. Approximately 30% of total sulfate S in the discharge were organically cycled. At Načetı´n, the same sequence of δ34S IN > δ34S OUT > δ34S SOIL was observed. The seasonality found in atmospheric input (higher δ 34S in summer, lower δ 34S in winter) was preserved in shallow (<10 cm) soil water, but not in deeper soil water. δ 34S values of deeper (>10 cm) soil water (4.8 ± 0.2‰) were intermediate between those of atmospheric input (5.9 ± 0.3‰) and Nac̆etín soils (2.4 ± 0.1‰), again suggesting that remobilization of soil S accounts for a significant fraction (roughly 40 ± 10%) of the S in soil water at Načetı´n. The inventories of soil S at both of these sites are legacies of more intense atmospheric pollution during previous decades, and are large enough (740

  5. A Sulfur-Based Survival Strategy for Putative Phototrophic Life in the Venusian Atmosphere

    NASA Astrophysics Data System (ADS)

    Schulze-Makuch, Dirk; Grinspoon, David H.; Abbas, Ousama; Irwin, Louis N.; Bullock, Mark A.

    2004-03-01

    Several observations indicate that the cloud deck of the venusian atmosphere may provide a plausible refuge for microbial life. Having originated in a hot proto-ocean or been brought in by meteorites from Earth (or Mars), early life on Venus could have adapted to a dry, acidic atmospheric niche as the warming planet lost its oceans. The greatest obstacle for the survival of any organism in this niche may be high doses of ultraviolet (UV) radiation. Here we make the argument that such an organism may utilize sulfur allotropes present in the venusian atmosphere, particularly S8, as a UV sunscreen, as an energy-converting pigment, or as a means for converting UV light to lower frequencies that can be used for photosynthesis. Thus, life could exist today in the clouds of Venus.

  6. Massive impact-induced release of carbon and sulfur gases in the early Earth's atmosphere

    NASA Astrophysics Data System (ADS)

    Marchi, S.; Black, B. A.; Elkins-Tanton, L. T.; Bottke, W. F.

    2016-09-01

    Recent revisions to our understanding of the collisional history of the Hadean and early-Archean Earth indicate that large collisions may have been an important geophysical process. In this work we show that the early bombardment flux of large impactors (>100 km) facilitated the atmospheric release of greenhouse gases (particularly CO2) from Earth's mantle. Depending on the timescale for the drawdown of atmospheric CO2, the Earth's surface could have been subject to prolonged clement surface conditions or multiple freeze-thaw cycles. The bombardment also delivered and redistributed to the surface large quantities of sulfur, one of the most important elements for life. The stochastic occurrence of large collisions could provide insights on why the Earth and Venus, considered Earth's twin planet, exhibit radically different atmospheres.

  7. A sulfur-based survival strategy for putative phototrophic life in the venusian atmosphere.

    PubMed

    Schulze-Makuch, Dirk; Grinspoon, David H; Abbas, Ousama; Irwin, Louis N; Bullock, Mark A

    2004-01-01

    Several observations indicate that the cloud deck of the venusian atmosphere may provide a plausible refuge for microbial life. Having originated in a hot proto-ocean or been brought in by meteorites from Earth (or Mars), early life on Venus could have adapted to a dry, acidic atmospheric niche as the warming planet lost its oceans. The greatest obstacle for the survival of any organism in this niche may be high doses of ultraviolet (UV) radiation. Here we make the argument that such an organism may utilize sulfur allotropes present in the venusian atmosphere, particularly S(8), as a UV sunscreen, as an energy-converting pigment, or as a means for converting UV light to lower frequencies that can be used for photosynthesis. Thus, life could exist today in the clouds of Venus.

  8. Unsteady absorption of sulfur dioxide by an atmospheric water droplet with internal circulation

    NASA Astrophysics Data System (ADS)

    Chen, Wei-Hsin

    Unsteady absorption characteristics of sulfur dioxide by an atmospheric water droplet in motion are predicted numerically and analyzed theoretically to recognize the physical mass transport processes inside an aerosol droplet, which is frequently encountered in the atmosphere. Considering the absorption of sulfur dioxide by a droplet in cloud or fog with various velocities, three different Reynolds numbers, viz., Reg=0.643, 1.287, and 12.87 are studied and compared with each other. The results indicate that for the Reynolds number of 0.643, sulfur dioxide always penetrates toward the droplet centerline throughout the entire absorption period. This is due to the mass transfer dominated by diffusion along the radial direction. In contrast, when the Reynolds number is 12.87, the strength of the vortex motion inside the droplet is strong enough. It results in that, most of the time the concentration contours parallel the streamlines and the lowest SO 2 concentration is located at the vortex center. As a consequence, the diffusion distance is reduced by a factor of three and the absorption time for the droplet reaching the saturated state is shortened in a significant way. With regard to an intermediate Reynolds number such as 1.287, a two-stage mass transfer process can be clearly identified. In the first stage, it is dominated by one-dimensional diffusion, in which over 50% sulfur dioxide is absorbed before the saturated state is reached. In the second stage, the vortex motion mainly controls the mass transfer. However, the contour core is inconsistent with the vortex center. This is because the characteristic time of mass diffusion is in a comparable state with that of droplet internal circulation. The present study elucidates that the strength of a droplet's internal motion plays a vital role in determining SO 2 absorption process.

  9. Influence of chlorine, sulfur and phosphorus on the volatilization behavior of heavy metals during sewage sludge thermal treatment.

    PubMed

    Luan, Jingde; Li, Rundong; Zhang, Zhihui; Li, Yanlong; Zhao, Yun

    2013-10-01

    Chlorine, sulfur and phosphorus were selected as element donators to investigate their effect on the volatilization behavior of heavy metals in sludge sewage incineration. Principal component analysis indicated that the promotive effect on the volatilization of heavy metals was followed by chlorine, sulfur and phosphorus. This result was proved to be correct by total release of heavy metals in sewage sludge incineration using different element donators. The release of heavy metals was very chlorine dependent, especially cadmium (Cd), lead (Pb) and nickel (Ni). When chlorine content was in the range of 0.1-0.5wt%, the increase of the volatilization rate was 44.9% for Cd, 6.8% for Pb and 4.6% for Ni, respectively. Although sulfur contributed to the promotion of the volatilization of heavy metals, excess oxygen impaired the promotive effect of sulfur on the release of heavy metals from the condensed phase. For phosphorus, solidifying heavy metals was dominant. Energy analysis showed that metal chlorides and sulfides were prone to volatilize or to be decomposed at elevated temperature compared with sulfates and phosphates owing to low binding energy in absolute value (VLFA). It was the difference of binding energy that led to the different volatilization behavior of metal compounds in a high temperature, oxygen-enriched atmosphere.

  10. Indicating atmospheric sulfur by means of S-isotope in leaves of the plane, osmanthus and camphor trees.

    PubMed

    Xiao, Hua-Yun; Wang, Yan-Li; Tang, Cong-Guo; Liu, Cong-Qiang

    2012-03-01

    Foliar δ(34)S values of three soil-growing plant species (Platanus Orientalis L., Osmanthus fragrans L. and Cinnamomum camphora) have been analyzed to indicate atmospheric sulfur. The foliar δ(34)S values of the three plant species averaged -3.11±1.94‰, similar to those of both soil sulfur (-3.73±1.04‰) and rainwater sulfate (-3.07±2.74‰). This may indicate that little isotopic fractionation had taken place in the process of sulfur uptake by root or leaves. The δ(34)S values changed little in the transition from mature leaves to old/senescing leaves for both the plane tree and the osmanthus tree, suggestive of little isotope effect during sulfur redistribution in plant tissues. Significantly linear correlation between δ(34)S values of leaves and rainwater sulfate for the plane and osmanthus trees allowed the tracing of temporal variations of atmospheric sulfur by means of foliar sulfur isotope, while foliage δ(34)S values of the camphor is not an effective indicator of atmospheric sulfur.

  11. Sulfur Isotope Fractionation Due to SO2 Photolysis in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.; Blackie, D.; Stark, G.; Pickering, J.

    2012-12-01

    The discovery of unusual (i.e. mass-independent) sulfur isotope fractionation (or MIF) in Archean and Paleoproterozoic sedimentary rocks has promised to yield insights into the rise of O2 and the nature of the sulfur cycle on ancient Earth [1], but interpretation has been hampered by the lack of a clear mechanism for the sulfur isotope signature. Proposed MIF mechanisms include SO2 photolysis [1-4], atmospheric S3 (thiozone) formation, and thermal sulfate reduction in sediments [5]. Studies focusing only on SO2 photolysis, including measurements of isotopic cross sections [6], have yielded results differing greatly from theory [4], and have resulted in improbable interpretations [7]. In addition to ancient rocks, there are sulfur isotope MIF signatures in polar ice core sulfates associated with massive Plinian eruptions over the past ~1000 years (e.g., [8]). The ice core MIF signatures differ significantly from the ancient Earth MIF signatures, suggesting a different source mechanism. SO2 photolysis can generate sulfur isotope MIF signatures in two ways: 1) self-shielding by an optically-thick column of SO2, and 2) isotope-dependent differences in absorption line intensities and widths, which are espcially important for optically-thin conditions. The MIF signatures in ice core sulfates appear to be consistent with self-shielding in an optically-thick plume, but the Archean MIF clearly is not. To address the optically-thin case, we've made high-resolution ultraviolet cross section measurements of the sulfur isotopologues of SO2 made with the UV FTS at Imperial College. We measured cross sections at 1 cm-1 spectral resolution for 32SO2, 33SO2, 34SO2 and for a 36SO2/34SO2 mixture. Incorporating these cross sections into a simple atmospheric photochemical model with a solar UV flux, we find sulfur MIF signatures for SO and S that.are consistent with the Archean pyrites. We also find that additional mass-dependent fractionation during self-shielding by 32SO2 places an

  12. Spatial and temporal variability of atmospheric sulfur-containing gases and particles during the Albatross campaign

    NASA Astrophysics Data System (ADS)

    Sciare, J.; Baboukas, E.; Kanakidou, M.; Krischke, U.; Belviso, S.; Bardouki, H.; Mihalopoulos, N.

    2000-06-01

    To investigate the oxidation chemistry of dimethylsulfide (DMS) in the marine atmosphere, atmospheric DMS, SO2, as well as several DMS oxidation products in aerosol phase such as non-sea-salt sulfate (nss-SO4), methanesulfonate (MSA), and dimethylsulfoxide (DMSOp) have been measured during the Albatross campaign in the Atlantic Ocean from October 9 to November 2, 1996. Long-range transport, local sea-to-air flux of DMS (FDMS), marine boundary layer (MBL) height variation, and photochemistry were found to be the major factors controlling atmospheric DMS concentration which ranged from 29 to 396 parts per trillion by volume (pptv) (mean of 120±68 pptv) over the cruise. The spatial variability of MSA and DMSOp follows the latitudinal variations of FDMS. A 2-day period of intensive photochemistry associated with quite stable atmospheric conditions south of the equator allowed the observation of anticorrelated diurnal variations between DMS and its main oxidation products. A chemical box model describing sulfur chemistry in the marine atmosphere was used to reproduce these variations and investigate coherence of experimentally calculated fluxes FDMS with observed DMS atmospheric concentrations. The model results reveal that the measured OH levels are not sufficient to explain the observed DMS daytime variation. Oxidizing species other than OH, probably BrO, must be involved in the oxidation of DMS to reproduce the observed data.

  13. One possible source of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

    NASA Astrophysics Data System (ADS)

    Babikov, Dmitri; Semenov, Alexander; Teplukhin, Alexander

    2017-05-01

    Energy transfer mechanism for recombination of two sulfur atoms into a diatomic molecule, S2, is studied theoretically and computationally to determine whether the rate coefficient of this process can be significantly affected by isotopic substitutions, and whether the resultant isotope effect is expected to be mass-dependent or mass-independent. This is one of sulfur polymerization processes thought to be important in the anoxic atmosphere of the Archean Earth and, potentially, relevant to mass-independent fractionation of sulfur isotopes. A simplified theoretical approach is employed, in which all properties of S2 molecule are characterized rather accurately, whereas the process of stabilization of metastable S2∗ by bath gas collisions is described approximately. Properties of individual scattering resonances in S2 are studied in detail, and it is found that most important contributions to the recombination process come from ro-vibrational states formed near the top of centrifugal barrier, and that the number of such states is about 50 (in 32S32S). Absolute value of recombination rate coefficient is computed to be 1.22 × 10-33 cm6/s (for 32S32S at room temperature and atmospheric pressure), close to experimental result. Two distinct isotope effects are identified. One is a classical mass-dependent effect due to translational partition function, which leads to a weak, smooth, and negative mass-dependence of rate coefficient (4% decrease when the mass is raised from 32S32S to 34S34S). Second effect, due to quantized resonances, is two orders of magnitude stronger, but is local. In practice, due to presence of multiple individual resonances, this phenomenon leads to irregular mass-independent variations of rate coefficients in the ranges ±5%. It is also demonstrated that in real molecules this irregular behavior is expected to be somewhat smoother, and the isotope effect is somewhat smaller, due to dependence of stabilization cross section on properties of

  14. Chlorine, fluorine, and sulfur emissions from Mount Erebus, Antarctica and estimated contributions to the Antarctic atmosphere

    SciTech Connect

    Zreda-Gostynska, G.; Kyle, P.R. ); Finnegan, D.L. )

    1993-09-15

    The authors report a study of the atmospheric release of gases from Mount Erebus, in continental Antarctica, over the period Dec 1986 to Jan 1991. This provides a case study of gas releases in a region of the planet almost devoid of anthropogenic sources. The discharge rates of chlorine, fluorine, and sulfur compounds have been monitored. The emission rates of HF and HCl were observed to double over this period to levels of 6 and 13.3 Gg/yr. Measurements were made from filter paper samples, relative to SO[sub 2] emission rates measured independently of the filter samples.

  15. Oxaldihydroxamic acid as a new reagent for the fixation of atmospheric sulfur dioxide

    NASA Astrophysics Data System (ADS)

    Paul, Khana Rani; Gupta, V. K.

    In the present investigation 0.01 M aqueous oxaldihydroxamic acid has been used to stabilize the atmospheric sulfur dioxide. The collection efficiency of the reagent was found to be ~ 100% and the sulfite solution was stable for ⩾ 30 days at room temperature. The sulfite ion was estimated colorimetrically using acidified p-aminoazobenzene and formaldehyde. The pink coloured dye, λmax 505 nm, obeys Beer's law in the range of 0.1-1 ppm. The procedure has been optimized with respect to the acidity, time and reagent concentration. The method is simple, free from pH dependence and several commonly present air pollutants do not interfere.

  16. Trifluoromethyl sulfur pentafluoride and its relationship to sulfur hexafluoride and chlorofluorocarbon-12 in the atmosphere near the New York City metropolitan area

    NASA Astrophysics Data System (ADS)

    Erboy, Yasemin; Smethie, William M.

    2012-08-01

    Trifluoromethyl sulfur pentafluoride (SF5CF3), sulfur hexafluoride (SF6) and dichlorodifluoromethane (CCl2F2) (also referred to as CFC-12) were measured simultaneously in the atmosphere at a site 25 km north of New York City over a period of 6 months with continuous measurements every 25 min for 4 months. The SF5CF3 record showed little variability and its concentration appeared close to the remote atmospheric concentration. The concentrations of SF6 and CFC-12 had numerous spikes well in excess of their remote atmospheric concentrations indicating the presence of local sources. The lack of SF5CF3 spikes reveals that the usage of SF6 in the New York metropolitan area does not result in significant production of SF5CF3, and also that there is no significant production by industrial and manufacturing processes in the region.

  17. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules.

    PubMed

    Schobesberger, Siegfried; Junninen, Heikki; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-10-22

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions.

  18. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    PubMed Central

    Schobesberger, Siegfried; Junninen, Heikki; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K.; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J.; Dunne, Eimear M.; Flagan, Richard C.; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P.; Rondo, Linda; Santos, Filipe D.; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S.; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M.; Worsnop, Douglas R.

    2013-01-01

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions. PMID:24101502

  19. Variations in the magnitude of non mass dependent sulfur fractionation in the Archean atmosphere

    NASA Astrophysics Data System (ADS)

    Claire, M.; Kasting, J. F.

    2010-12-01

    Recent experimental data have enabled quantitatively meaningful computations of the non-mass dependent fractionation of sulfur’s isotopes (Δ33S) that exemplify the Archean rock record. The Δ33S signal originates as a result of fine structure in the absorption cross-section of SO2 isotopologues [1], which only undergo significant photolysis in reducing atmospheres [2]. The Δ33S signal produced by SO2 photolysis varies significantly between 190 and 220 nm, and thus is strongly dependent on any other atmospheric gases which absorb photons in this range [3], as well as the height at which photolysis occurs. A model that is capable of resolving the altitude-dependent radiative transfer through a realistic self-consistent reducing atmosphere is therefore essential when making direct comparisons between atmospheric Δ33S production and the rock record. In this work, we investigate how the magnitude of Δ33S might vary as function of atmospheric composition, which in turn allows the rock record to constrain the Archean atmosphere. Other recent work on this topic using simplied atmospheric models has implicated large concentrations of SO2 [5], OCS [3], and CO2 [6] as being responsible for the variations in Archean Δ33S. We present results from an altitude-dependent photochemical model of Archean photochemistry [4] of necessary complexity to resolve the complicated redox structure of the Archean atmosphere. We show that while increased concentrations of these gases all affect Δ33S in an unconstrained model, the atmospheric conditions required for OCS or SO2 shielding are unlikely to occur in an Archean atmosphere constrained by reasonable expectations of volcanic and biogenic fluxes. Within the context of plausible Archean atmospheres, we investigate how shielding due to changing amounts of CO2, biogenic sulfur gases, and fractal organic haze [7] affect the magnitude of Δ33S produced by the Archean atmosphere, and show why simplified atmospheric modeling may lead to

  20. Laboratory studies of atmospheric sulfur chemistry using tunable diode laser probes

    SciTech Connect

    Stickel, R.E.; Urbanski, S.P.; Zhao, Z.; Wine, P.H.

    1996-12-31

    Tunable lead-salt diode laser absorption spectroscopy (TDLAS) provides a sensitive and versatile probe for the study of the kinetics and mechanisms of atmospheric reactions. In the laboratory, the combination of laser flash photolysis with TDLAS detection of reactant and/or product species has proven useful in several studies of the gas phase oxidation of the atmospheric sulfur compound dimethylsulfide (DMS), a process which may play an important role in global climate modification/regulation. Typically a radical species is produced by UV laser photolysis of a stable precursor in a slowly flowing mixture of reactant and buffer gases. The concentration of this radical or a selected reaction product is then followed by TDLAS on a time scale of microseconds to milliseconds. This method allows direct determination of reaction rates and product branching ratios over a range of temperature, pressure and reactant concentrations in complete isolation from reactor surfaces.

  1. Impact of anthropogenic atmospheric nitrogen and sulfur deposition on ocean acidification and the inorganic carbon system.

    PubMed

    Doney, Scott C; Mahowald, Natalie; Lima, Ivan; Feely, Richard A; Mackenzie, Fred T; Lamarque, Jean-Francois; Rasch, Phil J

    2007-09-11

    Fossil fuel combustion and agriculture result in atmospheric deposition of 0.8 Tmol/yr reactive sulfur and 2.7 Tmol/yr nitrogen to the coastal and open ocean near major source regions in North America, Europe, and South and East Asia. Atmospheric inputs of dissociation products of strong acids (HNO(3) and H2SO(4)) and bases (NH(3)) alter surface seawater alkalinity, pH, and inorganic carbon storage. We quantify the biogeochemical impacts by using atmosphere and ocean models. The direct acid/base flux to the ocean is predominately acidic (reducing total alkalinity) in the temperate Northern Hemisphere and alkaline in the tropics because of ammonia inputs. However, because most of the excess ammonia is nitrified to nitrate (NO(3)(-)) in the upper ocean, the effective net atmospheric input is acidic almost everywhere. The decrease in surface alkalinity drives a net air-sea efflux of CO(2), reducing surface dissolved inorganic carbon (DIC); the alkalinity and DIC changes mostly offset each other, and the decline in surface pH is small. Additional impacts arise from nitrogen fertilization, leading to elevated primary production and biological DIC drawdown that reverses in some places the sign of the surface pH and air-sea CO(2) flux perturbations. On a global scale, the alterations in surface water chemistry from anthropogenic nitrogen and sulfur deposition are a few percent of the acidification and DIC increases due to the oceanic uptake of anthropogenic CO(2). However, the impacts are more substantial in coastal waters, where the ecosystem responses to ocean acidification could have the most severe implications for mankind.

  2. Impact of anthropogenic atmospheric nitrogen and sulfur deposition on ocean acidification and the inorganic carbon system

    PubMed Central

    Doney, Scott C.; Mahowald, Natalie; Lima, Ivan; Feely, Richard A.; Mackenzie, Fred T.; Lamarque, Jean-Francois; Rasch, Phil J.

    2007-01-01

    Fossil fuel combustion and agriculture result in atmospheric deposition of 0.8 Tmol/yr reactive sulfur and 2.7 Tmol/yr nitrogen to the coastal and open ocean near major source regions in North America, Europe, and South and East Asia. Atmospheric inputs of dissociation products of strong acids (HNO3 and H2SO4) and bases (NH3) alter surface seawater alkalinity, pH, and inorganic carbon storage. We quantify the biogeochemical impacts by using atmosphere and ocean models. The direct acid/base flux to the ocean is predominately acidic (reducing total alkalinity) in the temperate Northern Hemisphere and alkaline in the tropics because of ammonia inputs. However, because most of the excess ammonia is nitrified to nitrate (NO3−) in the upper ocean, the effective net atmospheric input is acidic almost everywhere. The decrease in surface alkalinity drives a net air–sea efflux of CO2, reducing surface dissolved inorganic carbon (DIC); the alkalinity and DIC changes mostly offset each other, and the decline in surface pH is small. Additional impacts arise from nitrogen fertilization, leading to elevated primary production and biological DIC drawdown that reverses in some places the sign of the surface pH and air–sea CO2 flux perturbations. On a global scale, the alterations in surface water chemistry from anthropogenic nitrogen and sulfur deposition are a few percent of the acidification and DIC increases due to the oceanic uptake of anthropogenic CO2. However, the impacts are more substantial in coastal waters, where the ecosystem responses to ocean acidification could have the most severe implications for mankind. PMID:17804807

  3. Massive Impact-Induced Release of Carbon and Sulfur Gases in the Early Earth's Atmosphere

    NASA Astrophysics Data System (ADS)

    Marchi, S.; Black, B. A.; Elkins-Tanton, L. T.; Bottke, W. F., Jr.

    2016-12-01

    Atmospheric and surface conditions during the first billion years of Earth's history are poorly understood due to the paucity of geological and geochemical constraints. Early atmospheric models indicate that the Earth could have been in a frozen state for hundreds of millions of years due to the reduced luminosity of the young Sun, which was approximately 20-30% less intense than today at visible wavelengths. However, the oldest terrestrial zircons dating back to 4.3-4.4 Gyr ago hint at protoliths that interacted with liquid water at or near the surface of the Earth based on deviation of stable oxygen isotope ratios (δ18O) from mantle values. Recent developments in scientific understanding of the collisional history of the Hadean and early-Archean Earth indicate that large collisions may have been a fundamental geophysical process. In addition to altering the near surface environment by excavation and melting of large volumes of terrestrial rocks, these energetic events may also have resulted in massive release of volatiles to the primordial atmosphere. In this work we show that the early bombardment flux of large impactors ( >100 km) facilitated the atmospheric release of greenhouse gases from Earth's mantle. The picture emerging is one in which after the transient havoc of hot, silicate-rich atmospheres has passed, impact-generated melt outgassing could have substantially altered surface conditions. Release of greenhouse gases such as CO2 may have been sufficient to temporarily offset weaker insolation from the faint young Sun. Depending on the timescale for atmospheric CO2 drawdown, impact-induced outgassing could have sustained clement surface conditions episodically (1-10 Myr) or for a protracted time (100s of Myr). The bombardment also delivered and redistributed to the surface large quantities of sulfur, one of the most important elements for life. The stochastic occurrence of large collisions could provide insights on why the Earth and Venus, considered

  4. Multiple sulfur isotope geochemistry of Dharwar Supergroup, Southern India: Late Archean record of changing atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    Mishima, Kaoru; Yamazaki, Rie; Satish-Kumar, Madhusoodhan; Ueno, Yuichiro; Hokada, Tomokazu; Toyoshima, Tsuyoshi

    2017-04-01

    Earth's tectonic and climatic systems may have changed fundamentally before the Great Oxidation Event (GOE) at about 2.3 Ga. Sulfur Mass Independent Fractionation (S-MIF) has demonstrated that Earth's atmosphere was virtually oxygen-free before the GOE. During 3.0 to 2.4 Ga, the change in Δ33S and Δ36S signals may reflect the perturbation of atmospheric chemistry, though the mechanisms of the change are uncertain. Here, we reported multiple sulfur isotopic studies of Archean volcano-sedimentary sequences of the Dharwar Supergroup, distributed in the Chitradurga Schist Belt (CSB), Southern India. New field mapping and zircon U-Pb dating allows us to reconstruct detailed lithostratigraphy of the Dharwar Supergroup. The lower unit consists of post-3.0 Ga conglomerate, stromatolitic carbonate, siliciclastics with diamictite, chert/BIF and pillowed basalt in ascending order, all of which are older than the 2676 Ma dacite dyke that had intruded into the lower unit. The upper unit unconformably overlies the pillow basalts at the top of the lower unit, and consists of conglomerate/sandstone with ∼2600 Ma detrital zircons, komatiitic basalt, BIF and siliciclastic sequence with mafic volcanics. Sulfur isotope analysis of extracted sulfides shows MIF signals (Δ33S > + 1 ‰) with clear Δ33S- Δ36S correlations. The lower group of the Dharwar Supergroup shows a Δ36S / Δ33S slope of -1.48, the middle group shows -1.16 and -1.07, and the upper group shows -0.94. Reassessment of all the Archean S-MIF records from sedimentary rocks indicates that the Δ36S / Δ33S slope systematically changed during the Archean period. The observed trend in the Indian section is similar to those of its Pilbara-Kaapvaal equivalents, thus it could reflect a global atmospheric signature. Moreover, the isotopic trend seems to correlate with mid-Archean glaciation. Thus, the Δ36S / Δ33S slope could be a useful tracer for atmospheric chemistry and its link with climate change before the GOE.

  5. Enhanced acid rain and atmospheric deposition of nitrogen, sulfur and heavy metals in Northern China

    NASA Astrophysics Data System (ADS)

    Pan, Y.; Wang, Y.

    2013-12-01

    Atmospheric deposition is known to be important mechanism reducing air pollution. In response to the growing concern on the potential effects of the deposited material entering terrestrial and aquatic environments as well as their subsequent health effects, since 2007 we have established a 10-site monitoring network in Northern China, where particularly susceptible to severe air pollution. Wet and dry deposition was collected using an automatic wet-dry sampler. The presentation will focus on the new results of atmospheric deposition flux for a number of chemical species, such as nutrients (e.g. nitrogen and phosphorus), acidic matters (e.g. sulfur and proton), heavy metals and Polycyclic Aromatic Hydrocarbons, etc. This is to our knowledge the first detailed element budget study in the atmosphere across Northern China. We find that: (1) Over the 3 year period, 26% of precipitation events in the target area were more acid than pH 5.60 and these acidic events occurred in summer and autumn. The annual volume-weighted mean (VWM) pH value of precipitation was lower than 5.60 at most sites, which indicated the acidification of precipitation was not optimistic. The primary ions in precipitation were NH4+, Ca2+, SO42- and NO3-, with 10-sites-average concentrations of 221, 216, 216 and 80 μeq L-1, respectively. The ratio of SO42- to NO3- was 2.7; suggesting SO42- was the dominant acid component. (2) The deposited particles were neutral in general and the pH value increased from rural area to industrial and coastal sites. It is not surprising to note that the annual VWM pH value of precipitation was higher than 5.60 at three urban sites (Beijing and Tianjin mega cities) and one coastal site near the Bohai Bay, considering the fact that high buffer capacity of alkaline component, gas NH3 and mineral aerosols, at these sites compared to other places. (3) The 10-sites annual total deposition amounts for sulfur and nitrogen compounds were 60 and 65 kg N/S ha-1 yr-1

  6. Decreased atmospheric sulfur deposition across the southeastern U.S.: When will watersheds release stored sulfate?

    USGS Publications Warehouse

    Rice, Karen C.; Scanlon, Todd M.; Lynch, Jason A.; Cosby, Bernard J.

    2014-01-01

    Emissions of sulfur dioxide (SO2) to the atmosphere lead to atmospheric deposition of sulfate (SO42-), which is the dominant strong acid anion causing acidification of surface waters and soils in the eastern United States (U.S.). Since passage of the Clean Air Act and its Amendments, atmospheric deposition of SO2 in this region has declined by over 80%, but few corresponding decreases in stream-water SO42- concentrations have been observed in unglaciated watersheds. We calculated SO42- mass balances for 27 forested, unglaciated watersheds from Pennsylvania to Georgia, by using total atmospheric deposition (wet plus dry) as input. Many of these watersheds still retain SO42-, unlike their counterparts in the northeastern U.S. and southern Canada. Our analysis showed that many of these watersheds should convert from retaining to releasing SO42- over the next two decades. The specific years when the watersheds crossover from retaining to releasing SO42- correspond to a general geographical pattern of later net watershed release from north to south. The single most important variable that explained the crossover year was the runoff ratio, defined as the ratio of annual mean stream discharge to precipitation. Percent clay content and mean soil depth were secondary factors in predicting crossover year. The conversion of watersheds from net SO42- retention to release anticipates more widespread reductions in stream-water SO42- concentrations in this region.

  7. Geological sulfur isotopes indicate elevated OCS in the Archean atmosphere, solving faint young sun paradox

    PubMed Central

    Ueno, Yuichiro; Johnson, Matthew S.; Danielache, Sebastian O.; Eskebjerg, Carsten; Pandey, Antra; Yoshida, Naohiro

    2009-01-01

    Distributions of sulfur isotopes in geological samples would provide a record of atmospheric composition if the mechanism producing the isotope effects could be described quantitatively. We determined the UV absorption spectra of 32SO2, 33SO2, and 34SO2 and use them to interpret the geological record. The calculated isotopic fractionation factors for SO2 photolysis give mass independent distributions that are highly sensitive to the atmospheric concentrations of O2, O3, CO2, H2O, CS2, NH3, N2O, H2S, OCS, and SO2 itself. Various UV-shielding scenarios are considered and we conclude that the negative Δ33S observed in the Archean sulfate deposits can only be explained by OCS shielding. Of relevant Archean gases, OCS has the unique ability to prevent SO2 photolysis by sunlight at λ >202 nm. Scenarios run using a photochemical box model show that ppm levels of OCS will accumulate in a CO-rich, reducing Archean atmosphere. The radiative forcing, due to this level of OCS, is able to resolve the faint young sun paradox. Further, the decline of atmospheric OCS may have caused the late Archean glaciation. PMID:19706450

  8. Sulfur in the early martian atmosphere revisited: Experiments with a 3-D Global Climate Model

    NASA Astrophysics Data System (ADS)

    Kerber, Laura; Forget, François; Wordsworth, Robin

    2015-11-01

    Volcanic SO2 in the martian atmosphere has been invoked as a way to create a sustained or transient greenhouse during early martian history. Many modeling studies have been performed to test the feasibility of this hypothesis, resulting in a range of conclusions, from highly feasible to highly improbable. In this study we perform a wide range of simulations using the 3-D Laboratoire de Météorologie Dynamique Generic Global Climate Model (GCM) in order to place earlier results into context and to explore the sensitivity of model outcomes to parameters such as SO2 mixing ratio, atmospheric H2O content, background atmospheric pressure, and aerosol size, abundance, and composition. We conclude that SO2 is incapable of creating a sustained greenhouse on early Mars, and that even in the absence of aerosols, local and daily temperatures rise above 273 K for only for limited periods with favorable background CO2 pressures. In the presence of even small amounts of aerosols, the surface is dramatically cooled for realistic aerosol sizes. Brief, mildly warm conditions require the co-occurrence of many improbable factors, while cooling is achieved for a wide range of model parameters. Instead of causing warming, sulfur in the martian atmosphere may have caused substantial cooling, leading to the end of clement climate conditions on early Mars.

  9. Decreased atmospheric sulfur deposition across the Southeastern U.S.: when will watersheds release stored sulfate?

    PubMed

    Rice, Karen C; Scanlon, Todd M; Lynch, Jason A; Cosby, Bernard J

    2014-09-02

    Emissions of sulfur dioxide (SO2) to the atmosphere lead to atmospheric deposition of sulfate (SO4(2-)), which is the dominant strong acid anion causing acidification of surface waters and soils in the eastern United States. Since passage of the Clean Air Act and its Amendments, atmospheric deposition of SO2 in this region has declined by over 80%, but few corresponding decreases in streamwater SO4(2-) concentrations have been observed in unglaciated watersheds. We calculated SO4(2-) mass balances for 27 forested, unglaciated watersheds from Pennsylvania to Georgia, by using total atmospheric deposition (wet plus dry) as input. Many of these watersheds still retain SO4(2-), unlike their counterparts in the northeastern U.S. and southern Canada. Our analysis showed that many of these watersheds should convert from retaining to releasing SO4(2-) over the next two decades. The specific years when the watersheds crossover from retaining to releasing SO4(2-) correspond to a general geographical pattern of later net watershed release from north to south. The single most important variable that explained the crossover year was the runoff ratio, defined as the ratio of annual mean stream discharge to precipitation. Percent clay content and mean soil depth were secondary factors in predicting crossover year. The conversion of watersheds from net SO4(2-) retention to release anticipates more widespread reductions in streamwater SO4(2-) concentrations in this region.

  10. Decreased Atmospheric Sulfur Deposition Across the Southeastern U.S.: When Will Watersheds Release Stored Sulfate?

    NASA Astrophysics Data System (ADS)

    Rice, K. C.; Scanlon, T. M.; Lynch, J. A.; Cosby, B. J., Jr.

    2014-12-01

    Emissions of sulfur dioxide (SO2) to the atmosphere lead to atmospheric deposition of sulfate (SO42-), which is the dominant strong acid anion causing acidification of surface waters and soils in the eastern United States (U.S.). Since passage of the Clean Air Act and its Amendments, atmospheric deposition of SO2 in this region has declined by over 80%, but few corresponding decreases in stream-water SO42- concentrations have been observed in unglaciated watersheds. We calculated SO42- mass balances for 27 forested, unglaciated watersheds from Pennsylvania to Georgia, by using total atmospheric deposition (wet plus dry) as input. Many of these watersheds still retain SO42-, unlike their counterparts in the northeastern U.S. and southern Canada. Our analysis showed that many of these watersheds should convert from retaining to releasing SO42- over the next two decades. The specific years when the watersheds crossover from retaining to releasing SO42- correspond to a general geographical pattern of later net watershed release from north to south. The single most important variable that explained the crossover year was the runoff ratio, defined as the ratio of annual mean stream discharge to precipitation. Percent clay content and mean soil depth were secondary factors in predicting crossover year. The conversion of watersheds from net SO42- retention to release anticipates more widespread reductions in stream-water SO42- concentrations in this region.

  11. Properties and Atmospheric Implication of Methylamine-Sulfuric Acid-Water Clusters.

    PubMed

    Lv, Sha-Sha; Miao, Shou-Kui; Ma, Yan; Zhang, Miao-Miao; Wen, Yang; Wang, Chun-Yu; Zhu, Yu-Peng; Huang, Wei

    2015-08-13

    The presence of amines can increase aerosol formation rates. Most studies have been devoted to dimethylamine as the representative of amine; however, there have been a few works devoted to methylamine. In this study, theoretical calculations are performed on CH3NH2(H2SO4)m(H2O)n (m = 0-3, n = 0-3) clusters. In addition to the structures and energetics, we focused on determining the following characteristics: (1) the growth mechanism, (2) the hydrate distributions and the influences of humidity and temperature, (3) Rayleigh scattering properties. We explored the cluster growth mechanism from a thermodynamics aspect by calculating the Gibbs free energy of adding a water or sulfuric acid molecule step by step at three atmospherically relevant temperatures. The relative ease of the reaction at each step is discussed. From the analysis of hydrate distributions, we find that CH3NH2(H2SO4)(H2O)2, CH3NH2(H2SO4)2, and CH3NH2(H2SO4)3 are most likely to exist in the atmosphere. The general trend of hydration in all cases is more extensive with the growing relative humidity (RH), whereas the distributions do not significantly change with the temperature. Analysis of the Rayleigh scattering properties showed that both H2SO4 and H2O molecules could increase the Rayleigh scattering intensities and isotropic mean polarizabilities, with greater influence by the sulfuric acid molecules. This work sheds light on the mechanism for further research on new particle formation (NPF) containing methylamine in the atmosphere.

  12. Modelling of the Chemistry of Sulfur Oxides in the Middle Atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Mills, F. P.; Johri, S.; Yung, Y. L.; Allen, M.

    2009-05-01

    Venus' middle atmosphere (˜ 60-110 km) is a dynamic region in which photochemistry dominates and the time scales for chemical loss and transport are roughly comparable for many species. It is also a region where it has been difficult to observe the abundances of species that play important roles in two of the dominant chemical cycles on Venus. The CO2 cycle comprises photodissociation of CO2 to produce CO and O, transport of some CO and O to the night side, production of O2 from 2O+M→O2+M on the day and night sides, and production of CO2 from CO and O2. The sulfur oxidation cycle comprises oxidation of SO2 to form H2SO4, condensation, subsidence of some particles to the lower atmosphere, evaporation, and thermal decomposition or photodissociation to produce SO2 and H2O. Recent mesospheric observations have provided clear evidence of diurnal variability in the abundances of sulfur oxides. Observed SO has its peak abundance on the day side and observed SO2 has its peak abundance on the night side (Sandor et al, 2008). We have used global average model calculations (Pernice et al, 2004; Mills and Allen, 2007) to derive approximate analytic expressions for [SO], [SO2], and [SO]/[SO2] on the day and night sides. The results are generally consistent across a broad range of atmospheric oxidation states (Mills and Allen, 2007). Our model results and the key uncertainties will be discussed. A related topic is the identity of the UV-blue absorber that is responsible for the absorption observed in the upper cloud layer (˜ 60-70 km) at 320-500 nm. One proposed suggestion is S2O (Hapke and Graham, 1985; Na and Esposito, 1997). Our model results for S2O and their implications will be discussed and compared with previous work.

  13. Atmospheric Sulfur Cycle Simulated in The Global Model GOCART: Model Description and Global Properties

    NASA Technical Reports Server (NTRS)

    Chin, Mian; Rood, Richard B.; Lin, Shian-Jiann; Mueller, Jean-Francois; Thompson, Anne M.

    2000-01-01

    The Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model is used to simulate the atmospheric sulfur cycle. The model uses the simulated meteorological data from the Goddard Earth Observing System Data Assimilation System (GEOS DAS). Global sulfur budgets from a 6-year simulation for SO2, sulfate, dimethylsulfide (DMS), and methanesulfonic acid (MSA) are presented in this paper. In a normal year without major volcanic perturbations, about 20% of the sulfate precursor emission is from natural sources (biogenic and volcanic) and 80% is anthropogenic: the same sources contribute 339% and 67% respectively to the total sulfate burden. A sulfate production efficiency of 0.41 - 0.42 is estimated in the model, an efficiency which is defined as a ratio of the amount oi sulfate produced to the total amount of SO2 emitted and produced in the atmosphere. This value indicates that less than half of the SO2 entering the atmosphere contributes to the sulfate production, the rest being removed by dry and wet depositions. In a simulation for 1990, we estimate a total sulfate production of 39 Tg S /yr with 36% and 64% respectively from in-air and in-cloud oxidation of SO2. We also demonstrate that major volcanic eruptions, such as the Mt. Pinatubo eruption in 1991, can significantly change the sulfate formation pathways, distributions, abundance, and lifetime. Comparison with other models shows that the parameterizations for wet removal or wet production of sulfate are the most critical factors in determining the burdens of SO2 and sulfate. Therefore, a priority for future research should be to reduce the large uncertainties associated with the wet physical and chemical processes.

  14. Sulfur isotope fractionation by broadband UV radiation to optically thin SO2 under reducing atmosphere

    NASA Astrophysics Data System (ADS)

    Endo, Yoshiaki; Ueno, Yuichiro; Aoyama, Shinnosuke; Danielache, Sebastian O.

    2016-11-01

    Photochemical mechanisms of Sulfur Mass-Independent Fractionation (S-MIF) are still poorly understood. Previous laboratory experiments have indicated that the S-MIF depends largely on the spectrum of the incident light source and the partial pressure of SO2, though the basic character of the Archean S-MIF (Δ36S / Δ33S = ∼ - 1) has never been reproduced. We have conducted new photochemical experiments at low pSO2 (1-10 Pa) conditions under the presence of CO and found a reasonable mechanism to reproduce the Δ36S/Δ33S slope about -1. As previously suggested (Ono et al., 2013), the low pSO2 is key to studying the self-shielding effect within a range of realistic atmospheric conditions. Also, reducing conditions are critical for simulating the O2-poor atmosphere, whereas photolysis of pure SO2 provides excess O atoms that significantly change the overall chemistry. Our experimental results confirmed that significant S-MIF (Δ36S / Δ33S = - 2.4) can be produced by self-shielding in the SO2 photolysis band (185-220 nm), even if the SO2 column density is as low as 1016 molecules cm-2. Thus, photolysis within a volcanic plume of ∼0.1 ppm SO2 is capable of producing a large S-MIF signature. The isotopic fractionations originating from the different absorption cross sections of SO2 isotopologues (i.e. wavelength dependent effect; without self-shielding) are only minor (potentially up to +4‰ for Δ33S). Under reducing conditions, however, another S-MIF signal with Δ36S/Δ33S ratio of ∼+0.7 is produced due to collision-induced intersystem crossing (ISC) from singlet to triplet states of SO2 (Whitehill et al., 2013), and should also be transferred into the final product that is responsible for changing the Δ36S/Δ33S slope. Based on a photochemical model of the S-O-C system with the two S-MIF-yielding reactions, the largest S-MIF observed in the late Archean Mt. McRae Fm. (Δ33S = + 9.4 ‰, Δ36S = - 7.5 ‰) can be reproduced by solar UV irradiation of a SO2

  15. Atmospheric Observations of Aerosol Sizes, Sulfuric Acid and Ammonia Measured in Kent, Ohio

    NASA Astrophysics Data System (ADS)

    Pavuluri, C.; Benson, D. R.; Dailey, B.; Lee, S.

    2008-12-01

    Atmospheric particles affect atmospheric composition, cloud formation, global radiation budget, and human health. Nucleation is a gas-to-particle conversion process in which new particles form directly from gas phase species and is a key process that controls particle number concentrations. The most common feature of the new particle formation events is a substantial increase of number concentrations of nucleation mode particles reaching up to 105-106 cm-3 in the condensable vapor-laden air. There are several nucleation mechanisms for tropopsheric aerosol formation, but it is unclear which nucleation process dominates. In particular, observations and modeling studies show that ammonia can be important for atmospheric nucleation in the boundary layer, but simultaneous measurements of aerosol sizes and precursors including sulfuric acid and ammonia are critically lacking. In order to overcome these shortcomings, we conduct atmospheric observations of new particle formation in Kent, OH. We have measured aerosol sizes and concentrations for particles in the size range from 3-102 nm semi- continuously from December 2005 and for particles from 3-1000 nm continuously from September 2007 in Kent State campus, Kent, OH (with an inlet placed at ~11.5 m above ground level). We also simultaneously measure sulfuric acid and ammonia, two most important inorganic aerosol precursors, with two chemical ionization mass spectrometers (CIMS) from August 2008. Kent, located in Northeastern Ohio, is relatively rural itself, but is also surrounded by several urban cities within 40 miles. Because of the combination of its relatively rural environment (hence low surface areas of aerosol particles), active vegetation (organic and NH3 emissions), and possible transport of aerosol precursors from the surrounding urban and industrialized areas, Kent is a unique location to make new particle formation studies. So far, most of new particle formation observations made typically in US were at

  16. Sulfur dioxide in the atmosphere of Venus 1 sounding rocket observations

    NASA Technical Reports Server (NTRS)

    Mcclintock, William E.; Barth, Charles A.; Kohnert, Richard A.

    1994-01-01

    In this paper we present ultraviolet reflectance spectra obtained during two sounding rocket observations of Venus made during September 1988 and March 1991. We describe the sensitivity of the derived reflectance to instrument calibration and show that significant artifacts can appear in that spectrum as a result of using separate instruments to observe both the planetary radiance and the solar irradiance. We show that sulfur dioxide is the primary spectral absorber in the 190 - 230 nm region and that the range of altitudes probed by these wavelengths is very sensitive to incidence and emission angles. In a following paper Na et. al. (1994) show that sulfur monoxide features are also present in these data. Accurate identification and measurement of additional species require observations in which both the planetary radiance and the solar irradiance are measured with the same instrument. The instrument used for these observations is uniquely suited for obtaining large phase angle coverage and for studying transient atmospheric events on Venus because it can observe targets within 18 deg of the sun while earth orbiting instruments are restricted to solar elongation angles greater than or equal to 45 deg.

  17. Sulfur dioxide in the atmosphere of Venus. 1: Sounding rocket observations

    NASA Technical Reports Server (NTRS)

    Mcclintock, William E.; Barth, Charles A.; Kohnert, Richard A.

    1994-01-01

    In this paper we present ultraviolet reflectance spectra obtained during two sounding rocket observations of Venus made during September 1988 and March 1991. We describe the sensitivity of the derived reflectance to instrument calibration and show that significant artifacts can appear in the spectrum as a result of using separate instruments to observe both the planetary radiance and the solar irradiance. We show that sulfur dioxide is the primary special absorber in the 190-230 nm region and that the range of altitudes probed by these wavelengths is very sensitive to incidence and emission angles. In a following paper Na et al. (1994) show that sulfur monixide features are also present intese data. Accurate identification and measurement of additional species require observations in which both the planetary radiance and the solar irradiance are measured with the same instrument. The instrument used for these observations is uniquely suited for obtaining large phase angle coverage and for studying transient atmospheric events on Venus because it can observe targents within 18 deg of the Sun while Earth-orbiting instruments are restricted to solar elongation angles greater than or equal to 45 deg.

  18. Reduced sulfur compounds in the atmosphere of sewer networks in Australia: geographic (and seasonal) variations.

    PubMed

    Wang, B; Sivret, E C; Parcsi, G; Le, N M; Kenny, S; Bustamante, H; Stuetz, R M

    2014-01-01

    The management of odorous emissions from sewer networks has become an important issue for sewer system operators resulting in the need to better understand the composition of reduced sulfur compounds (RSCs). Gaseous RSCs including hydrogen sulfide (H2S), methanethiol (MeSH), dimethyl sulfide (DMS), carbon disulfide (CS2), dimethyl disulfide (DMDS) and dimethyl trisulfide (DMTS) were measured in the atmosphere of selected sewer networks in two major Australian cities (Sydney and Melbourne) during 2011-2012. The RSC concentrations in the sewer air were detected in a highly variable range. H2S and MeSH were found at the highest concentrations, followed by DMS (39.2-94.0 μg/m(3)), CS2 (18.3-19.6 μg/m(3)), DMDS (7.8-49.6 μg/m(3)) and DMTS (10.4-35.3 μg/m(3)). Temporal trends in the occurrence of targeted RSCs were observed and the highest sulfur concentration occurred either in summer or spring, which are typically regarded as the warmer seasons. Statistical significant difference in the magnitude of targeted RSCs was found between samples collected in Sydney and Melbourne.

  19. Direct night-time ejection of particle-phase reduced biogenic sulfur compounds from the ocean to the atmosphere.

    PubMed

    Gaston, Cassandra J; Furutani, Hiroshi; Guazzotti, Sergio A; Coffee, Keith R; Jung, Jinyoung; Uematsu, Mitsuo; Prather, Kimberly A

    2015-04-21

    The influence of oceanic biological activity on sea spray aerosol composition, clouds, and climate remains poorly understood. The emission of organic material and gaseous dimethyl sulfide (DMS) from the ocean represents well-documented biogenic processes that influence particle chemistry in marine environments. However, the direct emission of particle-phase biogenic sulfur from the ocean remains largely unexplored. Here we present measurements of ocean-derived particles containing reduced sulfur, detected as elemental sulfur ions (e.g., (32)S(+), (64)S2(+)), in seven different marine environments using real-time, single particle mass spectrometry; these particles have not been detected outside of the marine environment. These reduced sulfur compounds were associated with primary marine particle types and wind speeds typically between 5 and 10 m/s suggesting that these particles themselves are a primary emission. In studies with measurements of seawater properties, chlorophyll-a and atmospheric DMS concentrations were typically elevated in these same locations suggesting a biogenic source for these sulfur-containing particles. Interestingly, these sulfur-containing particles only appeared at night, likely due to rapid photochemical destruction during the daytime, and comprised up to ∼67% of the aerosol number fraction, particularly in the supermicrometer size range. These sulfur-containing particles were detected along the California coast, across the Pacific Ocean, and in the southern Indian Ocean suggesting that these particles represent a globally significant biogenic contribution to the marine aerosol burden.

  20. Emissions of industrial furnaces burning diesel fuel oils of various sulfur contents with NaCl - contained atmospheric air

    SciTech Connect

    Lin, C.Y.; Hsieh, M.J.

    1996-04-01

    A small furnace associated with an industrial automatic burner was employed in this study to investigate the influences of sulfur content of fuel oils burned with NaCl contained atmospheric air on the emission characteristics of marine or industrial power-plants. The sulfur contents of 0.3 wt% and 1.0 wt% were considered. Diesel fuel oil A which approximates ASTM No. 2 fuel oil was atomized by the inlet air added with NaCl of 1.5 ppm concentration and thereafter burned within the furnace. It was found that under this burning condition the CO, SO{sub 2}, and O{sub 2} emissions increased with the addition of sulfur in the fuel oil. However, the gas temperature and NO{sub x} concentration were affected by the increase of sulfur content to only a minor extent. 14 refs., 10 figs.

  1. Neutral molecular cluster formation of sulfuric acid-dimethylamine observed in real time under atmospheric conditions.

    PubMed

    Kürten, Andreas; Jokinen, Tuija; Simon, Mario; Sipilä, Mikko; Sarnela, Nina; Junninen, Heikki; Adamov, Alexey; Almeida, João; Amorim, Antonio; Bianchi, Federico; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Hutterli, Manuel; Kangasluoma, Juha; Kirkby, Jasper; Laaksonen, Ari; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Praplan, Arnaud P; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Schobesberger, Siegfried; Seinfeld, John H; Steiner, Gerhard; Tomé, António; Tröstl, Jasmin; Winkler, Paul M; Williamson, Christina; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Kenneth S; Kulmala, Markku; Worsnop, Douglas R; Curtius, Joachim

    2014-10-21

    For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even though the neutral particles are stable against evaporation from the SA dimer onward, the formation rates of particles at 1.7-nm size, which contain about 10 SA molecules, are up to 4 orders of magnitude smaller compared with those of the dimer due to coagulation and wall loss of particles before they reach 1.7 nm in diameter. This demonstrates that neither the atmospheric particle formation rate nor its dependence on SA can simply be interpreted in terms of cluster evaporation or the molecular composition of a critical nucleus.

  2. Neutral molecular cluster formation of sulfuric acid–dimethylamine observed in real time under atmospheric conditions

    PubMed Central

    Kürten, Andreas; Jokinen, Tuija; Simon, Mario; Sipilä, Mikko; Sarnela, Nina; Junninen, Heikki; Adamov, Alexey; Almeida, João; Amorim, Antonio; Bianchi, Federico; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M.; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C.; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Hutterli, Manuel; Kangasluoma, Juha; Kirkby, Jasper; Laaksonen, Ari; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Praplan, Arnaud P.; Riccobono, Francesco; Rissanen, Matti P.; Rondo, Linda; Schobesberger, Siegfried; Seinfeld, John H.; Steiner, Gerhard; Tomé, António; Tröstl, Jasmin; Winkler, Paul M.; Williamson, Christina; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Kenneth S.; Kulmala, Markku; Worsnop, Douglas R.; Curtius, Joachim

    2014-01-01

    For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even though the neutral particles are stable against evaporation from the SA dimer onward, the formation rates of particles at 1.7-nm size, which contain about 10 SA molecules, are up to 4 orders of magnitude smaller compared with those of the dimer due to coagulation and wall loss of particles before they reach 1.7 nm in diameter. This demonstrates that neither the atmospheric particle formation rate nor its dependence on SA can simply be interpreted in terms of cluster evaporation or the molecular composition of a critical nucleus. PMID:25288761

  3. Theoretical and global scale model studies of the atmospheric sulfur/aerosol system

    NASA Technical Reports Server (NTRS)

    Kasibhatla, Prasad

    1996-01-01

    The primary focus during the third-phase of our on-going multi-year research effort has been on 3 activities. These are: (1) a global-scale model study of the anthropogenic component of the tropospheric sulfur cycle; (2) process-scale model studies of the factors influencing the distribution of aerosols in the remote marine atmosphere; and (3) an investigation of the mechanism of the OH-initiated oxidation of DMS in the remote marine boundary layer. In this paper, we describe in more detail our research activities in each of these areas. A major portion of our activities during the fourth and final phase of this project will involve the preparation and submission of manuscripts describing the results from our model studies of marine boundary-layer aerosols and DMS-oxidation mechanisms.

  4. Production of furfural from xylose at atmospheric pressure by dilute sulfuric acid and inorganic salts.

    PubMed

    Rong, Chunguang; Ding, Xuefeng; Zhu, Yanchao; Li, Ying; Wang, Lili; Qu, Yuning; Ma, Xiaoyu; Wang, Zichen

    2012-03-01

    In this paper, the dehydration of xylose to furfural was carried out under atmospheric pressure and at the boiling temperature of a biphasic mixture of toluene and an aqueous solution of xylose, with sulfuric acid as catalyst plus an inorganic salt (NaCl or FeCl(3)) as promoter. The best yield of furfural was 83% under the following conditions: 150 mL of toluene and 10 mL of aqueous solution of 10% xylose (w/w), 10% H(2)SO(4) (w/w), 2.4g NaCl , and heating for 5h. FeCl(3) as promoter was found to be more efficient than NaCl. The addition of DMSO to the aqueous phase in the absence of an inorganic salt was shown to improve the yield of furfural.

  5. Titanium leaching from red mud by diluted sulfuric acid at atmospheric pressure.

    PubMed

    Agatzini-Leonardou, S; Oustadakis, P; Tsakiridis, P E; Markopoulos, Ch

    2008-09-15

    Laboratory-scale research has focused on the recovery of titanium from red mud, which is obtained from bauxite during the Bayer process for alumina production. The leaching process is based on the extraction of this element with diluted sulfuric acid from red mud under atmospheric conditions and without using any preliminary treatment. Statistical design and analysis of experiments were used, in order to determine the main effects and interactions of the leaching process factors, which were: acid normality, temperature and solid to liquid ratio. The titanium recovery efficiency on the basis of red mud weight reached 64.5%. The characterization of the initial red mud, as well as this of the leached residues was carried out by X-ray diffraction, TG-DTA and scanning electron microscopy.

  6. Missing SO2 oxidant in the coastal atmosphere? - Evidence from high resolution measurements of OH and atmospheric sulfur compounds

    NASA Astrophysics Data System (ADS)

    Berresheim, H.; Adam, M.; Monahan, C.; O'Dowd, C.; Plane, J. M. C.; Bohn, B.; Rohrer, F.

    2014-01-01

    Diurnal and seasonal variations of gaseous sulfuric acid (H2SO4) and methane sulfonic acid (MSA) were measured in N.E. Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected ion/chemical ionization mass spectrometry (SI/CIMS) with a detection limit for both compounds of 4.3 × 10 4 cm-3 at 5 min signal integration. The H2SO4 and MSA gas-phase concentrations were analysed in conjunction with the condensational sink for both compounds derived from 3 nm-10 μm (diameter) aerosol size distributions. Accommodation coefficients of 1.0 for H2SO4 and 0.12 for MSA were assumed leading to estimated atmospheric lifetimes of the order of 7 min and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH) signal evidence was obtained for the presence of one or more unknown oxidants of SO2 in addition to OH. Depending on the nature of the oxidant(s) their ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO2 oxidant was additionally confirmed by direct measurements of SO2 in conjunction with calculated H2SO4 concentrations. The calculated concentrations were consistently lower than the measured concentrations by a factor 4.8 ± 3.4 when considering the oxidation of SO2 by OH as the only source of H2SO4. Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J(O1D), and were followed by peaks in both H2SO4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s), OH chemistry, and the atmospheric photo-oxidation of biogenic iodine compounds. As to the identity of the oxidant(s), we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on ab initio calculations. Stabilized Criegee intermediates (sCI) produced from

  7. Changes in Atmospheric Sulfur Dioxide (SO2) over the English Channel - 1.5 Years of Measurements from the Penlee Point Atmospheric Observatory

    NASA Astrophysics Data System (ADS)

    Yang, Mingxi; Bell, Thomas; Hopkins, Frances; Smyth, Timothy

    2016-04-01

    Atmospheric sulfur dioxide (SO2) was measured continuously from the Penlee Point Atmospheric Observatory near Plymouth, United Kingdom between May 2014 and November 2015. This coastal site is exposed to marine air across a wide wind sector. The predominant southwesterly winds carry relatively clean background Atlantic air. In contrast, air from the southeast is heavily influenced by exhaust plumes from ships in the English Channel as well as near near the Plymouth Sound. International Maritime Organization regulation came into force in January 2015 to reduce sulfur emissions tenfold in Sulfur Emission Control Areas such as the English Channel. We observed a three-fold reduction from 2014 to 2015 in the estimated ship-emitted SO2 during southeasterly winds. Dimethylsulfide (DMS) is an important source of atmospheric SO2 even in this semi-polluted region. The relative contribution of DMS oxidation to the SO2 burden over the English Channel increased from ~1/3 in 2014 to ~1/2 in 2015 due to the reduction in ship sulfur emissions. Our diel analysis suggests that SO2 is removed from the marine atmospheric boundary layer in about half a day, with dry deposition to the ocean accounting for a quarter of the total loss.

  8. The behavior of sulfur in industrial pyrometallurgical slags

    NASA Astrophysics Data System (ADS)

    Nagamori, Meguru

    1994-08-01

    Dissolution of sulfur in industrial slags, even at such a low level as 1 mass% S or so, increases the solubility of certain valuable metals by an order of magnitude. The phenomenon is accounted for in terms of Flood-Førland-Grjotheim's model for dianionic salt solutions, whereas its rigorous analysis requires the digaseous Gibbs-Duhem integration. In the research described here, the distribution of sulfur among gas, slag, and metallic iron phases in the bath smelting of iron ore was computer-simulated based on a two-sites model coupled with sulfide capacity data. The solubilities of Ag, Cu, Co, and Ni in industrial slags are reviewed by applying the sulfidic-oxidic dissolution model to copper-matte smelting, nickel-slag cleaning (Falconbridge, Canada), and the imperial smelting process for zinc and lead (Hachinohe, Japan).

  9. A three-dimensional modelling study of the seasonal cycle of sulfur species in the Antarctic atmosphere

    NASA Astrophysics Data System (ADS)

    Cosme, E.; Boucher, O.; Genthon, C.; Hourdin, F.; Krinner, G.; Legrand, M.; Martinerie, P.; Pham, M.

    2002-12-01

    The high-southern latitudes are one of the last regions of the globe where the sulfur cycle remains dominated by its natural component. Moreover, a good understanding of the processes involved in dimethylsulfide (DMS) oxidation is needed to interpret polar ice core records of sulfate and methanesulfonic acid (MSA). Both reasons motivated this modelling study of the sulfur cycle in Antarctica. For this purpose, the Antarctic version (with high resolution and improved physics in the high-southern latitudes) and the sulfur version of the Laboratoire de Météorologie Dynamique Atmospheric General Circulation Model (AGCM), LMD-ZT, have been merged and used to study the seasonal cycle of sulfur species. In a first step, the model results are compared with available measurements of sulfur compounds at high- and mid- southern latitudes. They are realistic but some defects are identified (Cosme et al., Sulfur cycle in the high southern latitudes in the LMD-ZT General Circulation Model, JGR, in press). In a second step, the seasonal cycle of sulfur compounds at an inland site (Dome Concordia) is presented and compared to the analogous results at the coastal site Dumont d'Urville. This comparison suggests that the relative roles of each process of the sulfur cycle (emissions, chemistry, transport) strongly differ from the coastal site to the inland site. At last, an adjoint of the model has been run to provide an inverse history of DMS, sulfate and MSA observed at two Antarctic sites: Dumont d'Urville (coastal Antarctica) and Vostok (inland Antarctica). For both sites, the origins of the sulfur species (type of sources, age, and latitudinal origin) are presented and discussed.

  10. STREAMWATER ACID-BASED CHEMISTRY AND CRITICAL LOADS OF ATMOSPHERIC SULFUR DEPOSITION IN SHENANDOAH NATIONAL PARK, VIRGINIA

    EPA Science Inventory

    A modeling study was conducted to evaluate the acid-base chemistry of streams within Shenandoah National Park, Virginia and to project future responses to sulfur (S) and nitrogen (N) atmospheric emissions controls. Many of the major stream systems in the Park have acid neutraliz...

  11. STREAMWATER ACID-BASED CHEMISTRY AND CRITICAL LOADS OF ATMOSPHERIC SULFUR DEPOSITION IN SHENANDOAH NATIONAL PARK, VIRGINIA

    EPA Science Inventory

    A modeling study was conducted to evaluate the acid-base chemistry of streams within Shenandoah National Park, Virginia and to project future responses to sulfur (S) and nitrogen (N) atmospheric emissions controls. Many of the major stream systems in the Park have acid neutraliz...

  12. A comparison of sulfur-free and ambient air enclosure techniques for measuring the exchange of reduced sulfur gases between soils and the atmosphere

    NASA Astrophysics Data System (ADS)

    Castro, Mark S.; Galloway, James N.

    1991-08-01

    The exchange of reduced sulfur gases between the atmosphere and forest soils in the Shaver Hollow watershed (Shenandoah National Park, Virginia) were measured with sulfur-free and ambient air enclosures at least twice a month from March through November 1989. Soils within sulfur-free enslosures were sources of carbonyl sulfide (COS) and carbon disulfide (CS2). Atmospheric fluxes of COS and CS2 ranged from 0.77 to 13.03 ng COS-S/sq m-min and from 2.04 to 15.74 ng CS2-S/sq m-min. In contrast, soils within ambient air enclosures were sinks for COS and CS2. Uptake rates of COS and CS2 ranged from 2.78 to 16.20 ng COS-S/sq m-min and from 3.42 to 26.62 ng CS2-S/sq m-min. The discrepancy in the direction of these fluxes was caused by the flux-measurement techniques.

  13. International Global Atmospheric Chemistry Programme global emissions inventory activity: Sulfur emissions from volcanoes, current status

    SciTech Connect

    Benkovitz, C.M.

    1995-07-01

    Sulfur emissions from volcanoes are located in areas of volcanic activity, are extremely variable in time, and can be released anywhere from ground level to the stratosphere. Previous estimates of global sulfur emissions from all sources by various authors have included estimates for emissions from volcanic activity. In general, these global estimates of sulfur emissions from volcanoes are given as global totals for an ``average`` year. A project has been initiated at Brookhaven National Laboratory to compile inventories of sulfur emissions from volcanoes. In order to complement the GEIA inventories of anthropogenic sulfur emissions, which represent conditions circa specific years, sulfur emissions from volcanoes are being estimated for the years 1985 and 1990.

  14. Multiple oxygen and sulfur isotope compositions of atmospheric sulfate in Baton Rouge, LA, USA

    NASA Astrophysics Data System (ADS)

    Jenkins, Kathryn A.; Bao, Huiming

    Secondary atmospheric sulfates (SAS) is the ultimate oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. Their presence in the atmosphere as aqueous or solid phases contributes to acid rain and climate change, thus, understanding SAS formation pathways is pertinent. There has been extensive measurement of δ34S values for SAS, which mainly aimed at source identification. Relatively fewer oxygen isotope compositions ( δ18O, Δ 17O), which are most useful for resolving competing oxidation pathways, were available, however. This study represents the first effort to characterize the Δ 17O, δ18O, and δ34S simultaneously for SAS in a tropospheric air shed. We measured a total of 20 samples collected in Baton Rouge (LA, USA) during a 600-day period. The isotope compositions for atmospheric sulfate range from +0.25‰ to +1.43‰ for Δ 17O, +11.8‰ to +19.3‰ for δ18O, and -1.4‰ to +3.8‰ for δ34S. No apparent correlation is found among Δ 17O, δ18O, or δ34S values. The Δ 17O has no seasonal variation and its values are consistent with an oxidation pathway dominated by aqueous H 2O 2. The δ18O and δ34S are within the range of those observed in other sites around the world and are not characteristic for Baton Rouge. Despite the huge variability in atmospheric condition among mid-latitude sites, the long-term average Δ 17O value for SAS appears to fall within a fairly narrow range from +0.6‰ to +0.8‰, which is ˜1‰ to 2‰ lower than those in polar sites.

  15. Identification of sources and formation processes of atmospheric sulfate by sulfur isotope and scanning electron microscope measurements

    NASA Astrophysics Data System (ADS)

    Guo, Zhaobing; Li, Zhanqing; Farquhar, James; Kaufman, Alan J.; Wu, Nanping; Li, Can; Dickerson, Russell R.; Wang, Pucai

    2010-04-01

    Atmospheric sulfate aerosols have a cooling effect on the Earth's surface and can change cloud microphysics and precipitation. China has heavy loading of sulfate, but their sources and formation processes remain uncertain. In this study we characterize possible sources and formation processes of atmospheric sulfate by analyzing sulfur isotope abundances (32S, 33S, 34S, and 36S) and by detailed X-ray diffraction and scanning electron microscope (SEM) imaging of aerosol samples acquired at a rural site in northern China from March to August 2005. The comparison of SEM images from coal fly ash and the atmospheric aerosols suggests that direct emission from coal combustion is a substantial source of primary atmospheric sulfate in the form of CaSO4. Airborne gypsum (CaSO4·2H2O) is usually attributed to eolian dust or atmospheric reactions with H2SO4. SEM imaging also reveals mineral particles with soot aggregates adhered to the surface where they could decrease the single scattering albedo of these aerosols. In summer months, heterogeneous oxidation of SO2, derived from coal combustion, appears to be the dominant source of atmospheric sulfate. Our analyses of aerosol sulfate show a seasonal variation in Δ33S (Δ33S describes either a 33S excess or depletion relative to that predicted from consideration of classical mass-dependent isotope effects). Similar sulfur isotope variations have been observed in other atmospheric samples and in (homogenous) gas-phase reactions. On the basis of atmospheric sounding and satellite data as well as a possible relationship between Δ33S and Convective Available Potential Energy (CAPE) during the sampling period, we attribute the sulfur isotope anomalies (Δ33S and Δ36S) in Xianghe aerosol sulfates to another atmospheric source (upper troposphere or lower stratosphere).

  16. Ahead of his time: Jacob Lipman's 1930 estimate of atmospheric sulfur deposition for the conterminous United States

    USGS Publications Warehouse

    Landa, Edward R.; Shanley, James B.

    2015-01-01

    A 1936 New Jersey Agricultural Experiment Station Bulletin provided an early quantitative assessment of atmospheric deposition of sulfur for the United States that has been compared in this study with more recent assessments. In the early 20th century, anthropogenic sulfur additions from the atmosphere to the soil by the combustion of fossil fuels were viewed as part of the requisite nutrient supply of crops. Jacob G. Lipman, the founding editor of Soil Science, and his team at Rutgers University, made an inventory of such additions to soils of the conterminous United States during the economic depression of the 1930s as part of a federally funded project looking at nutrient balances in soils. Lipman's team gathered data compiled by the US Bureau of Mines on coal and other fuel consumption by state and calculated the corresponding amounts of sulfur emitted. Their work pioneered a method of assessment that became the norm in the 1970s to 1980s—when acid rain emerged as a national issue. Lipman's estimate of atmospheric sulfur deposition in the 1930 is in reasonable agreement with recent historic reconstructions.

  17. Atmospheric dry deposition of sulfur and nitrogen in the Athabasca Oil Sands Region, Alberta, Canada.

    PubMed

    Hsu, Yu-Mei; Bytnerowicz, Andrzej; Fenn, Mark E; Percy, Kevin E

    2016-10-15

    Due to the potential ecological effects on terrestrial and aquatic ecosystems from atmospheric deposition in the Athabasca Oil Sands Region (AOSR), Alberta, Canada, this study was implemented to estimate atmospheric nitrogen (N) and sulfur (S) inputs. Passive samplers were used to measure ambient concentrations of ammonia (NH3), nitrogen dioxide (NO2), nitric acid/nitrous acid (HNO3/HONO), and sulfur dioxide (SO2) in the AOSR. Concentrations of NO2 and SO2 in winter were higher than those in summer, while seasonal differences of NH3 and HNO3/HONO showed an opposite trend, with higher values in summer. Concentrations of NH3, NO2 and SO2 were high close to the emission sources (oil sands operations and urban areas). NH3 concentrations were also elevated in the southern portion of the domain indicating possible agricultural and urban emission sources to the southwest. HNO3, an oxidation endpoint, showed wider ranges of concentrations and a larger spatial extent. Concentrations of NH3, NO2, HNO3/HONO and SO2 from passive measurements and their monthly deposition velocities calculated by a multi-layer inference model (MLM) were used to calculate dry deposition of N and S. NH3 contributed the largest fraction of deposited N across the network, ranging between 0.70-1.25kgNha(-1)yr(-1), HNO3/HONO deposition ranged between 0.30-0.90kgNha(-1)yr(-1), and NO2 deposition between 0.03-0.70kgNha(-1)yr(-1). During the modeled period, average dry deposition of the inorganic gaseous N species ranged between 1.03 and 2.85kgNha(-1)yr(-1) and SO4-S deposition ranged between 0.26 and 2.04kgha(-1)yr(-1). Comparisons with co-measured ion exchange resin throughfall data (8.51kgSha(-1)yr(-1)) indicate that modeled dry deposition combined with measured wet deposition (1.37kgSha(-1)yr(-1)) underestimated S deposition. Gas phase NH3 (71%) and HNO3 plus NO2 (79%) dry deposition fluxes dominated the total deposition of NH4-N and NO3-N, respectively. Copyright © 2016 British Geological Survey

  18. Missing SO2 oxidant in the coastal atmosphere? - observations from high-resolution measurements of OH and atmospheric sulfur compounds

    NASA Astrophysics Data System (ADS)

    Berresheim, H.; Adam, M.; Monahan, C.; O'Dowd, C.; Plane, J. M. C.; Bohn, B.; Rohrer, F.

    2014-11-01

    Diurnal and seasonal variations of gaseous sulfuric acid (H2SO4) and methane sulfonic acid (MSA) were measured in NE Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected-ion chemical ionization mass spectrometry (SI/CIMS) with a detection limit for both compounds of 4.3 × 104 cm-3 at 5 min signal integration. The H2SO4 and MSA gas-phase concentrations were analyzed in conjunction with the condensational sink for both compounds derived from 3 nm to 10 μm (aerodynamic diameter) aerosol size distributions. Accommodation coefficients of 1.0 for H2SO4 and 0.12 for MSA were assumed, leading to estimated atmospheric lifetimes on the order of 7 and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH) signal, evidence was obtained for the presence of one or more unknown oxidants of SO2 in addition to OH. Depending on the nature of the oxidant(s), its ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO2 oxidant was additionally confirmed by direct measurements of SO2 in conjunction with calculated H2SO4 concentrations. The calculated H2SO4 concentrations were consistently lower than the measured concentrations by a factor of 4.7 ± 2.4 when considering the oxidation of SO2 by OH as the only source of H2SO4. Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J(O1D), and were followed by peaks in both H2SO4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s), OH chemistry, and the atmospheric photolysis and photooxidation of biogenic iodine compounds. As to the identity of the atmospheric SO2 oxidant(s), we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on {ab initio} calculations

  19. Measurement of Peroxides and Elucidation of Their Behavior in Subtropical Atmosphere

    NASA Astrophysics Data System (ADS)

    Ikota, H.; Arakaki, T.

    2005-12-01

    Peroxides include hydrogen peroxide and organic peroxides. Peroxides oxidize sulfur dioxide in cloud water, and the reaction produces sulfuric acid that causes acid rain and enhances aerosol formation. Thus, understanding behavior of atmospheric peroxides can help understand sources and behavior of aerosols. However, measurement of atmospheric peroxides is still scarce in Japan. We have tried to elucidate the behavior of peroxides in Okinawa Island, Japan. Okinawa Island is located in subtropical climate and close to East Asian countries such as China and Korea. In this study, concentrations of peroxides were determined by p-hydroxyphenyl acetic acid (POHPAA) dimmer technique. Hydrogen peroxide and organic peroxides were separated by a high performance liquid chromatography (HPLC). Atmospheric peroxides were collected by the scrubbing coil method by using phosphoric acid (pH=3.5) as an absorbing solution. We have observed clear diurnal pattern for hydrogen peroxide concentrations; lowest at night and highest at solar noon time. Hydrogen peroxide concentrations ranged from 1.5 to 3.0 ppbv. For organic peroxides, the concentrations were almost constant at 0.5 ppbv all day long. Concentrations of peroxides found in Okinawa Island appeared to be higher than those found in other parts of Japan.

  20. Estimates of the atmospheric deposition of sulfur and nitrogen species: Clean Air Status and Trends Network 1990-2000.

    PubMed

    Baumgardner, Ralph E; Lavery, Thomas F; Rogers, Christopher M; Isil, Selma S

    2002-06-15

    The Clean Air Status and Trends Network (CASTNet) was established by the U.S. EPA in response to the requirements of the 1990 Clean Air Act Amendments. To satisfy these requirements CASTNet was designed to assess and report on geographic patterns and long-term, temporal trends in ambient air pollution and acid deposition in order to gauge the effectiveness of current and future mandated emission reductions. This paper presents an analysis of the spatial patterns of deposition of sulfur and nitrogen pollutants for the period 1990-2000. Estimates of deposition are provided for two 4-yr periods: 1990-1993 and 1997-2000. These two periods were selected to contrast deposition before and after the large decrease in SO2 emissions that occurred in 1995. Estimates of dry deposition were obtained from measurements at CASTNet sites combined with deposition velocities that were modeled using the multilayer model, a 20-layer model that simulates the various atmospheric processes that contribute to dry deposition. Estimates of wet deposition were obtained from measurements at sites operated bythe National Atmospheric Deposition Program. The estimates of dry and wet deposition were combined to calculate total deposition of atmospheric sulfur (dry SO2, dry and wet SO4(2-)) and nitrogen (dry HNO3, dry and wet NO3-, dry and wet NH4+). An analysis of the deposition estimates showed a significant decline in sulfur deposition and no change in nitrogen deposition. The highest rates of sulfur deposition were observed in the Ohio River Valley and downwind states. This region also observed the largest decline in sulfur deposition. The highest rates of nitrogen deposition were observed in the Midwest from Illinois to southern New York State. Sulfur and nitrogen deposition fluxes were significantly higher in the eastern United States as compared to the western sites. Dry deposition contributed approximately 38% of total sulfur deposition and 30% of total nitrogen deposition in the eastern

  1. Early Mars volcanic sulfur storage in the upper cryosphere and formation of transient SO2-rich atmospheres during the Hesperian

    NASA Astrophysics Data System (ADS)

    Schmidt, F.; Chassefière, E.; Tian, F.; Dartois, E.; Herri, J.-M.; Mousis, O.

    2016-11-01

    In a previous paper (Chassefière et al.), we have shown that most volcanic sulfur released to the early Mars atmosphere could have been trapped in the upper cryosphere under the form of CO2-SO2 clathrates. Huge amounts of sulfur, up to the equivalent of an 1 bar atmosphere of SO2, would have been stored in the Noachian upper cryosphere, then massively released to the atmosphere during the Hesperian due to rapidly decreasing CO2 pressure. It could have resulted in the formation of the large sulfate deposits observed mainly in Hesperian terrains, whereas no or little sulfates are found at the Noachian. In the present paper, we first clarify some aspects of our previous work. We discuss the possibility of a smaller cooling effect of sulfur particles, or even of a net warming effect. We point out the fact that CO2-SO2 clathrates formed through a progressive enrichment of a pre-existing reservoir of CO2 clathrates and discuss processes potentially involved in the slow formation of a SO2-rich upper cryosphere. We show that episodes of sudden destabilization at the Hesperian may generate 1000 ppmv of SO2 in the atmosphere and contribute to maintaining the surface temperature above the water freezing point.

  2. Bimodal Distribution of Sulfuric Acid Aerosols in the Atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Gao, Peter; Zhang, X.; Crisp, D.; Bardeen, C. G.; Yung, Y. L.

    2013-10-01

    Observations by the SPICAV/SOIR instruments aboard Venus Express have revealed that the upper haze of Venus, between 70 and 90 km, is variable on the order of days and that it is populated by two particle modes. In this work, we posit that the observed phenomena are caused by the transient mixing of the clouds and the haze, as well as another source of sulfuric acid aerosols in the upper haze that nucleate on meteoric dust. We test this hypothesis by simulating a column of the Venus atmosphere from 40 to 100 km above the surface using a model based upon the Community Aerosol and Radiation Model for Atmospheres and consider the effects of meteoric dust and polysulfur acting as condensation nuclei in the upper haze and upper cloud, respectively, as well as transient winds at the cloud tops caused by subsolar convection. Our aerosol number density results are consistent with Pioneer Venus data from Knollenberg and Hunten (1980), while our gas distribution results match the Magellan radio occultation data as analyzed by Kolodner and Steffes (1998) below 55 km. The size distribution of cloud particles shows two distinct modes in the upper clouds region and three distinct modes in the middle and lower clouds regions, qualitatively matching the observations of Pioneer Venus. The UH size distribution shows one distinct mode that is likely an upwelled cloud particle population with which an in situ meteoric dust condensation particle population has coagulated. The results of the transient wind simulations yield a variability timescale that is consistent with Venus Express observations, as well as a clear bimodal size distribution in the UH.

  3. Atmospheric measurements of carbonyl sulfide, dimethyl sulfide, and carbon disulfide using the electron capture sulfur detector

    NASA Technical Reports Server (NTRS)

    Johnson, James E.; Bates, Timothy S.

    1993-01-01

    Measurements of atmospheric dimethyl sulfide (DMS), carbonyl sulfide (COS), and carbon disulfide (CS2) were conducted over the Atlantic Ocean on board the NASA Electra aircraft during the Chemical Instrumentation Test and Evaluation (CITE 3) project using the electron capture sulfur detector (ECD-S). The system employed cryogenic preconcentration of air samples, gas chromatographic separation, catalytic fluorination, and electron capture detection. Samples collected for DMS analysis were scrubbed of oxidants with NaOH impregnated glass fiber filters to preconcentration. The detection limits (DL) of the system for COS, DMS, and CS2 were 5, 5, and 2 ppt, respectively. COS concentrations ranged from 404 to 603 ppt with a mean of 489 ppt for measurements over the North Atlantic Ocean (31 deg N to 41 deg N), and from 395 to 437 ppt with a mean of 419 ppt for measurements over the Tropical Atlantic Ocean (11 deg S to 2 deg N). DMS concentrations in the lower marine boundary layer, below 600-m altitude, ranged from below DL to 150 ppt from flights over the North Atlantic, and from 9 to 104 ppt over the Tropical Atlantic. CS2 concentrations ranged from below DL to 29 ppt over the North Atlantic. Almost all CS2 measurements over the Tropical Atlantic were below DL.

  4. Sulfur dioxide in the Venus Atmosphere: II. Spatial and temporal variability

    NASA Astrophysics Data System (ADS)

    Vandaele, A. C.; Korablev, O.; Belyaev, D.; Chamberlain, S.; Evdokimova, D.; Encrenaz, Th.; Esposito, L.; Jessup, K. L.; Lefèvre, F.; Limaye, S.; Mahieux, A.; Marcq, E.; Mills, F. P.; Montmessin, F.; Parkinson, C. D.; Robert, S.; Roman, T.; Sandor, B.; Stolzenbach, A.; Wilson, C.; Wilquet, V.

    2017-10-01

    The vertical distribution of sulfur species in the Venus atmosphere has been investigated and discussed in Part I of this series of papers dealing with the variability of SO2 on Venus. In this second part, we focus our attention on the spatial (horizontal) and temporal variability exhibited by SO2. Appropriate data sets - SPICAV/UV nadir observations from Venus Express, ground-based ALMA and TEXES, as well as UV observation on the Hubble Space Telescope - have been considered for this analysis. High variability both on short-term and short-scale are observed. The long-term trend observed by these instruments shows a succession of rapid increases followed by slow decreases in the SO2 abundance at the cloud top level, implying that the transport of air from lower altitudes plays an important role. The origins of the larger amplitude short-scale, short-term variability observed at the cloud tops are not yet known but are likely also connected to variations in vertical transport of SO2 and possibly to variations in the abundance and production and loss of H2O, H2SO4, and Sx.

  5. Disentangling natural and anthropogenic sources of atmospheric sulfur in an industrial region using biomonitors.

    PubMed

    Barros, Ceres; Pinho, Pedro; Durão, Rita; Augusto, Sofia; Máguas, Cristina; Pereira, Maria João; Branquinho, Cristina

    2015-02-17

    Despite reductions in atmospheric sulfur (S) concentrations due to abatement policies in some countries, modeling the dispersion of this pollutant and disentangling anthropogenic sources from natural ones is still of great concern. Lichens have been used as biomonitors of the impacts of S for over 40 years, but their potential as source-tracers of specific sources, including natural ones, remains unexplored. In fact, few attempts have been made to try to distinguish and spatially model different sources of S using lichens. We have measured S concentrations and isotopic values in lichens within an industrial coastal region where different sources of S, natural and anthropogenic, interplay. We detected a prevailing influence of natural sea-originated S that mixed with anthropogenic sources of S. We were then able to disentangle the sources of S, by removing the ocean influence on S isotopic values, enabling us to model the impact of different anthropogenic sources on S deposition and highlighting the potential use of lichens to evaluate the weight of different types of anthropogenic sources.

  6. The impact of particle size, relative humidity, and sulfur dioxide on iron solubility in simulated atmospheric marine aerosols.

    PubMed

    Cartledge, Benton T; Marcotte, Aurelie R; Herckes, Pierre; Anbar, Ariel D; Majestic, Brian J

    2015-06-16

    Iron is a limiting nutrient in about half of the world's oceans, and its most significant source is atmospheric deposition. To understand the pathways of iron solubilization during atmospheric transport, we exposed size segregated simulated marine aerosols to 5 ppm sulfur dioxide at arid (23 ± 1% relative humidity, RH) and marine (98 ± 1% RH) conditions. Relative iron solubility increased as the particle size decreased for goethite and hematite, while for magnetite, the relative solubility was similar for all of the fine size fractions (2.5-0.25 μm) investigated but higher than the coarse size fraction (10-2.5 μm). Goethite and hematite showed increased solubility at arid RH, but no difference (p > 0.05) was observed between the two humidity levels for magnetite. There was no correlation between iron solubility and exposure to SO2 in any mineral for any size fraction. X-ray absorption near edge structure (XANES) measurements showed no change in iron speciation [Fe(II) and Fe(III)] in any minerals following SO2 exposure. SEM-EDS measurements of SO2-exposed goethite revealed small amounts of sulfur uptake on the samples; however, the incorporated sulfur did not affect iron solubility. Our results show that although sulfur is incorporated into particles via gas-phase processes, changes in iron solubility also depend on other species in the aerosol.

  7. Dynamic behavior of the bray-liebhafsky oscillatory reaction controlled by sulfuric acid and temperature

    NASA Astrophysics Data System (ADS)

    Pejić, N.; Vujković, M.; Maksimović, J.; Ivanović, A.; Anić, S.; Čupić, Ž.; Kolar-Anić, Lj.

    2011-12-01

    The non-periodic, periodic and chaotic regimes in the Bray-Liebhafsky (BL) oscillatory reaction observed in a continuously fed well stirred tank reactor (CSTR) under isothermal conditions at various inflow concentrations of the sulfuric acid were experimentally studied. In each series (at any fixed temperature), termination of oscillatory behavior via saddle loop infinite period bifurcation (SNIPER) as well as some kind of the Andronov-Hopf bifurcation is presented. In addition, it was found that an increase of temperature, in different series of experiments resulted in the shift of bifurcation point towards higher values of sulfuric acid concentration.

  8. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

    NASA Astrophysics Data System (ADS)

    Babikov, Dmitri

    2017-03-01

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: 33S, 34S, and 36S. Interestingly, the ratio of capital ΔΔ values obtained within this model for 33S and 36S is -1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth.

  9. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

    PubMed Central

    Babikov, Dmitri

    2017-01-01

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: 33S, 34S, and 36S. Interestingly, the ratio of capital Δ values obtained within this model for 33S and 36S is −1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth. PMID:28258172

  10. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth.

    PubMed

    Babikov, Dmitri

    2017-03-21

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: (33)S, (34)S, and (36)S. Interestingly, the ratio of capital [Formula: see text] values obtained within this model for (33)S and (36)S is -1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth.

  11. Application of Atmospheric Pressure Photoionization H/D-exchange Mass Spectrometry for Speciation of Sulfur-containing Compounds.

    PubMed

    Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Ha, Ji-Hyoung; Kim, Sunghwan

    2017-08-01

    Herein we report the observation of atmospheric pressure in-source hydrogen-deuterium exchange (HDX) of thiol group for the first time. The HDX for thiol group was optimized for positive atmospheric pressure photoionization (APPI) mass spectrometry (MS). The optimized HDX-MS was applied for 31 model compounds (thiols, thiophenes, and sulfides) to demonstrate that exchanged peaks were observed only for thiols. The optimized method has been successfully applied to the isolated fractions of sulfur-rich oil samples. The exchange of one and two thiol hydrogens with deuterium was observed in the thiol fraction; no HDX was observed in the other fractions. Thus, the results presented in this study demonstrate that the HDX-MS method using APPI ionization source can be effective for speciation of sulfur compounds. This method has the potential to be used to access corrosion problems caused by thiol-containing compounds. Graphical Abstract ᅟ.

  12. Application of Atmospheric Pressure Photoionization H/D-exchange Mass Spectrometry for Speciation of Sulfur-containing Compounds

    NASA Astrophysics Data System (ADS)

    Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Ha, Ji-Hyoung; Kim, Sunghwan

    2017-08-01

    Herein we report the observation of atmospheric pressure in-source hydrogen-deuterium exchange (HDX) of thiol group for the first time. The HDX for thiol group was optimized for positive atmospheric pressure photoionization (APPI) mass spectrometry (MS). The optimized HDX-MS was applied for 31 model compounds (thiols, thiophenes, and sulfides) to demonstrate that exchanged peaks were observed only for thiols. The optimized method has been successfully applied to the isolated fractions of sulfur-rich oil samples. The exchange of one and two thiol hydrogens with deuterium was observed in the thiol fraction; no HDX was observed in the other fractions. Thus, the results presented in this study demonstrate that the HDX-MS method using APPI ionization source can be effective for speciation of sulfur compounds. This method has the potential to be used to access corrosion problems caused by thiol-containing compounds.

  13. Effect of various alkaline metal ions on electrochemical behavior of lead electrode in sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Hirai, Nobumitsu; Yamamoto, Yui

    2015-10-01

    The effect of various alkaline metal ions on electrochemical behavior of lead electrode in sulfuric acid solution has been investigated. It was found that ;the specific anodic oxidation peak; appears at the cathodic scan in cyclic voltammogram of lead electrode in sulfuric acid solution containing Li2SO4, K2SO4, Na2SO4, Rb2SO4, or Cs2SO4. The height of the specific anodic oxidation peak varies with the alkaline sulfate in the solution; K2SO4 >> Na2SO4 > Cs2SO4 > Rb2SO4 > Li2SO4. It should be note that alkaline ions exist in lead sulfate formed on lead electrode in sulfuric acid solution containing potassium sulfate when the electrode was immersed in the solution at the rest potential for more than 1 h.

  14. Submillimeter spectroscopy of Venus's atmosphere with ALMA: CO, HDO and sulfur species

    NASA Astrophysics Data System (ADS)

    Moullet, Arielle; Moreno, R.; Encrenaz, T.; Lellouch, E.; Fouchet, T.

    2013-10-01

    The study of the composition of the upper mesosphere of Venus is necessary to characterize several atmospheric processes such as photochemistry, condensation and dynamics. At this altitude level (80-110 km), several species have been detected thanks to their (sub)millimeter rotational lines, in particular sulfur species SO2 and SO, that may be indicative of Venus' volcanic activity, and showed an abundance increase with altitude suggesting a local sulfur-bearing aerosol source[1,2]. H2O, which takes part in the formation of H2SO4 clouds, was also detected as well as its isotope HDO; their analyses revealed significant diurnal and long-term temporal variations [3,4]. To explore this case in greater detail and better assess local, diurnal and temporal variations of minor species, heterodyne spectroscopic observations were obtained in November 2011 during the first Early Science observation cycle of the Atacama Large Millimeter Array (ALMA), the largest (sub)millimeter interferometer, which at the time offered 16 12-m large antennas. These observations allowed us to map the day side of Venus with a spatial resolution down to 1.2-2.4"" (for a disk of 11"), targeting SO2, SO, HDO and CO transitions around 0.85mm (335-346 GHz). All of these transitions were well detected and their modeling yielded abundances consistent with previous single-dish assessments. We will present a detailed analysis of the data in terms of spatial distribution (horizontal and vertical) and temporal variations, and we will discuss their interpretation with regard to the efficiency of photochemical destruction in the mesosphere and aerosol sources. In addition, by mapping the CO(3-2) line's Doppler-shifts, we have been able to derive the wind field near the upper boundary of the mesosphere, whichs corresponds to a region of dynamic transition between the retrograde zonal wind regime of the troposphere and the subsolar-to-antisolar flow that dominates at higher altitudes. [1] Sandor et al., 2010

  15. The carbon and sulfur cycles and atmospheric oxygen from middle Permian to middle Triassic

    NASA Astrophysics Data System (ADS)

    Berner, Robert A.

    2005-07-01

    The results of a theoretical isotope mass balance model are presented for the time dependence of burial and weathering-plus-degassing fluxes within the combined long-term carbon and sulfur cycles. Averaged data for oceanic δ 13C and δ 34S were entered for every million years from 270 to 240 Ma (middle Permian to middle Triassic) to study general trends across the Permian-Triassic boundary. Results show a drop in the rate of global organic matter burial during the late Permian and a predominance of low values during the early-to-middle Triassic. This overall decrease with time is ascribed mainly to epochs of conversion of high biomass forests to low biomass herbaceous vegetation resulting in a decrease in the production of terrestrially derived organic debris. Additional contributions to lessened terrestrial carbon burial were increased aridity and a drop in sea level during the late Permian which led to smaller areas of low-lying coastal wetlands suitable for coal and peat deposition. Mirroring the drop in organic matter deposition was an increase in the burial of sedimentary pyrite, and a dramatic increase in the calculated global mean ratio of pyrite-S to organic-C. High S/C values resulted from an increase of deposition in marine euxinic basins combined with a decrease in the burial of low-pyrite associated terrestrial organic matter. The prediction of increased oceanic anoxia during the late Permian and early Triassic agrees with independent studies of the composition of sedimentary rocks. Weathering plus burial fluxes for organic carbon and pyrite sulfur were used to calculate changes in atmospheric oxygen. The striking result is a continuous drop in O 2 concentration from ˜30% to ˜13% over a twenty million year period. This drop was brought about mainly by a decrease in the burial of terrestrially derived organic matter. but with a possible contribution from the weathering of older organic matter on land. It must have exerted a considerable influence on

  16. Atmospheric behavior of the Chelyabinsk impactor

    NASA Astrophysics Data System (ADS)

    Borovička, J.; Spurný, P.; Brown, P.; Kalenda, P.; Shrbený, L.

    2014-07-01

    containing thermal hot spots, which retained their forward momentum and continued the flight in the original asteroid direction after formation. The usual assumption that the positions of dust concentrations are identical with the fragmentation points proved invalid in the case of Chelyabinsk. The nature of the hot spots will be discussed. The fragmentation analysis confirms that the Chelyabinsk asteroid was not a rubble pile, which would be expected to disintegrate under the atmospheric ram pressures experienced in the beginning of entry. On the other hand, Chelyabinsk was not a particularly strong body. About 95 % of mass was lost at heights above 30 km under the action of dynamic pressure less than 5 MPa. In many respects, the Chelyabinsk fragmentation resembles the fragmentation behavior exhibited by the Košice meteoroid (H5 chondrite, 1 meter size) [5]. Both events were characterized by catastrophic disruption above the height of 30 km and the survival of only a few large pieces in addition to numerous small meteorites. Since the bulk strength and fragmentation behavior of meter-sized objects varies from case to case [6], we do not expect that all Chelyabinsk-sized impactors will behave similarly.

  17. Influence of cell voltage and current on sulfur poisoning behavior of solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Cheng, Zhe; Zha, Shaowu; Liu, Meilin

    The sulfur poisoning behavior of nickel-yttria stabilized zirconia (YSZ) cermet anodes in solid oxide fuel cells (SOFCs) was investigated under both potentiostatic and galvanostatic conditions. While the observed relative drop in cell power output caused by sulfur poisoning decreases as the cell-terminal voltage is lowered potentiostatically (thus more current passing through the cell), it increases as more current is drawn from the cell galvanostatically (thus leading to lower terminal voltage). The apparent contradictory trends in relative performance loss due to sulfur poisoning are explained using a simple equivalent circuit analysis, which was further validated by impedance measurements of cells before and after poisoning by trace amounts of hydrogen sulfide (H 2S) under different conditions. Results suggest that the relative increase in cell internal resistance caused by sulfur poisoning is smaller when more current is drawn from the cell (or the cell-terminal voltage is lowered) under either potentiostatic or galvanostatic conditions. Thus, the increase in anode polarization resistance, not the drop in cell power output, should be used to describe the degree of sulfur poisoning in order to avoid any confusion.

  18. Effect of tritium on corrosion behavior of chromium in 0.01 N sulfuric acid solution

    SciTech Connect

    Oyaidzu, M.; Isobe, K.; Hayashi, T.

    2015-03-15

    The effects of tritium on the corrosion behavior of chromium in 0.01 N sulfuric solution have been investigated in the present study. Electrochemical experiments have been carried our for pure chromium. At first, the concentration dependence of sulfuric acid solution on anodic polarization behavior of chromium was experimented, resulting in that 0.01 N one was found appropriate. The dependence of both dissolved oxygen and tritium concentration on anodic behavior of chromium were performed. It was found from that the self-passivation of chromium induced by dissolved oxygen was inhibited in tritiated solution resulting in the enhancement of the corrosion. As a consequence it is highly likely that the elution of chromium by highly oxidative radiolysis products would explain the passivation inhibitory effect of SUS304 stainless steel observed in tritiated solutions.

  19. A Kinetic Study of the Gas Phase Neutral-Neutral Reactions Between Sulfur- and Chlorine-Containing Molecules Present in the Atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Maffucci, D. M.; Woon, D. E.; Herbst, E.

    2017-05-01

    Using updated electronic structures, we employ a variety of kinetic theories to calculate the reaction rate constants for neutral-neutral chemical reactions between sulfur- and chlorine-containing molecules observed in the atmosphere of Venus.

  20. Boreal Forest Fires - Behavior and Atmospheric Impacts

    NASA Astrophysics Data System (ADS)

    Stocks, B. J.

    2003-12-01

    behavior on the ground, presenting a solid opportunity for mutually-beneficial collaboration between atmospheric modelers and the wildland fire research community.

  1. Sulfur Nanowires

    NASA Astrophysics Data System (ADS)

    Carvajal, Eliel; Santiago, Patricia; Escudero, Roberto; Mendoza, Doroteo

    2000-03-01

    We have synthetized sulfur nanowires by a template approach using nanoporous anodic alumina. High resolution electron microscopy shows that isolated sulfur nanowires (15 nanometers of diameter) present crystalline structure different to that observed in the stable bulk allotrope (orthorhombic alfa-sulfur). Melting behavior of the sulfur nanowires embedded into the nanoporous alumina matrix was studied by differential scanning calorimetry, showing again very different behavior of the nanowires compared to that of the bulk sulfur. On the other hand, in order to study the bonding configuration of the sulfur atoms in the nanowires, we will present infrared spectroscopy characterization of the nanowires confined into the nanoporous alumina. Finally, on the base of the experimental observations, we will present a structural model for the sulfur nanowires.

  2. Sulfur, Chlorine, and Flourine Degassing and Atmospheric Loading by the 1783 - 1784 AD Laki (Skaftar Fires) Eruption in Iceland

    NASA Technical Reports Server (NTRS)

    Thordarson, T.; Self, S.; Hulsebosch, T.; Oskarsson, N.; McPhie, Jocelyn (Editor)

    1996-01-01

    The 1783-1784 Laki tholeiitic basalt fissure eruption in Iceland was one of the greatest atmospheric pollution events of the past 250 years, with widespread effects in the northern hemisphere. The degassing history and volatile budget of this event are determined by measurements of pre-eruption and residual contents of sulfur, chlorine, and fluorine in the products of all phases of the eruption. In fissure eruptions such as Laki, degassing occurs in two stages: by explosive activity or lava fountaining at the vents, and from the lava as it flows away from the vents. Using the measured sulfur concentrations in glass inclusions in phenocrysts and in groundmass glasses of quenched eruption products, we calculate that the total accumulative atmospheric mass loading of sulfur dioxide was 122 Mt over a period of 8 months. This volatile release is sufficient to have generated approximately 250 Mt of H2SO4 aerosols, an amount which agrees with an independent estimate of the Laki aerosol yield based on atmospheric turbidity measurements. Most of this volatile mass (approximately 60 wt.%) was released during the first 1.5 months of activity. The measured chlorine and fluorine concentrations in the samples indicate that the atmospheric loading of hydrochloric acid and hydrofluoric acid was approximately 7.0 and 15.0 Mt, respectively. Furthermore, approximately 75% of the volatile mass dissolved by the Laki magma was released at the vents and carried by eruption columns to altitudes between 6 and 13 km. The high degree of degassing at the vents is attributed to development of a separated two-phase flow in the upper magma conduit, and implies that high-discharge basaltic eruptions such as Laki are able to loft huge quantities of gas to altitudes where the resulting aerosols can reside for months, or even 1-2 years. The atmospheric volatile contribution due to subsequent degassing of the Laki lava flow is only 18 wt.% of the total dissolved in the magma, and these emissions were

  3. Riverine Response of Sulfate to Declining Atmospheric Sulfur Deposition in Agricultural Watersheds.

    PubMed

    David, Mark B; Gentry, Lowell E; Mitchell, Corey A

    2016-07-01

    Sulfur received extensive study as an input to terrestrial ecosystems from acidic deposition during the 1980s. With declining S deposition inputs across the eastern United States, there have been many studies evaluating ecosystem response, with the exception of agricultural watersheds. We used long-term (22 and 18 yr) sulfate concentration data from two rivers and recent (6 yr) data from a third river to better understand cycling and transport of S in agricultural, tile-drained watersheds. Sulfate concentrations and yields steadily declined in the Embarras (from ∼10 to 6 mg S L) and Kaskaskia rivers (from 7 to 3.5 mg S L) during the sampling period, with an overall -23.1 and -12.8 kg S ha yr balance for the two watersheds. There was evidence of deep groundwater inputs of sulfate in the Salt Fork watershed, with a much smaller input to the Embarras and none to the Kaskaskia. Tiles in the watersheds had low sulfate concentrations (<10 mg S L), similar to the Kaskaskia River, unless the field had received some form of S fertilizer. A multiple regression model of runoff (cm) and S deposition explained much of the variation in Embarras River sulfate ( = 0.86 and 0.80 for concentrations and yields; = 46). Although atmospheric deposition was much less than outputs (grain harvest + stream export of sulfate), riverine transport of sulfate reflected the decline in inputs. Watershed S balances suggest a small annual depletion of soil organic S pools, and S fertilization will likely be needed at some future date to maintain crop yields.

  4. Atmospheric wet deposition of sulfur and nitrogen in Jiuzhaigou National Nature Reserve, Sichuan Province, China.

    PubMed

    Qiao, Xue; Xiao, Weiyang; Jaffe, Daniel; Kota, Sri Harsha; Ying, Qi; Tang, Ya

    2015-04-01

    In the last two decades, remarkable ecological changes have been observed in Jiuzhaigou National Nature Reserve (JNNR). Some of these changes might be related to excessive deposition of sulfur (S) and nitrogen (N), but the relationship has not been quantified due to lack of monitoring data, particularly S and N deposition data. In this study, we investigated the concentrations, fluxes, and sources of S and N wet deposition in JNNR from April 2010 to May 2011. The results show that SO4(2-), NO3-, and NH4+ concentrations in the wet deposition were 39.4-170.5, 6.2-34.8, and 0.2-61.2 μeq L(-1), with annual Volume-Weighted Mean (VWM) concentrations of 70.5, 12.7, and 13.4 μeq L(-1), respectively. Annual wet deposition fluxes of SO4(2-), NO3-, and NH4+ were 8.06, 1.29, and 1.39 kg S(N)ha(-1), respectively, accounting for about 90% of annual atmospheric inputs of these species at the monitoring site. The results of Positive Matrix Factorization (PMF) analysis show that fossil fuel combustion, agriculture, and aged sea salt contributed to 99% and 83% of annual wet deposition fluxes of SO4(2-) and NO3-, respectively. Agriculture alone contributed to 89% of annual wet deposition flux of NH4+. Although wet deposition in JNNR was polluted by anthropogenic acids, the acidity was largely neutralized by the Ca2+ from crust and 81% of wet deposition samples had a pH higher than 6.00. However, acid rain mainly caused by SO4(2-) continued to occur in the wet season, when ambient alkaline dust concentration was lower. Since anthropogenic emissions have elevated S and N deposition and caused acid rain in JNNR, further studies are needed to better quantify the regional sources and ecological effects of S and N deposition for JNNR.

  5. Atmospheric record in the Hadean Eon from multiple sulfur isotope measurements in Nuvvuagittuq Greenstone Belt (Nunavik, Quebec).

    PubMed

    Thomassot, Emilie; O'Neil, Jonathan; Francis, Don; Cartigny, Pierre; Wing, Boswell A

    2015-01-20

    Mass-independent fractionation of sulfur isotopes (S-MIF) results from photochemical reactions involving short-wavelength UV light. The presence of these anomalies in Archean sediments [(4-2.5 billion years ago, (Ga)] implies that the early atmosphere was free of the appropriate UV absorbers, of which ozone is the most important in the modern atmosphere. Consequently, S-MIF is considered some of the strongest evidence for the lack of free atmospheric oxygen before 2.4 Ga. Although temporal variations in the S-MIF record are thought to depend on changes in the abundances of gas and aerosol species, our limited understanding of photochemical mechanisms complicates interpretation of the S-MIF record in terms of atmospheric composition. Multiple sulfur isotope compositions (δ(33)S, δ(34)S, and δ(36)S) of the >3.8 billion-year-old Nuvvuagittuq Greenstone Belt (Ungava peninsula) have been investigated to track the early origins of S-MIF. Anomalous S-isotope compositions (Δ(33)S up to +2.2‰) confirm a sedimentary origin of sulfide-bearing banded iron and silica-rich formations. Sharp isotopic transitions across sedimentary/igneous lithological boundaries indicate that primary surficial S-isotope compositions have been preserved despite a complicated metamorphic history. Furthermore, Nuvvuagittuq metasediments recorded coupled variations in (33)S/(32)S, (34)S/(32)S, and (36)S/(32)S that are statistically indistinguishable from those identified several times later in the Archean. The recurrence of the same S-isotope pattern at both ends of the Archean Eon is unexpected, given the complex atmospheric, geological, and biological pathways involved in producing and preserving this fractionation. It implies that, within 0.8 billion years of Earth's formation, a common mechanism for S-MIF production was established in the atmosphere.

  6. Atmospheric record in the Hadean Eon from multiple sulfur isotope measurements in Nuvvuagittuq Greenstone Belt (Nunavik, Quebec)

    PubMed Central

    Thomassot, Emilie; O’Neil, Jonathan; Francis, Don; Cartigny, Pierre; Wing, Boswell A.

    2015-01-01

    Mass-independent fractionation of sulfur isotopes (S-MIF) results from photochemical reactions involving short-wavelength UV light. The presence of these anomalies in Archean sediments [(4–2.5 billion years ago, (Ga)] implies that the early atmosphere was free of the appropriate UV absorbers, of which ozone is the most important in the modern atmosphere. Consequently, S-MIF is considered some of the strongest evidence for the lack of free atmospheric oxygen before 2.4 Ga. Although temporal variations in the S-MIF record are thought to depend on changes in the abundances of gas and aerosol species, our limited understanding of photochemical mechanisms complicates interpretation of the S-MIF record in terms of atmospheric composition. Multiple sulfur isotope compositions (δ33S, δ34S, and δ36S) of the >3.8 billion-year-old Nuvvuagittuq Greenstone Belt (Ungava peninsula) have been investigated to track the early origins of S-MIF. Anomalous S-isotope compositions (Δ33S up to +2.2‰) confirm a sedimentary origin of sulfide-bearing banded iron and silica-rich formations. Sharp isotopic transitions across sedimentary/igneous lithological boundaries indicate that primary surficial S-isotope compositions have been preserved despite a complicated metamorphic history. Furthermore, Nuvvuagittuq metasediments recorded coupled variations in 33S/32S, 34S/32S, and 36S/32S that are statistically indistinguishable from those identified several times later in the Archean. The recurrence of the same S-isotope pattern at both ends of the Archean Eon is unexpected, given the complex atmospheric, geological, and biological pathways involved in producing and preserving this fractionation. It implies that, within 0.8 billion years of Earth’s formation, a common mechanism for S-MIF production was established in the atmosphere. PMID:25561552

  7. Sulfur in Earth's Mantle and Its Behavior During Core Formation

    NASA Technical Reports Server (NTRS)

    Chabot, Nancy L.; Righter,Kevin

    2006-01-01

    The density of Earth's outer core requires that about 5-10% of the outer core be composed of elements lighter than Fe-Ni; proposed choices for the "light element" component of Earth's core include H, C, O, Si, S, and combinations of these elements [e.g. 1]. Though samples of Earth's core are not available, mantle samples contain elemental signatures left behind from the formation of Earth's core. The abundances of siderophile (metal-loving) elements in Earth's mantle have been used to gain insight into the early accretion and differentiation history of Earth, the process by which the core and mantle formed, and the composition of the core [e.g. 2-4]. Similarly, the abundance of potential light elements in Earth's mantle could also provide constraints on Earth's evolution and core composition. The S abundance in Earth's mantle is 250 ( 50) ppm [5]. It has been suggested that 250 ppm S is too high to be due to equilibrium core formation in a high pressure, high temperature magma ocean on early Earth and that the addition of S to the mantle from the subsequent accretion of a late veneer is consequently required [6]. However, this earlier work of Li and Agee [6] did not parameterize the metalsilicate partitioning behavior of S as a function of thermodynamic variables, limiting the different pressure and temperature conditions during core formation that could be explored. Here, the question of explaining the mantle abundance of S is revisited, through parameterizing existing metal-silicate partitioning data for S and applying the parameterization to core formation in Earth.

  8. Estimating Sulfur hexafluoride (SF6) emissions in China using atmospheric observations and inverse modeling

    NASA Astrophysics Data System (ADS)

    Fang, X.; Thompson, R.; Saito, T.; Yokouchi, Y.; Li, S.; Kim, J.; Kim, K.; Park, S.; Graziosi, F.; Stohl, A.

    2013-12-01

    With a global warming potential of around 22800 over a 100-year time horizon, sulfur hexafluoride (SF6) is one of the greenhouse gases regulated under the Kyoto Protocol. Global SF6 emissions have been increasing since circa the year 2000. The reason for this increase has been inferred to be due to rapidly increasing emissions in developing countries that are not obligated to report their annual emissions to the United Nations Framework Convention on Climate Change, notably China. In this study, SF6 emissions during the period 2006-2012 for China and other East Asian countries were determined using in-situ atmospheric measurements and inverse modeling. We performed various inversion sensitivity tests, which show the largest uncertainties in the a posteriori Chinese emissions are associated with the a priori emissions used and their uncertainty, the station network, as well as the meteorological input data. The overall relative uncertainty of the a posteriori emissions in China is estimated to be 17% in 2008. Based on sensitivity tests, we employed the optimal parameters in our inversion setup and performed yearly inversions for the study period. Inversion results show that the total a posteriori SF6 emissions from China increased from 1420 × 245 Mg/yr in 2006 to 2741 × 472 Mg/yr in 2009 and stabilized thereafter. The rapid increase in emissions reflected a fast increase in SF6 consumption in China, a result also found in bottom-up estimates. The a posteriori emission map shows high emissions concentrated in populated parts of China. During the period 2006-2012, emissions in northwestern and northern China peaked around the year 2009, while emissions in eastern, central and northeastern China grew gradually during almost the whole period. Fluctuating emissions are observed for southwestern China. These regional differences should be caused by changes of provincial SF6 usage and by shifts of usage among different sectors. Fig. 1. Footprint emission sensitivity

  9. Multiple oxygen and sulfur isotopic analyses on water-soluble sulfate in bulk atmospheric deposition from the southwestern United States

    USGS Publications Warehouse

    Bao, H.; Reheis, M.C.

    2003-01-01

    Sulfate is a major component of bulk atmospheric deposition (including dust, aerosol, fog, and rain). We analyzed sulfur and oxygen isotopic compositions of water-soluble sulfate from 40 sites where year-round dust traps collect bulk atmospheric deposition in the southwestern United States. Average sulfur and oxygen isotopic compositions (??34S and ??18O) are 5.8 ?? 1.4 (CDT) and 11.2 ?? 1.9 (SMOW) (n = 47), respectively. Samples have an oxygen 17 anomaly (?? 17O), with an average value of 1.0 ?? 0.6???. Except for a weak positive correlation between ??18O and ??17O values (r2 ??? 0.4), no correlation exists for ??18O versus ??34S, ?? 17O versus ??34S, or any of the three isotopic compositions versus elevation of the sample site. Exceptional positive ?? 17O values (up to 4.23???) are found in samples from sites in the vicinity of large cities or major highways, and near-zero ?? 17O values are found in samples close to dry lakes. Comparison of isotopic values of dust trap sulfate and desert varnish sulfate from the region reveals that varnish sulfate has average isotopic values that are ???4.8??? lower for ??18O, ???2.1??? higher for ??34S , and ???0.3??? lower for ?? 17O than those of the present-day bulk deposition sulfate. Although other factors could cause the disparity, this observation suggests a possibility that varnish sulfate may have recorded a long-term atmospheric sulfate deposition during the Holocene or Pleistocene, as well as the differences between sulfur and oxygen isotopic compositions of the preindustrial bulk deposition sulfate and those of the industrial era.

  10. Spatial distribution and seasonal variations of atmospheric sulfur deposition over Northern China

    NASA Astrophysics Data System (ADS)

    Pan, Y. P.; Wang, Y. S.; Tang, G. Q.; Wu, D.

    2012-09-01

    The increasing anthropogenic emissions of acidic compounds have induced acid deposition accompanied by acidification in the aquatic and terrestrial ecosystems worldwide. However, comprehensive assessment of spatial patterns and long-term trends of acid deposition in China remains a challenge due to a paucity of field-based measurement data, in particular for dry deposition. Here we quantify the sulfur (S) deposition on a regional scale via precipitation, particles and gases during a 3-yr observation campaign at ten selected sites in Northern China. Results show that the total S deposition flux in the target area ranged from 35.0 to 100.7 kg S ha-1 yr-1, categorized as high levels compared to those documented in Europe, North America, and East Asia. The ten-site, 3-yr average total S deposition was 64.8 kg S ha-1 yr-1, with 32% attributed to wet deposition, and the rest attributed to dry deposition. Compared with particulate sulfate, gaseous SO2 was the major contributor of dry-deposited S, contributing approximately 49% to the total flux. Wet deposition of sulfate showed pronounced seasonal variations with maximum in summer and minimum in winter, corresponding to precipitation patterns in Northern China. However, the spatial and inter-annual differences in the wet deposition were not significant, which were influenced by the precipitation amount, scavenging ratio and the concentrations of atmospheric S compounds. In contrast, the relatively large dry deposition of SO2 and sulfate during cold season, especially at industrial areas, was reasonably related to the local emissions from home heating. Although seasonal fluctuations were constant, clear spatial differences were observed in the total S deposition flux and higher values were also found in industrial areas with huge emissions of SO2. These findings indicate that human activity has dramatically altered the atmospheric S deposition and thus regional S cycles. To systematically illustrate the potential effects

  11. Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere

    PubMed Central

    Muller, Élodie; Philippot, Pascal; Rollion-Bard, Claire; Cartigny, Pierre

    2016-01-01

    Sulfur isotopic anomalies (∆33S and ∆36S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ34S values at ∼+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆33S between −1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ34S peak at +9‰ is associated with non–33S-anomalous barites displaying negative ∆36S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere. PMID:27330111

  12. Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere

    NASA Astrophysics Data System (ADS)

    Muller, Élodie; Philippot, Pascal; Rollion-Bard, Claire; Cartigny, Pierre

    2016-07-01

    Sulfur isotopic anomalies (∆33S and ∆36S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ34S values at ˜+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆33S between -1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ34S peak at +9‰ is associated with non-33S-anomalous barites displaying negative ∆36S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere.

  13. Atmospheric depositional fluxes of cosmogenic 35S and 7Be: Implications for the turnover rate of sulfur through the biosphere

    NASA Astrophysics Data System (ADS)

    Cho, Hyung-Mi; Hong, Young-Lim; Kim, Guebuem

    2011-08-01

    The wet depositional fluxes of cosmogenic 35S and 7Be, together with 210Pb, were measured in Seoul, Korea, from April 2004 to April 2005. Approximately half of the annual fluxes occurred in summer, during which about 60% of the precipitations occurred. Our simple box model shows that the theoretical scavenging ratio of 35S/ 7Be to the ground is approximately 0.013, which accounts for the decay for the duration of oxidation and settling. However, we observed ˜50% higher 35S/ 7Be activity ratios than the theoretical removal ratio over the entire sampling period, with particularly higher (˜133%) ratios during November 2004-April 2005. These higher ratios in the winter cannot be explained by sudden incursions of the stratospheric air or longer aerosol residence times, on the basis of 7Be/ 210Pb ratios. We hypothesize that the ratios could occur owing to biomass burning or as plants go dormant and dry during the autumn and winter. Based on this hypothesis, we developed a 35S/ 7Be mass balance model which yields the turnover rate of sulfur in the atmosphere through the biosphere to be 0.015 ± 0.007 d -1. Such a rapid sulfur turnover rate should be applied to the prediction model of sulfur inventory changes.

  14. Development of a pretreatment system for the analysis of atmospheric reduced sulfur compounds.

    PubMed

    Son, Youn-Suk; Lee, Gangwoong; Kim, Jo-Chun; Han, Jin-Seok

    2013-11-05

    A new pretreatment system was used to evaluate a technology to analyze reduced sulfur compounds (RSCs). To conduct this research, a self-developed custom dryer (Desolvator) and a thermal desorber system (TDS) were installed in the front of GC/PFPD. The syringe pump inside the TDS was devised in such a way that it can be desorbed in a relatively low desorption temperature and low vacuum (730 Pa). When comparing water removal efficiency of the Desolvator and frequently used Nafion dryer, the removal efficiency of the Desolvator stood between 94.6 and 96.1%, considerably higher and more stable than the Nafion dryer (81.3-94.5%). Moreover, analyses were made under various conditions in order to minimize the loss of samples when analyzing sulfur compounds using the TDS, and it was determined that adsorption temperatures less than -25 °C and a flow rate of 50 mL/min were appropriate for the efficient analysis of these sulfur compounds. Moreover, the desorption flow rate and the degree of a vacuum were found to be significant variables for the RSCs desorption. Besides, it was observed that a peculiar peak was formed by thermal decomposition when some sulfur compounds were rapidly desorbed at high desorption temperatures.

  15. Atmospheric Sulfur Dioxide in the United States: Can the Standards be Justified or Afforded?

    ERIC Educational Resources Information Center

    Megonnell, William H.

    1975-01-01

    Recent reviews have concluded that there is no basis for changing the standards set by the EPA in 1971, even though the data base was insufficient then for a quantifiable, scientific definition of clean air. Examination of data shows that the United States does not have a sulfur dioxide problem. (Author/BT)

  16. Atmospheric Sulfur Dioxide in the United States: Can the Standards be Justified or Afforded?

    ERIC Educational Resources Information Center

    Megonnell, William H.

    1975-01-01

    Recent reviews have concluded that there is no basis for changing the standards set by the EPA in 1971, even though the data base was insufficient then for a quantifiable, scientific definition of clean air. Examination of data shows that the United States does not have a sulfur dioxide problem. (Author/BT)

  17. Regional source identification of atmospheric aerosols in Beijing based on sulfur isotopic compositions

    NASA Astrophysics Data System (ADS)

    Lianfang, Wei; Pingqing, Fu; Xiaokun, Han; Qingjun, Guo; Yele, Sun; Zifa, Wang

    2016-04-01

    65 daily PM2.5 (aerosol particle with aerodynamic diameter less than 2.5 μm) samples were collected from an urban site in Beijing in four months representing the four seasons between September 2013 and July 2014. Inorganic ions, organic/elemental carbon and stable sulfur isotopes of sulfate aerosols were analyzed systematically. The "fingerprint" characteristics of the stable sulfur isotopic composition, together with trajectory clustering modeled by HYSPLIT-4 and potential source contribution function (PSCF), were employed for identifying potential regional sources. Results obviously exhibited the distinctive seasonality for various aerosol speciation associated with PM2.5 in Beijing with sulfate, nitrate, ammonium, organic matter, and element carbon being the dominant species. Elevated chloride associated with higher concentration of organics were found in autumn and winter, due to enhanced coal combustion emissions. The δ34S values of Beijing aerosol samples ranged from 2.94‰ to 10.2‰ with an average value of 6.18±1.87‰ indicating that the major sulfur source is direct fossil fuel burning-related emissions. Owning to a temperature-dependent fractionation and elevated biogenic sources of isotopically light sulfur in summer, the δ34S values had significant seasonal variations with a winter maximum ( 8.6‰)and a summer minimum ( 5.0‰). The results of trajectory clustering and the PSCF method demonstrated that higher concentrations of sulfate with lower sulfur isotope ratios ( 4.83‰) were associated with air masses from the south, southeast or east, whereas lower sulfate concentrations with higher δ34S values ( 6.69‰) when the air masses were mainly from north or northwest. These results suggested two main different kinds of regional coal combustion sources contributed to the pollution in Beijing.

  18. Sulfur dioxide and other cloud-related gases as the source of the microwave opacity of the middle atmosphere of Venus

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.; Eshleman, V. R.

    1981-01-01

    Spacecraft radio occultation measurements imply the presence of a nonuniformly mixed gaseous absorber within, but mostly below, the main cloud layer of sulfuric acid-water droplets measured by Pioneer-Venus. Preliminary considerations of the amount, distribution, and effects of sulfur dioxide and other gases, which apparently are associated with and produce the cloud, indicate that they constitute an important, and probably the predominant, source of the observed microwave opacity of the middle atmosphere of Venus.

  19. Observation of wavelength-sensitive mass-independent sulfur isotope effects during SO2 photolysis: Implications for the early atmosphere

    NASA Astrophysics Data System (ADS)

    Farquhar, James; Savarino, Joel; Airieau, Sabine; Thiemens, Mark H.

    2001-12-01

    Mass-independent isotopic signatures for δ33S, δ34S, and δ36S produced in the photolysis of sulfur dioxide exhibit a strong wavelength dependence. Photolysis experiments with three light sources (ArF excimer laser (193 nm), mercury resonance lamp (184.9 and 253.7 nm), and KrF excimer laser (248 nm) are presented. Products of sulfur dioxide photolysis undertaken with 193-nm radiation exhibit characteristics that are similar to sulfur multiple-isotope data for terrestrial sedimentary rock samples older than 2450 Ma (reported by Farquhar et al. [2000a]), while photolysis experiments undertaken with radiation at other wavelengths (longer than 220 nm and at 184.9 nm) exhibit different characteristics. The spectral window between 190 and 220 nm falls between the Schumann-Runge bands of oxygen and the Hartley bands of ozone, and its absorption is therefore more sensitive to changes in altitude and atmospheric oxygen content than neighboring wavelengths. These two observations are used to suggest a link between sulfur dioxide photolysis at 193 nm and sulfur isotope anomalies in Archean rocks. This hypothesis includes the suggestion that UV wavelengths shorter than 200 nm penetrated deep in the Earth's atmosphere during the Archean. Potential implications of this hypothesis for the chemistry, composition, and UV absorption of the atmosphere are explored. We also explore the implications of these observations for documentation of bacterial sulfur metabolisms early in Earth's history.

  20. Reactions of SIV species with organic compounds: formation mechanisms of organo-sulfur derivatives in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Passananti, Monica; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; George, Christian

    2015-04-01

    Secondary organic aerosol (SOA) have an important impact on climate, air quality and human health. However the chemical reactions involved in their formation and growth are not fully understood or well-constrained in climate models. It is well known that inorganic sulfur (mainly in oxidation states (+IV) and (+VI)) plays a key role in aerosol formation, for instance sulfuric acid is known to be a good nucleating gas. In addition, acid-catalyzed heterogeneous reactions of organic compounds has shown to produce new particles, with a clear enhancement in the presence of ozone (Iinuma 2013). Organosulfates have been detected in tropospheric particles and aqueous phases, which suggests they are products of secondary organic aerosol formation process (Tolocka 2012). Originally, the production of organosulfates was explained by the esterification reaction of alcohols, but this reaction in atmosphere is kinetically negligible. Other formation pathways have been suggested such as hydrolysis of peroxides and reaction of organic matter with sulfite and sulfate radical anions (SO3-, SO4-) (Nozière 2010), but it remains unclear if these can completely explain atmospheric organo-sulfur aerosol loading. To better understand the formation of organo-sulfur compounds, we started to investigate the reactivity of SIV species (SO2 and SO32-) with respect to specific functional groups (organic acids and double bonds) on atmospherically relevant carboxylic acids and alkenes. The experiments were carried out in the homogeneous aqueous phase and at the solid-gas interface. A custom built coated-wall flow tube reactor was developed to control relativity humidity, SO2 concentration, temperature and gas flow rate. Homogeneous and heterogeneous reaction kinetics were measured and resulting products were identified using liquid chromatography coupled with an orbitrap mass spectrometer (LC-HR-MS). The experiments were performed with and without the presence of ozone in order to evaluate any

  1. Corrosion behavior of niobium and Nb-25 wt% Ta alloy in sulfuric acid solutions

    SciTech Connect

    Robin, A.; Nunes, C.A. ); de Almeida, M.E. )

    1991-06-01

    In this paper the corrosion behavior of niobium and Nb-25 wt% Ta alloy in H{sub 2} SO{sub 4} solutions has been studied. Using mass-loss techniques, the influences of H{sub 2}SO{sub 4} concentration, temperature, and exposure time have been examined. The Nb-Ta alloy is more corrosion resistant than pure niobium. The obtained corrosion data allowed the construction of iso-corrosion curves of both materials in sulfuric acid below and above the boiling point.

  2. Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

  3. Watershed-scale changes in terrestrial nitrogen cycling during a period of decreased atmospheric nitrate and sulfur deposition

    NASA Astrophysics Data System (ADS)

    Sabo, Robert D.; Scanga, Sara E.; Lawrence, Gregory B.; Nelson, David M.; Eshleman, Keith N.; Zabala, Gabriel A.; Alinea, Alexandria A.; Schirmer, Charles D.

    2016-12-01

    sites. Other factors, such as decreased sulfur deposition, disturbance, long-term successional trends, and/or increasing atmospheric CO2 concentrations, may also influence trends in tree-ring δ15N values. Furthermore, declines in terrestrial N availability inferred from tree-ring δ15N values do not always correspond with decreased stream nitrate export or increased retention of atmospherically deposited N.

  4. Tinkering With AGCMs To Investigate Atmospheric Behavior

    NASA Astrophysics Data System (ADS)

    Bitz, C. M.

    2014-12-01

    My experience teaching a course in global climate modeling has proven that students (and instructors) with wide-ranging backgrounds in earth-science learn effectively about the complexity of climate by tinker with model components. As an example, I will present a series of experiments in an AGCM with highly simplified geometries for ocean and land to test the response of the atmosphere to variations in basic parameters. The figure below shows an example of how the zonal wind changes with surface roughness and orography. The pinnacle of experiments explored in my course was the outcome of a homework assignment where students reduced the cloud droplet radius by 40% over ocean, and the results surprised students and instructor alike.

  5. The Sulfur Cycle

    ERIC Educational Resources Information Center

    Kellogg, W. W.; And Others

    1972-01-01

    A model estimating the contributions of sulfur compounds by natural and human activities, and the rate of removal of sulfur from the atmosphere, is based on a review of the existing literature. Areas requiring additional research are identified. (AL)

  6. The Sulfur Cycle

    ERIC Educational Resources Information Center

    Kellogg, W. W.; And Others

    1972-01-01

    A model estimating the contributions of sulfur compounds by natural and human activities, and the rate of removal of sulfur from the atmosphere, is based on a review of the existing literature. Areas requiring additional research are identified. (AL)

  7. Np(V) reduction by humic acid: contribution of reduced sulfur functionalities to the redox behavior of humic acid.

    PubMed

    Schmeide, K; Sachs, S; Bernhard, G

    2012-03-01

    The role of sulfur-containing functional groups in humic acids for the Np(V) reduction in aqueous solution has been studied with the objective to specify individual processes contributing to the overall redox activity of humic substances. For this, humic acid model substances type M1-S containing different amounts of sulfur (1.9, 3.9, 6.9 wt.%) were applied. The sulfur functionalities in these humic acids are dominated by reduced-sulfur species, such as thiols, dialkylsulfides and/or disulfides. The Np(V) reduction behavior of these humic acids has been studied in comparison to that of the sulfur-free humic acid type M1 at pH 5.0, 7.0 and 9.0 under anaerobic conditions by means of batch experiments. For Np redox speciation in solution, solvent extraction and ultrafiltration were applied. In addition, redox potentials of the sample solutions were monitored. At pH 5.0, both rate and extent of Np(V) to Np(IV) reduction were found to increase with increasing sulfur content of the humic acids. At pH 7.0 and 9.0, sulfur functional groups had only a slight influence on the reduction behavior of humic acid toward Np(V). Thus, in addition to quinoid moieties and non-quinoid phenolic OH groups, generally acknowledged as main redox-active sites in humic substances, sulfur functional groups have been identified as further redox-active moieties of humic substances being active especially in the slightly acidic pH range as shown for Np(V). Due to the low sulfur content of up to 2 wt.% in natural humic substances, their contribution to the total reducing capacity is smaller than that of the other redox-active functional groups. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Holocene Concentrations of Methane in the Atmosphere are in Part Proportional to Concentrations of Sulfur Dioxide and Inversely Proportional to the Oxidizing Capacity of the Atmosphere

    NASA Astrophysics Data System (ADS)

    Ward, P. L.

    2008-12-01

    The atmosphere cleans itself by oxidizing pollutants. The primary oxidant is the hydroxyl radical (OH) formed by photodissociation of ozone in the near ultra-violet. Ozone and OH are in limited supply. Sulfur dioxide (SO2) absorbs near ultraviolet light limiting production of OH and reacts immediately with any available OH, forming sulfuric acid. Methane reacts more slowly with OH and will typically not be oxidized until there is little SO2. Thus a high concentration of methane indicates low oxidizing capacity. The rate at which SO2 is injected into the atmosphere controls oxidizing capacity and climate change in four ways: 1. Moderate rate: Large volcanic eruptions (VEI >=6) lower global temperatures for a few years when they are separated by years to decades so the oxidizing capacity of the atmosphere can fully recover. In 1991, Pinatubo volcano in the Philippines erupted 20 Mt SO2 and 491 Mt H2O, the largest volcanic eruption since 1912. The SO2 was oxidized primarily by OH to form a 99% pure aerosol of sulfuric acid and water at an elevation of 20-23 km. This aerosol reflected sunlight, lowering the world's temperature on average 0.4°C for three years. Ozone levels were reduced by 10%. Methane increased by 15 ppb for a year. The e-folding time for SO2 was 35 days. 2. High rate: When large eruptions occur once to several times per year, there is insufficient oxidizing capacity leading to increases in methane and other greenhouse gases and global warming. There were 15 times in the Holocene when large volcanoes erupted on average at least every year for 7 to 21 years. Man is now putting as much SO2 from burning fossil fuels into the atmosphere every year as one large volcano, causing current global warming. The two previous times were from 818-838 AD, the onset of the Medieval Warming Period, and from 180-143 BC, the onset of the Roman Warm Period. 3. Low rate: When there are no large eruptions for decades, the oxidizing capacity can catch up, cleaning the

  9. Modeling HOx/O3 chemistry in the tropical marine boundary during the Pacific Atmospheric Sulfur Experiment

    NASA Astrophysics Data System (ADS)

    Gu, D.; Gray, B. A.; Wang, Y.; Mauldin, L.; Cantrell, C.; Heikes, B. G.; Higbie, A.; O'Sullivan, D. W.; Campos, T.; Pollack, I. B.; Heizer, C. G.; Weinheimer, A. J.

    2008-12-01

    C-130 observations of OH, RO2, O3, CO, H2O2, and CH3OOH in the tropical marine boundary layer during the 2007 Pacific Atmospheric Sulfur Experiment are analyzed using a one- dimensional chemistry transport model. Meteorological parameters are simulated from the Weather Research and Forecasting model. The coupling of low-NOx photochemistry and mixing processes is examined over the relatively homogeneous region. Simulated vertical profiles of HOx radicals and peroxides are not always in agreement with the measurements. Potential factors contributing to the discrepancies are investigated. The large ozone decrease towards the surface is driven in part by large photochemical loss in the marine boundary layer. The vertical gradient is also regulated by the influx of ozone from free troposphere and diffusion transport in the boundary layer. This experimental constraint on model simulated vertical transport is evaluated.

  10. Microwave Remote Sensing of the Temperature and Distribution of Sulfur Compounds in the Lower Atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Jenkins, Jon M.; Kolodner, Marc A.; Butler, Bryan J.; Suleiman, Shady H.; Steffes, Paul G.

    2002-08-01

    A multi-wavelength radio frequency observation of Venus was performed on April 5, 1996, with the Very Large Array to investigate potential variations in the vertical and horizontal distribution of temperature and the sulfur compounds sulfur dioxide (SO 2) and sulfuric acid vapor (H 2SO 4(g)) in the atmosphere of the planet. Brightness temperature maps were produced which feature significantly darkened polar regions compared to the brighter low-latitude regions at both observed frequencies. This is the first time such polar features have been seen unambiguously in radio wavelength observations of Venus. The limb-darkening displayed in the maps helps to constrain the vertical profile of H 2SO 4(g), temperature, and to some degree SO 2. The maps were interpreted by applying a retrieval algorithm to produce vertical profiles of temperature and abundance of H 2SO 4(g) given an assumed sub-cloud abundance of SO 2. The results indicate a substantially higher abundance of H 2SO 4(g) at high latitudes (above 45°) than in the low-latitude regions. The retrieved temperature profiles are up to 25 K warmer than the profile obtained by the Pioneer Venus sounder probe at altitudes below 40 km (depending on location and assumed SO 2 abundance). For 150 ppm of SO 2, it is more consistent with the temperature profile obtained by Mariner 5, extrapolated to the surface via a dry adiabat. The profiles obtained for H 2SO 4(g) at high latitudes are consistent with those derived from the Magellan radio occultation experiments, peaking at around 8 ppm at an altitude of 46 km and decaying rapidly away from that altitude. At low latitudes, no significant H 2SO 4(g) is observed, regardless of the assumed SO 2 content. This is well below that measured by Mariner 10 (Lipa and Tyler 1979, Icarus39, 192-208), which peaked at ˜14 ppm near 47 km. Our results favor ≤100 ppm of SO 2 at low latitudes and ≤50 ppm in polar regions. The low-latitude value is statistically consistent with the

  11. Spatial patterns of atmospheric deposition of nitrogen and sulfur using ion-exchange resin collectors in Rocky Mountain National Park, USA

    Treesearch

    David W. Clow; Heidi A. Roop; Leora Nanus; Mark E. Fenn; Graham A. Sexstone

    2015-01-01

    Lakes and streams in Class 1 wilderness areas in the western United States (U.S.) are at risk from atmospheric deposition of nitrogen (N) and sulfur (S), and protection of these resources is mandated under the Federal Clean Air Act and amendments. Assessment of critical loads, which are the maximum exposure to pollution an area can receive without adverse effects on...

  12. Fractionation of sulfur isotopes during atmospheric processes: SO2 oxidation and photolysis

    NASA Astrophysics Data System (ADS)

    Harris, E. J.; Sinha, B.; Hoppe, P.; Crowley, J.; Foley, S. F.

    2010-12-01

    Measurements of stable sulfur isotopes can be used to investigate the chemistry of SO2 in the environment. The oxidation pathway of SO2 plays an important role in determining its environmental effect: gaseous oxidation by OH radicals produces gas-phase sulfuric acid that can nucleate to produce new particles and CCN, while heterogeneous oxidation can change the surface properties of existing particles. Stable isotopes have been used in the investigation of these oxidation pathways, but a major limitation is the lack of laboratory studies of the isotopic fractionation factor for the gaseous reaction (Castleman et al., 1974; Leung et al., 2001; Tanaka et al., 1994). An experimental set-up to investigate the kinetic fractionation of 34S/32S (α = k34/k32) during this reaction has been developed. OH radicals are generated by flowing humidified nitrogen past a mercury lamp producing high-energy UV light. SO2 gas with a known isotopic composition reacts with the OH radicals to produce sulfuric acid gas. Collection methods for both H2SO4 and SO2 gases have been characterised. H2SO4 gas is collected in a glass condenser system and washed out with MilliQ water. This collection method introduces no significant isotopic fractionation. SO2 gas is collected in two bubblers containing 6% H2O2 solution at 273 K, which introduces fractionation of 13 ± 2‰ (α = 1.013 ± 0.002) at 273 K, agreeing with aqueous uptake and oxidation (Saltzman et al., 1983). Following collection, BaCl2 is added to precipitate the sulfur as BaSO4 and the solutions are filtered to collect the BaSO4 grains for analysis in the NanoSIMS. Photolytic and aqueous oxidation of SO2 are the main interfering reactions occurring in the system, and were investigated by running the reaction set-up without generating OH radicals. High humidity conditions produce fractionation of 11 ± 7‰ (α = 1.011 ± 0.007) at 293 K, which corresponds well with previous results for the SO2(g)-HSO3-(aq) system (Eriksen, 1972

  13. Spectral properties of condensed phases of disulfur monoxide, polysulfur oxide, and irradiated sulfur. [in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Hapke, Bruce; Graham, Francis

    1989-01-01

    The spectral reflectances of S2O, as well as the polysulfur oxide (PSO) condensate dissociation products of SO2 and condensates of elemental sulfur irradiated with UV light and X-rays, have been ascertained in the 200-1700 nm range with a view to the relevance of these compounds to the interpretation of planetary data. While S2O is a dark red solid, PSO is a pale yellow one that absorbs strongly in the UV but exhibits no bands in either the visible or near IR. Elemental S produces strong bands in the UV, and while it is normally white at room temperature, UV irradiation causes it to turn yellow. X-ray irradiation of S turns it orange.

  14. Spectral properties of condensed phases of disulfur monoxide, polysulfur oxide, and irradiated sulfur. [In planetary atmospheres

    SciTech Connect

    Hapke, B.; Graham, F. )

    1989-05-01

    The spectral reflectances of S2O, as well as the polysulfur oxide (PSO) condensate dissociation products of SO2 and condensates of elemental sulfur irradiated with UV light and X-rays, have been ascertained in the 200-1700 nm range with a view to the relevance of these compounds to the interpretation of planetary data. While S2O is a dark red solid, PSO is a pale yellow one that absorbs strongly in the UV but exhibits no bands in either the visible or near IR. Elemental S produces strong bands in the UV, and while it is normally white at room temperature, UV irradiation causes it to turn yellow. X-ray irradiation of S turns it orange. 24 refs.

  15. Stability of chromium (III) sulfate in atmospheres containing oxygen and sulfur

    NASA Technical Reports Server (NTRS)

    Jacob, K. T.; Rao, B. D.; Nelson, H. G.

    1978-01-01

    The stability of chromium sulfate in the temperature range from 880 K to 1040 K was determined by employing a dynamic gas-solid equilibration technique. The solid chromium sulfate was equilibrated in a gas stream of controlled SO3 potential. Thermogravimetric and differential thermal analyses were used to follow the decomposition of chromium sulfate. X-ray diffraction analysis indicated that the decomposition product was crystalline Cr2O3 and that the mutual solubility between Cr2(SO4)3 and Cr2O3 was negligible. Over the temperature range investigated, the decomposition pressure were significantly high so that chromium sulfate is not expected to form on commercial alloys containing chromium when exposed to gaseous environments containing oxygen and sulfur (such as those encountered in coal gasification).

  16. Spectral properties of condensed phases of disulfur monoxide, polysulfur oxide, and irradiated sulfur. [in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Hapke, Bruce; Graham, Francis

    1989-01-01

    The spectral reflectances of S2O, as well as the polysulfur oxide (PSO) condensate dissociation products of SO2 and condensates of elemental sulfur irradiated with UV light and X-rays, have been ascertained in the 200-1700 nm range with a view to the relevance of these compounds to the interpretation of planetary data. While S2O is a dark red solid, PSO is a pale yellow one that absorbs strongly in the UV but exhibits no bands in either the visible or near IR. Elemental S produces strong bands in the UV, and while it is normally white at room temperature, UV irradiation causes it to turn yellow. X-ray irradiation of S turns it orange.

  17. Modeling Atmospheric Sulfur Over the Northern Hemisphere during the Aerosol Characterization Experiment 2 Experimental Period

    SciTech Connect

    Benkovitz, C; Schwartz, Stephen E.; Jensen, Michael P.; Miller, Mark A.; Easter, Richard C.; Bates, Timothy S.

    2004-11-25

    A high-resolution (1{sup o} x 1{sup o}, 27 vertical levels) Eulerian chemical transport and transformation model for sulfate, SO{sub 2}, and related species driven by analyzed forecast meteorological data has been run for the Northern Hemisphere for June-July 1997 and extensively evaluated with observational data, mainly from air-quality and precipitation chemistry networks. For {approx}5000 evaluations, 50% of the modeled sulfate 24-h mixing ratios were within a factor of 1.85 of the observations; 50% of {approx}328 concurrent subgrid observations were within a factor of 1.33. Much greater subgrid variation for 24-h SO{sub 2} mixing ratios (50% of {approx}3552 observations were within a factor of 2.32) reflects high variability of this primary species; for {approx}12,600 evaluations 50% of modeled mixing ratios were within a factor of 2.54 of the observations. These results indicate that a substantial fraction of the modeled and observed differences is due to subgrid variation and/or measurement error. Sulfate mixing ratios are identified by source type (biogenic, volcanic, and anthropogenic) and production mechanism (primary and by gas-phase and aqueous-phase oxidation). Examination of key diagnostics showed substantial variation for the different types of sulfur, e.g., SO{sub 2} aqueous-phase oxidation rates of 29 to 102% day{sup -1}, sulfate residence times of 4 to 9 days. Volcanic emissions contributed 10% of the sulfate burden and 6% of emissions, because the elevated release allows 2 large fractional conversion of SO{sub 2} and long residence time. Biogenic SO{sub 2} was generally at lower concentrations than H{sub 2}O{sub 2}, resulting in efficient aqueous-phase oxidation; this source type contributed 13% of emissions but only 5% of sulfate burden. Anthropogenic sources were the dominant contributors to sulfur emissions, 80%, and sulfate burden, 84%.

  18. N2-, O2- and He-collision-induced broadening of sulfur dioxide ro-vibrational lines in the 9.2 μm atmospheric window

    NASA Astrophysics Data System (ADS)

    Tasinato, Nicola; Pietropolli Charmet, Andrea; Stoppa, Paolo; Giorgianni, Santi; Buffa, Giovanni

    2014-01-01

    Sulfur dioxide (SO2) is a molecule of considerable interest for both atmospheric chemistry and astrophysics. In the Earth's atmosphere, it enters in the sulfur cycle and it is ubiquitous present in polluted atmospheres, where it is responsible for acid rains. It is also of astrophysical and planetological importance, being present on Venus and in interstellar clouds. In this work the collisional broadening of a number of ν1 ro-vibrational lines of SO2 perturbed by N2, O2 and He are investigated at room temperature in the 9 μm atmospheric region by means of high resolution tunable diode laser (TDL) infrared spectroscopy. From N2- and O2-broadening coefficients, the broadening parameters of sulfur dioxide in air, useful for atmospheric applications, are derived as well. From the present measurements some conclusions on the quantum number dependence of the N2-, O2- and He-broadening coefficients are drawn. While the J dependence is weak for all the perturbers investigated, different trends with Ka are reported. N2-broadening coefficients show a slight decrease with increasing values of Ka, whereas O2 and He broadening cross sections first increase up to Ka″≈6 and then they keep a nearly constant value. A comparison and a brief discussion on the efficiency of self-, N2-, O2- and He-collisional dynamics are given. The data obtained represent a significant analysis on foreign broadening of SO2 useful for atmospheric remote sensing and astrophysical applications.

  19. Determination of the atmospheric lifetime and global warming potential of sulfur hexafluoride using a three-dimensional model

    NASA Astrophysics Data System (ADS)

    Kovács, Tamás; Feng, Wuhu; Totterdill, Anna; Plane, John M. C.; Dhomse, Sandip; Gómez-Martín, Juan Carlos; Stiller, Gabriele P.; Haenel, Florian J.; Smith, Christopher; Forster, Piers M.; García, Rolando R.; Marsh, Daniel R.; Chipperfield, Martyn P.

    2017-01-01

    We have used the Whole Atmosphere Community Climate Model (WACCM), with an updated treatment of loss processes, to determine the atmospheric lifetime of sulfur hexafluoride (SF6). The model includes the following SF6 removal processes: photolysis, electron attachment and reaction with mesospheric metal atoms. The Sodankylä Ion Chemistry (SIC) model is incorporated into the standard version of WACCM to produce a new version with a detailed D region ion chemistry with cluster ions and negative ions. This is used to determine a latitude- and altitude-dependent scaling factor for the electron density in the standard WACCM in order to carry out multi-year SF6 simulations. The model gives a mean SF6 lifetime over an 11-year solar cycle (τ) of 1278 years (with a range from 1120 to 1475 years), which is much shorter than the currently widely used value of 3200 years, due to the larger contribution (97.4 %) of the modelled electron density to the total atmospheric loss. The loss of SF6 by reaction with mesospheric metal atoms (Na and K) is far too slow to affect the lifetime. We investigate how this shorter atmospheric lifetime impacts the use of SF6 to derive stratospheric age of air. The age of air derived from this shorter lifetime SF6 tracer is longer by 9 % in polar latitudes at 20 km compared to a passive SF6 tracer. We also present laboratory measurements of the infrared spectrum of SF6 and find good agreement with previous studies. We calculate the resulting radiative forcings and efficiencies to be, on average, very similar to those reported previously. Our values for the 20-, 100- and 500-year global warming potentials are 18 000, 23 800 and 31 300, respectively.

  20. Responses of Hawaiian plants to volcanic sulfur dioxide: stomatal behavior and foliar injury

    SciTech Connect

    Not Available

    1980-11-14

    Hawaiian plants exposed to volcanic sulfur dioxide showed interspecific differences in leaf injury that are related to sulfur dioxide-induced changes in stomatal conductance. Species with leaves that did not close stomata developed either chlorosis or necrosis, whereas leaves of Metrosideros collina closed stomata and showed no visual symptoms of sulfur dioxide stress.

  1. Martian Atmospheric Plumes: Behavior, Detectability and Plume Tracing

    NASA Astrophysics Data System (ADS)

    Banfield, Don; Mischna, M.; Sykes, R.; Dissly, R.

    2013-10-01

    We will present our recent work simulating neutrally buoyant plumes in the martian atmosphere. This work is primarily directed at understanding the behavior of discrete plumes of biogenic tracer gases, and thus increasing our understanding of their detectability (both from orbit and from in situ measurements), and finally how to use the plumes to identify their precise source locations. We have modeled the detailed behavior of martian atmospheric plumes using MarsWRF for the atmospheric dynamics and SCIPUFF (a terrestrial state of the art plume modeling code that we have modified to represent martian conditions) for the plume dynamics. This combination of tools allows us to accurately simulate plumes not only from a regional scale from which an orbital observing platform would witness the plume, but also from an in situ perspective, with the instantaneous concentration variations that a turbulent flow would present to a point sampler in situ instrument. Our initial work has focused on the detectability of discrete plumes from an orbital perspective and we will present those results for a variety of notional orbital trace gas detection instruments. We have also begun simulating the behavior of the plumes from the perspective of a sampler on a rover within the martian atmospheric boundary layer. The detectability of plumes within the boundary layer has a very strong dependence on the atmospheric stability, with plume concentrations increasing by a factor of 10-1000 during nighttime when compared to daytime. In the equatorial regions of the planet where we have simulated plumes, the diurnal tidal “clocking” of the winds is strongly evident in the plume trail, which similarly “clocks” around its source. This behavior, combined with the strong diurnal concentration variations suggests that a rover hunting a plume source would be well suited to approach it from a particular azimuth (downwind at night) to maximize detectability of the plume and the ability to

  2. TRENDS IN ATMOSPHERIC SULFUR AND NITROGEN SPECIES IN THE EASTERN UNITED STATES 1989-1995

    EPA Science Inventory

    Emission reductions were mandated in the Clean Air Act Amendments of 1990 with the expectation that they would result in major reductions in the concentrations of atmospherically transported pollutants. This paper investigates the form and magnitude of trends from 1989 to 1995 i...

  3. TRENDS IN ATMOSPHERIC SULFUR AND NITROGEN SPECIES IN THE EASTERN UNITED STATES 1989-1995

    EPA Science Inventory

    Emission reductions were mandated in the Clean Air Act Amendments of 1990 with the expectation that they would result in major reductions in the concentrations of atmospherically transported pollutants. This paper investigates the form and magnitude of trends from 1989 to 1995 i...

  4. Atmospheric halocarbons, hydrocarbons, and sulfur hexafluoride: global distributions, sources, and sinks.

    PubMed

    Singh, H B; Salas, L J; Shigeishi, H; Scribner, E

    1979-03-02

    The global distribution of fluorocarbon-12 and fluorocarbon-11 is used to establish a relatively fast interhemispheric exchange rate of 1 to 1.2 years. Atmospheric residence times of 65 to 70 years for fluorocarbon-12 and 40 to 45 years for fluorocarbon-l1 best fit the observational data. These residence times rule out the possibility of any significant missing sinks that may prevent these fluorocarbons from entering the stratosphere. Atmospheric measurements of methyl chloroform support an 8-to 10-year residence time and suggest global average hydroxyl radical (HO) concentrations of 3 x 10(5) to 4 x 10(5) molecules per cubic centimeter. These are a factor of 5 lower than predicted by models. Additionally, methyl chloroform global distribution supports Southern Hemispheric HO levels that are a factor of 1.5 or more larger than the Northern Hemispheric values. The long residence time and the rapid growth of methyl chloroform cause it to be a potentially significant depleter of stratospheric ozone. The oceanic sink for atmospheric carbon tetrachloride is about half as important as the stratospheric sink. A major source of methyl chloride (3 x 10(12)grams per year), sufficient to account for nearly all the atmospheric methyl chloride, has been identified in the ocean.

  5. Laboratory Measurement of the Temperature Dependence of Gaseous Sulfur Dioxide (SO2) Microwave Absorption with Application to the Venus Atmosphere

    NASA Technical Reports Server (NTRS)

    Suleiman, Shady H.; Kolodner, Marc A.; Steffes, Paul G.

    1996-01-01

    High-accuracy laboratory measurements of the temperature dependence of the opacity from gaseous sulfur dioxide (SO2) in a carbon dioxide (CO2) atmosphere at temperatures from 290 to 505 K and at pressures from 1 to 4 atm have been conducted at frequencies of 2.25 GHz (13.3 cm), 8.5 GHz (3.5 cm), and 21.7 GHz (1.4 cm). Based on these absorptivity measurements, a Ben-Reuven (BR) line shape model has been developed that provides a more accurate characterization of the microwave absorption of gaseous S02 in the Venus atmosphere as compared with other formalisms. The developed BR formalism is incorporated into a radiative transfer model. The resulting microwave emission spectrum of Venus is then used to set an upper limit on the disk-averaged abundance of gaseous S02 below the main cloud layer. It is found that gaseous S02 has an upper limit of 150 ppm, which compares well with previous spacecraft in situ measurements and Earth-based radio astronomical observations.

  6. The Effects of Particle Size, Relative Humidity, and Sulfur Dioxide on Iron Solubility in Atmospheric Particulate Matter

    NASA Astrophysics Data System (ADS)

    Cartledge, B. T.; Marcotte, A.; Anbar, A. D.; Herckes, P.; Majestic, B. J.

    2014-12-01

    The current study focuses on studying how iron (Fe) solubility is affected by particle size, relative humidity, and exposure to sulfur dioxide (SO2). Fe, the most abundant transition metal in atmospheric particulate matter, plays a critical role in the atmospheric sulfur cycle and is a micronutrient for phytoplankton in remote regions of the ocean. To mimic oceanic particles, iron-containing minerals (hematite, magnetite, goethite, and illite) were resuspended with sodium chloride and size-segregated on Teflon filters into five different size fractions: 10-2.5 μm, 2.5-1.0 μm, 1.0-0.5 μm, 0.5-0.25 μm, and <0.25 μm. Mineral phases were then exposed to 5 ppm SO2 in air at marine environment humidity (>80%) and arid environment humidity (24%). Trials with no SO2 ­were also performed as comparisons. Total Fe was determined by using microwave-assisted acid digestion and soluble Fe was determined by extracting the samples in a simulated cloud water buffer (pH 4.25, 0.5 mM acetate, 0.5 mM formate, and 0.2 mM ammonium nitrate). Both total and soluble Fe concentrations were determined via inductively-coupled plasma mass spectrometry (ICP-MS). We found that, as particle size decreased, Fe percent solubility increased for hematite, magnetite, and goethite. The percent solubility of Fe in these mineral phases steadily increased from 0.5-10% as particle size decreased. In contrast, the Fe percent solubility in illite was relatively constant for the largest four size fractions but increased dramatically in the smallest size fraction. The percent solubility of Fe in illite ranged from 5-20% as the particle size decreased. Additionally, increased Fe solubility was linked to increased relative humidity with higher percent solubility generally observed in all mineral phases for the samples exposed at the higher humidity. No correlation was observed for the effects of the SO2 on Fe percent solubility. The likely lack of Fe-SO2 interactions were also supported by synchrotron

  7. Multiple oxygen and sulfur isotope compositions of secondary atmospheric sulfate in the city of Wuhan, central China

    NASA Astrophysics Data System (ADS)

    Li, X.; Bao, H.; Zhou, A.; Wang, D.

    2012-12-01

    Secondary atmospheric sulfate (SAS) is the oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. SAS can be produced from gas-phase OH-radical oxidation and five aqueous-phase chemical reactions including aqueous-phase S (IV) oxidation reactions by H2O2, O3, oxygen catalyzed by Fe3+ and Mn2+, and methyle hydrogen peroxide and peroxyacetic acid. The tropospheric sulfur oxidation pathway is therefore determined by cloud-water pH, dissolved [Fe2+] or [Mn2+] content, S emission rate, meteorological condition, and other factors. The S isotope composition is a good tracer for the source while the O isotopes, especially the triple O isotope compositions are a good tracer for S oxidation pathway. Jerkins and Bao (2006) provided the first set of multiple stable isotope compositions (δ34S, δ18O and Δ17O) for SAS collected from bulk atmosphere in Baton Rouge in the relatively rural southern USA. Their study revealed a long-tern average Δ17O value of ~+0.7‰ for SAS, and speculated that much of the Earth mid-latitudes may have a similar average SAS Δ17O value. Additional sampling campaign at different sites is necessarily for constructing and testing models on sulfur oxidation and transport in the troposphere. A total of 33 sulfate samples were collected from bulk atmospheric deposition over a 950-day period from May 2009 to December 2011 in the city of Wuhan, Hubei Province, China. Differing from Baton Rouge, Wuhan is an industrial metropolis with a population of 9.8 million and a high particulate matter content (115 μg/m3). It also has a subtropical monsoon climate, with rainwater pH at ~5.3 year-around. The rainwater ion concentrations have seasonal variations, typically low in summer and high in winter. The anions are dominated by SO42-, at an average concentration of 8.5 mg/L. There is little sulfate contribution from sea-salt (SS) sulfate or dusts in Wuhan. The isotopic compositions for bulk atmospheric sulfate

  8. Hydrogen Peroxide and Methylhydroperoxide Budgets in the Marine Boundary Layer During the Pacific Atmospheric Sulfur Experiment

    NASA Astrophysics Data System (ADS)

    O'Sullivan, D. W.; Heikes, B. G.; Higbie, A.; Merrill, J. T.; Bandy, A. R.; Mauldin, L.; Cantrell, C.; Anderson, R. S.; Campos, T.; Lenschow, D.; Bloomquist, B.; Faloona, I. C.; Conley, S. A.; Wang, Y.; Pollack, I. B.; Heizer, C. G.; Weinheimer, A. J.

    2008-12-01

    Airborne gas phase measurements of hydrogen peroxide, methylhydroperoxide, ozone, carbon monoxide, dimethylsulfide, sulfur dioxide, hydroxyl, and perhydroxyl, together with meteorological parameters are used to assess the photochemical budget of hydrogen peroxide and methylhydroperoxide in the marine boundary layer (MBL). The observations come from 14 research flights using the NCAR C-130 flown mostly southeast of Kiritimati in relatively cloud- and precipitation-free MBL air. This region was expected to have extremely low nitrogen oxide mixing ratios and minimal horizontal gradients in composition. Eddy-correlation methods are used to estimate entrainment rates at the top of the MBL. Surface deposition rates are calculated from wind and molecular properties. Gas phase photolysis rates are calculated and reaction rate constants are estimated from the literature. The measurements and budgets are discussed in terms of their ability to constrain net ozone production, nitrogen oxide levels, reactive hydrocarbons, and halogen radical chemistry. On occasion the aircraft flew within its advected exhaust plume and a decrease in methylhydroperoxide, but not in hydrogen peroxide, was noted.

  9. Can sulfate fluxes in forest canopy throughfall be used to estimate atmospheric sulfur deposition

    SciTech Connect

    Lindberg, S.E.; Garten, C.T. Jr. ); Cape, J.N. ); Ivens, W. )

    1991-01-01

    The flux of sulfate is forest throughfall and stemflow (the sum of which is designated here as TF) may be an indicator of the atmospheric deposition of S, particularly if foliar leaching of internal plant S is small relative to washoff of deposition. Extensive data from 13 forests indicate that annual sulfate fluxes in TF and in atmospheric deposition are very similar, and recent studies with {sup 35}S tracers indicate that leaching is only a few percent of total TF. However, some short-term deposition/TF comparisons show large differences, and there remain questions about interpretation of tracer results. Considering the data, we conclude that TF may be used under some conditions to estimate deposition within acceptable uncertainty limits, but that some assumptions need further testing. If TF does reflect deposition, these data suggest that commonly used methods and models seriously underestimate total S deposition at some sites. 39 refs. ,4 figs., 1 tab.

  10. Rayleigh light scattering properties of atmospheric molecular clusters consisting of sulfuric acid and bases.

    PubMed

    Elm, Jonas; Norman, Patrick; Mikkelsen, Kurt V

    2015-06-28

    The Rayleigh light scattering properties of (H2SO4)a(NH3)b and (H2SO4)a((CH3)2NH)b atmospheric molecular clusters have been investigated using a response theory approach. Using density functional theory the molecular structures and stepwise formation free energies of clusters with a and b up to 4 have been re-investigated. The Rayleigh scattering intensities are calculated from the dipole polarizability tensor α using the CAM-B3LYP functional by applying linear response methods. The intrinsic scattering properties of (H2SO4)a(NH3)b and (H2SO4)a((CH3)2NH)b indicate that amine containing clusters scatter light significantly more efficiently then their ammonia containing counterparts. Using the Atmospheric Cluster Dynamics Code (ACDC) the steady state cluster concentrations are estimated and the effective scattering is calculated. The effective scattering is shown to be highly dependent on the estimated concentrations and indicates that there exist competitive pathways, such as nucleation and coagulation, which influence the cluster distributions. The frequency dependence of the scattering is found to depend on the cluster composition and show increased responses when clusters contain more bases than acid molecules. Based on structures obtained using semi-empirical molecular dynamics simulations the Rayleigh scattering properties of clusters with up to 20 acid-base pairs are evaluated. This study represents the first step towards gaining a fundamental understanding of the scattering properties of small atmospheric clusters in the ambient atmosphere.

  11. The enhancement mechanism of glycolic acid on the formation of atmospheric sulfuric acid-ammonia molecular clusters

    NASA Astrophysics Data System (ADS)

    Zhang, Haijie; Kupiainen-Määttä, Oona; Zhang, Xiuhui; Molinero, Valeria; Zhang, Yunhong; Li, Zesheng

    2017-05-01

    Highly oxidized multifunctional organic molecules, which span a wide range of low volatilities, are capable of driving particle formation as well as the initial growth of particles in the atmosphere. However, their participant mechanism in new particle formation still remains largely ambiguous. Here we present an investigation of the potentially participant mechanism of the simplest hydroxyl acid, glycolic acid (GA) on clusters formation by sulfuric acid (SA) and ammonia (A). Density functional theory calculations at the M062X/6-311++G(3df,3pd) level of theory combining with atmospheric cluster dynamics code simulations of (𝐒𝐀)xṡ𝐀yṡ(𝐆𝐀)z cluster (y≤x + z ≤ 3) systems at different temperatures (298, 278, 258, 238, and 218 K) give direct evidence of the enhancement effect of GA on the formation rates of SA-A-based clusters at high concentration of GA and T = 238 K and 218 K. Moreover, within GA's enhancement concentrations, the enhancement strength R of GA presents a positive dependence on its atmospheric concentrations and a negative dependence on temperature. A competitive relationship between SA and GA has been identified through the negative dependence of R on the concentrations of SA. The influence of A on R is more complex that R first increases, reaching a maximum value, and then decreases with the increasing concentration of A. Finally, the combination of the traced growth paths of the system with the enhancement strength of GA suggests a "catalytic" enhancement mechanism of GA where GA acts as a mediate bridge for the formation of pure SA-A-based clusters.

  12. Melting behavior of the iron-sulfur system and chemical convection in iron-rich planetary cores

    SciTech Connect

    Li, J.; Chen, B.

    2009-03-26

    We present experimental data on the high-pressure melting behavior of the Fe-S system from a synchrotron x-ray radiography study using the large volume press, with implications for the role of chemical convection in sulfur-bearing planetary cores. At present, Earth, Mercury and Ganymede are the only three solid bodies in the Solar System that possess intrinsic global magnetic fields. Dynamo simulation reveal that chemical buoyancy force associated with the formation of a solid inner core is critical for sustaining the Earth's magnetic field. Fluid motions in Mercury and Ganymede may be partially driven by chemical buoyancy force as well. The style of chemical convection and its influence on the thermal and chemical state and evolution of iron-rich cores are determined in part by the melting behavior of potential core-forming materials. Sulfur is widely accepted as a candidate light element in iron-rich planetary cores. In order to understand the role of chemical convection in sulfur-bearing cores, we studied the high-pressure melting behavior of Fe-S mixtures containing 9 wt% sulfur using the synchrotron x-ray radiographic method in a large volume press.

  13. What Does the Absence of Mass-independent Fractionation of Sulfur Isotopes at 2.8-3.2 Ga say About the Early Atmosphere?

    NASA Astrophysics Data System (ADS)

    Goldman, S. D.; Kasting, J. F.

    2005-12-01

    The presence of mass-independent fractionation (MIF) of sulfur isotopes in Archean sedimentary provides evidence for a low-O2 atmosphere prior to 2.4 Ga (1). Recent data hints at the possibility that S-MIF vanished transiently some time between 3.4 and 2.7 Ga (2). The absence of S-MIF after 2.4 Ga is commonly attributed to the rise of O2 in the atmosphere, since the presence of free O2 would have oxidized all sulfur before removal from the atmosphere, thereby erasing any MIF that had existed between reservoirs (3). However, if free O2 did not appear in the atmosphere until 2.4 Ga, then why did S-MIF disappear for hundreds of millions of year prior to 2.7 Ga? Could S-MIF have been eliminated from the rock record without the presence of free O2 in the atmosphere? Two different mechanisms will be discussed. The first possibility is that H2 levels decreased sufficiently to oxidize all MIF, but were still high enough to prevent free O2 from building up to appreciable levels in the atmosphere. Stabilization of H2 at these intermediate levels could have been triggered by a number of mechanisms controlling the H2 budget, the most promising of which is changes in the biogeochemical processing of sulfur itself (4). Before the advent of bacterial sulfate reduction (BSR), seawater sulfate would have reacted with Fe in basalts, removing sulfur from the surface in oxidized form. As removing sulfur from the surface as sulfate requires oxidation of SO2, this implies that H2 must have been generated by the geochemical S cycle. After the advent of BSR sulfur would be buried in reduced form as pyrite. Burial of sulfur as pyrite would require reduction of SO2, thus the biogeochemical S cycle would have consumed H2. This change in S cycling likely would have impacted the H2 budget more than any other change in element cycling, other than direct changes in the H2 fluxes into and out of the system. The second possibility is that the atmosphere was reduced with respect to the sulfur

  14. Sulfur in the Early Martian Atmosphere Revisited: Experiments with a 3-D Global Climate Model

    NASA Astrophysics Data System (ADS)

    Kerber, L.; Forget, F.; Wordsworth, R.

    2013-09-01

    Data returned from the surface of Mars during the 1970s revealed intriguing geological evidence for a warmer and wetter early martian climate. Dendritic valley networks were discovered by Mariner 9 on ancient Noachian terrain [1], indicating that liquid water had flowed across the surface in the distant past. Since this time, geological investigations into early Martian history have attempted to ascertain the nature and level of activity of the early Martian hydrological cycle [e.g. 2-5] while atmospheric modeling efforts have focused on how the atmosphere could be warmed to temperatures great enough to sustain such activity [see 6-7 for reviews]. Geological and spectroscopic investigations have refined the history and chronology of Noachian Mars over time, and circulation of liquid water has been invoked to explain several spatially and temporally distinct morphological and chemical signatures found in the geological record. Detections of iron and magnesium-rich clays are widespread in the oldest Martian terrains, suggesting a period of pH-neutral aqueous alteration [e.g., 8]. Valley network incision also took place during the Noachian period [9]. Some chains of river valleys and craters lakes extend for thousands of kilometers, suggesting temperatures at least clement enough for sustained ice-covered flow [3,10]. The commencement of valley network incision is not well constrained, but the period of Mg/Fe clay formation appears to have ended before the termination of valley network formation, as the visible fluvial systems appear to have remobilized existing clays rather than forming them [5,8]. There is also evidence that the cessation of valley network formation was abrupt [11]. Towards the end of the Noachian, erosion rates appear to have been significantly higher than during subsequent periods, a process that has also been attributed to aqueous processes [12]. A period of sulfate formation followed, likely characterized by acidic, evaporitic playa environments

  15. The Seasonal Behavior of Water Vapor in the Mars Atmosphere.

    NASA Astrophysics Data System (ADS)

    Jakosky, Bruce Martin

    Understanding the evolution of volatiles on Mars requires understanding the processes which are currently acting to cause exchange between the various reservoirs on annual and longer timescales. On the seasonal timescale, exchange of water can occur between the atmosphere and reservoirs of ice in the polar caps and of adsorbed water in the near-surface regolith covering the remainder of the planet. The water vapor content of the Mars atmosphere was measured from the Viking Orbiter Mars Atmospheric Water Detectors (MAWD) for a period of more than one Martian year, from June, 1976, through April, 1979, and the results are presented. The strong annual gradient of vapor from north to south implies a net annual flow of vapor toward the south. The perennially-cold nature of the south-polar residual cap, along with the relatively large summertime vapor abundances over the cap, implies a net annual condensation of vapor onto the cap. Estimates are made of the southward transport, and are consistent with the movement of ice being important in the formation and evolution of the polar layered terrain, and with the formation of the individual layers at the rate of one per obliquity cycle (10('5) years). Models have been constructed which include regolith exchange, polar cap formation, and atmospheric transport. The models are capable of satisfactorily explaining the gross features of the observed behavior using plausible values for the regolith and atmosphere mixing terms. In the region between the polar caps, the regolith contributes as much water to the seasonal cycle of vapor as does transport in from the more-poleward regions, to within a factor of two. Globally, 10-50% of the seasonal cycle of vapor results from exchange of water with the regolith, about 40% results from the behavior of the residual caps, and the remainder is due to exchange of water with the seasonal caps.

  16. Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

    NASA Technical Reports Server (NTRS)

    Margitan, J. J.

    1984-01-01

    A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

  17. Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

    NASA Technical Reports Server (NTRS)

    Margitan, J. J.

    1984-01-01

    A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

  18. Effects of background gas on sulfur hexafluoride removal by atmospheric dielectric barrier discharge plasma

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoxing; Xiao, Hanyan; Hu, Xiongxiong; Gui, Yingang

    2016-11-01

    The effects of background gases (He, Ar, N2 and air) on SF6 removal in a dielectric barrier reactor were investigated at atmospheric pressure. A comparison among these background gases was performed in terms of discharge voltage, discharge power, mean electron energy, electron density, removal efficiency and energy yield for the destruction of SF6. Results showed that the discharge voltage of He and Ar was lower than that of N2 and air, but the difference of their discharge power was small. Compared with three other background gases, Ar had a relatively superior destruction and removal rate and energy yield since the mean electron energy and electron density in SF6/H2O/Ar plasma were both maintained at a high level. Complete removal of 2% SF6 could be achieved at a discharge power of 48.86 W with Ar and the corresponding energy yield can reach 4.8 g/kWh.

  19. Streamwater acid-base chemistry and critical loads of atmospheric sulfur deposition in Shenandoah National Park, Virginia.

    PubMed

    Sullivan, T J; Cosby, B J; Webb, J R; Dennis, R L; Bulger, A J; Deviney, F A

    2008-02-01

    A modeling study was conducted to evaluate the acid-base chemistry of streams within Shenandoah National Park, Virginia and to project future responses to sulfur (S) and nitrogen (N) atmospheric emissions controls. Many of the major stream systems in the park have acid neutralizing capacity (ANC) less than 20 microeq/L, levels at which chronic and/or episodic adverse impacts on native brook trout are possible. Model hindcasts suggested that none of these streams had ANC less than 50 microeq/L in 1900. Model projections, based on atmospheric emissions controls representative of laws already enacted as of 2003, suggested that the ANC of those streams simulated to have experienced the largest historical decreases in ANC will increase in the future. The levels of S deposition that were simulated to cause streamwater ANC to increase or decrease to three specified critical levels (0, 20, and 50 microeq/L) ranged from less than zero (ANC level not attainable) to several hundred kg/ha/year, depending on the selected site and its inherent acid-sensitivity, selected ANC endpoint criterion, and evaluation year for which the critical load was calculated. Several of the modeled streams situated on siliciclastic geology exhibited critical loads <0 kg/ha/year to achieve ANC >50 microeq/L in the year 2040, probably due at least in part to base cation losses from watershed soil. The median modeled siliciclastic stream had a calculated critical load to achieve ANC >50 microeq/L in 2100 that was about 3 kg/ha/year, or 77% lower than deposition in 1990, representing the time of model calibration.

  20. Atmospheric wet deposition of nitrogen and sulfur in the agroecosystem in developing and developed areas of Southeastern China

    NASA Astrophysics Data System (ADS)

    Cui, Jian; Zhou, Jing; Peng, Ying; He, Yuanqiu; Yang, Hao; Mao, Jingdong; Zhang, Mingli; Wang, Yanhua; Wang, Shuwei

    2014-06-01

    Atmospheric nitrogen (N) and sulfur (S) deposition is a significant and growing issue for ecological environment in many parts of the world such as China. However, the study on atmospheric deposition, especially N deposition, is still at the initial stage and usually neglected in agro-ecosystems. To assess the characteristics of N and S wet deposition in agro-ecosystems, we selected Yingtan Station (YTS) located in the developing area and Changshu Station (CSS) in the developed area as typical, agricultural study sites in Southeastern China during 2010-2011. In the two areas, the total N and S wet deposition were in ranges of 30.49-37.37 kg ha-1 year-1 N and 56.02-59.06 kg ha-1 year-1 S, respectively, surpassing their corresponding critical loads in China. The annual means of NH4+-N, NO3--N and dissolved organic N (DON) deposition contributed 49.6%, 26.4% and 24.0% of the total deposition, respectively. Similar total N and S deposition data were observed in the two sites, but their N species, especially DON, were different due to different numbers of slaughter pigs and types of N fertilizers applied. In conclusion, DON was identified as an important contributor to the total N deposition and should also be monitored in the future. Such high N and S deposition would deteriorate agroecosystems in Southeastern China. Related political measures on livestock industries, managements of motor vehicles and technologies of coal and oil combustion should be improved timely and implemented effectively for reducing the regional N emission and deposition in the future.

  1. Effect of ions on sulfuric acid-water binary particle formation: 1. Theory for kinetic- and nucleation-type particle formation and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Merikanto, Joonas; Duplissy, Jonathan; Määttänen, Anni; Henschel, Henning; Donahue, Neil M.; Brus, David; Schobesberger, Siegfried; Kulmala, Markku; Vehkamäki, Hanna

    2016-02-01

    We derive a version of Classical Nucleation Theory normalized by quantum chemical results on sulfuric acid-water hydration to describe neutral and ion-induced particle formation in the binary sulfuric acid-water system. The theory is extended to treat the kinetic regime where the nucleation free energy barrier vanishes at high sulfuric acid concentrations or low temperatures. In the kinetic regime particle formation rates become proportional to sulfuric acid concentration to second power in the neutral system or first power in the ion-induced system. We derive simple general expressions for the prefactors in kinetic-type and activation-type particle formation calculations applicable also to more complex systems stabilized by other species. The theory predicts that the binary water-sulfuric acid system can produce strong new particle formation in the free troposphere both through barrier crossing and through kinetic pathways. At cold stratospheric and upper free tropospheric temperatures neutral formation dominates the binary particle formation rates. At midtropospheric temperatures the ion-induced pathway becomes the dominant mechanism. However, even the ion-induced binary mechanism does not produce significant particle formation in warm boundary layer conditions, as it requires temperatures below 0°C to take place at atmospheric concentrations. The theory successfully reproduces the characteristics of measured charged and neutral binary particle formation in CERN CLOUD3 and CLOUD5 experiments, as discussed in a companion paper.

  2. Target loads of atmospheric sulfur and nitrogen deposition for protection of acid sensitive aquatic resources in the Adirondack Mountains, New York

    USGS Publications Warehouse

    Sullivan, T.J.; Cosby, B.J.; Driscoll, C.T.; McDonnell, T.C.; Herlihy, A.T.; Burns, Douglas A.

    2012-01-01

    The dynamic watershed acid-base chemistry model of acidification of groundwater in catchments (MAGIC) was used to calculate target loads (TLs) of atmospheric sulfur and nitrogen deposition expected to be protective of aquatic health in lakes in the Adirondack ecoregion of New York. The TLs were calculated for two future dates (2050 and 2100) and three levels of protection against lake acidification (acid neutralizing capacity (ANC) of 0, 20, and 50 eq L -1). Regional sulfur and nitrogen deposition estimates were combined with TLs to calculate exceedances. Target load results, and associated exceedances, were extrapolated to the regional population of Adirondack lakes. About 30% of Adirondack lakes had simulated TL of sulfur deposition less than 50 meq m -2 yr to protect lake ANC to 50 eq L -1. About 600 Adirondack lakes receive ambient sulfur deposition that is above this TL, in some cases by more than a factor of 2. Some critical criteria threshold values were simulated to be unobtainable in some lakes even if sulfur deposition was to be decreased to zero and held at zero until the specified endpoint year. We also summarize important lessons for the use of target loads in the management of acid-impacted aquatic ecosystems, such as those in North America, Europe, and Asia. Copyright 2012 by the American Geophysical Union.

  3. Atmospheric So2 Emissions Since the Late 1800s Change Organic Sulfur Forms in Humic Substance Extracts of Soils

    SciTech Connect

    Lehmann,J.; Solomon, D.; Zhao, F.; McGrath, S.

    2008-01-01

    Atmospheric SO2 emissions in the UK and globally increased 6- and 20-fold, respectively, from the mid-1800s to the 1960s resulting in increased S deposition, acid rain, and concurrent acidification of terrestrial and aquatic ecosystems. Structural analyses using synchrotron-based X-ray near-edge spectroscopy (XANES) on humic substance extracts of archived samples from the Rothamsted Park Grass Experiment reveal a significant (R2 = -0.58; P < 0.05; N = 7) shift in soil organic sulfur (S) forms, from reduced to more oxidized organic S between 1876 and 1981, even though soil total S contents remained relatively constant. Over the last 30 years, a decrease in emissions and consequent S deposition has again corresponded with a change of organic S structures of humic extractsreverting in the direction of their early industrial composition. However, the observed reversal lagged behind reductions in emissions by 19 years, which was computed using cross correlations between time series data (R2 = 0.66; P = 0.0024; N = 11). Presently, the ratio of oxidized-to-reduced organic S in humic substance extracts is nearly double that of early industrial times at identical SO2 emission loads. The significant and persistent structural changes of organic S in humic substances as a response to SO2 emissions and S deposition may have effects on recuperation of soils and surface waters from acidification.

  4. Atmospheric SO2 emissions since the late 1800s change organic sulfur forms in humic substance extracts of soils.

    PubMed

    Lehmann, Johannes; Solomon, Dawit; Zhao, Fang-Jie; McGrath, Steve P

    2008-05-15

    Atmospheric SO2 emissions in the UK and globally increased 6- and 20-fold, respectively, from the mid-1800s to the 1960s resulting in increased S deposition, acid rain, and concurrent acidification of terrestrial and aquatic ecosystems. Structural analyses using synchrotron-based X-ray near-edge spectroscopy (XANES) on humic substance extracts of archived samples from the Rothamsted Park Grass Experiment reveal a significant (R2 = -0.58; P < 0.05; N = 7) shift in soil organic sulfur (S) forms, from reduced to more oxidized organic S between 1876 and 1981, even though soil total S contents remained relatively constant. Over the last 30 years, a decrease in emissions and consequent S deposition has again corresponded with a change of organic S structures of humic extracts-reverting in the direction of their early industrial composition. However, the observed reversal lagged behind reductions in emissions by 19 years, which was computed using cross correlations between time series data (R2 = 0.66; P = 0.0024; N = 11). Presently, the ratio of oxidized-to-reduced organic S in humic substance extracts is nearly double that of early industrial times at identical SO2 emission loads. The significant and persistent structural changes of organic S in humic substances as a response to SO2 emissions and S deposition may have effects on recuperation of soils and surface waters from acidification.

  5. Vertical Distributions of Sulfur Species Simulated by Large Scale Atmospheric Models in COSAM: Comparison with Observations

    SciTech Connect

    Lohmann, U.; Leaitch, W. R.; Barrie, Leonard A.; Law, K.; Yi, Y.; Bergmann, D.; Bridgeman, C.; Chin, M.; Christensen, J.; Easter, Richard C.; Feichter, J.; Jeuken, A.; Kjellstrom, E.; Koch, D.; Land, C.; Rasch, P.; Roelofs, G.-J.

    2001-11-01

    A comparison of large-scale models simulating atmospheric sulfate aerosols (COSAM) was conducted to increase our understanding of global distributions of sulfate aerosols and precursors. Earlier model comparisons focused on wet deposition measurements and sulfate aerosol concentrations in source regions at the surface. They found that different models simulated the observed sulfate surface concentrations mostly within a factor of two, but that the simulated column burdens and vertical profiles were very different amongst different models. In the COSAM exercise, one aspect is the comparison of sulfate aerosol and precursor gases above the surface. Vertical profiles of SO2, SO42-, oxidants and cloud properties were measured by aircraft during the North Atlantic Regional Experiment (NARE) experiment in August/September 1993 off the coast of Nova Scotia and during the Second Eulerian Model Evaluation Field Study (EMEFSII) in central Ontario in March/April 1990. While no single model stands out as being best or worst, the general tendency is that those models simulating the full oxidant chemistry tend to agree best with observations although differences in transport and treatment of clouds are important as well.

  6. Atmospheric Fate of Monoethanolamine: Enhancing New Particle Formation of Sulfuric Acid as an Important Removal Process.

    PubMed

    Xie, Hong-Bin; Elm, Jonas; Halonen, Roope; Myllys, Nanna; Kurtén, Theo; Kulmala, Markku; Vehkamäki, Hanna

    2017-08-01

    Monoethanolamine (MEA), a potential atmospheric pollutant from the capture unit of a leading CO2 capture technology, could be removed by participating H2SO4-based new particle formation (NPF) as simple amines. Here we evaluated the enhancing potential of MEA on H2SO4-based NPF by examining the formation of molecular clusters of MEA and H2SO4 using combined quantum chemistry calculations and kinetics modeling. The results indicate that MEA at the parts per trillion (ppt) level can enhance H2SO4-based NPF. The enhancing potential of MEA is less than that of dimethylamine (DMA), one of the strongest enhancing agents, and much greater than methylamine (MA), in contrast to the order suggested solely by their basicity (MEA < MA < DMA). The unexpectedly high enhancing potential is attributed to the role of -OH of MEA in increasing cluster binding free energies by acting as both a hydrogen bond donor and acceptor. After the initial formation of one H2SO4 and one MEA cluster, the cluster growth mainly proceeds by first adding one H2SO4, and then one MEA, which differs from growth pathways in H2SO4-DMA and H2SO4-MA systems. Importantly, the effective removal rate of MEA due to participation in NPF is comparable to that of oxidation by hydroxyl radicals at 278.15 K, indicating NPF as an important sink for MEA.

  7. Spatial and seasonal variations of atmospheric sulfur concentrations and dry deposition at 16 rural and suburban sites in China

    NASA Astrophysics Data System (ADS)

    Luo, Xiaosheng; Pan, Yuepeng; Goulding, Keith; Zhang, Lin; Liu, Xuejun; Zhang, Fusuo

    2016-12-01

    The large emissions of sulfur dioxide (SO2) in China have raised worldwide concerns due to its contribution to acid rain and particulate pollution. Monitoring sulfur (S) concentrations and estimating its deposition are important for evaluating air quality and its effects on ecosystems and human health. To date atmospheric dry S deposition in China remains unclear due to the paucity of measurements, especially in rural regions where the ecosystems are sensitive to acid deposition. In this study, we monitored both SO2 and particulate SO42- (pSO42-) concentrations at 8 sites south and 8 sites north of the Huai River in rural and suburban parts of China between 2010 and 2012. The measured concentration of SO2 and pSO42- were combined with GEOS-Chem modeled dry deposition velocities to estimate dry S deposition inputs to the surfaces. SO2 and pSO42- concentrations were high from October/November to next March/April and they (esp. SO2) decreased sharply since March/April at the northern sites, reflecting elevated SO2 emissions by winter heating (which normally starts in October/November and ends in March/April in the north of the Huai River). However the southern sites did not show this trend. Annual dry deposition of SO2 plus pSO42- in this study ranged from 3.1 to 27.1 kg S ha-1 across all the sites in the year 2011 (except one site from May 2011 to April 2012) and showed large spatial variation. The sites in northern China had greater dry deposition due to the higher S concentrations compared with sites in southern China. We also found relatively low pSO42-/pNO3- ratios at most sites, reflecting NOx emissions had a larger influence than SO2 emissions on particle composition during the 2010-2012 period at the measurement sites. Our results suggest that dry S deposition is still important input to ecosystems in spite of slow reduction of Chinese national SO2 emissions since 2005. More research on both wet and dry S deposition and their impacts on the environment and

  8. Behavior of sulfur mustard in sand, concrete, and asphalt matrices: Evaporation, degradation, and decontamination.

    PubMed

    Jung, Hyunsook; Choi, Seungki

    2017-07-24

    The evaporation, degradation, and decontamination of sulfur mustard on environmental matrices including sand, concrete, and asphalt are described. A specially designed wind tunnel and thermal desorber in combination with gas chromatograph (GC) produced profiles of vapor concentration obtained from samples of the chemical agent deposited as a drop on the surfaces of the matrices. The matrices were exposed to the chemical agent at room temperature, and the degradation reactions were monitored and characterized. A vapor emission test was also performed after a decontamination process. The results showed that on sand, the drop of agent spread laterally while evaporating. On concrete, the drop of the agent was absorbed immediately into the matrix while spreading and evaporating. However, the asphalt surface conserved the agent and slowly released parts of the agent over an extended period of time. The degradation reactions of the agent followed pseudo first order behavior on the matrices. Trace amounts of the residual agent present at the surface were also released as vapor after decontamination, posing a threat to the exposed individual and environment.

  9. Meteorite fractures and the behavior of meteoroids in the atmosphere

    NASA Astrophysics Data System (ADS)

    Bryson, K.; Ostrowski, D. R.; Sears, D. W. G.

    2015-12-01

    Arguably the major difficulty faced to model the atmospheric behavior of objects entering the atmosphere is that we know very little about the internal structure of these objects and their methods of fragmentation during fall. In a study of over a thousand meteorite fragments (mostly hand-sized, some 40 or 50 cm across) in the collections of the Natural History Museums in Vienna and London, we identified six kinds of fracturing behavior. (1) Chondrites usually showed random fractures with no particular sensitivity to meteorite texture. (2) Coarse irons fractured along kamacite grain boundaries, while (3) fine irons fragmented randomly, c.f. chondrites. (4) Fine irons with large crystal boundaries (e.g. Arispe) fragmented along the crystal boundaries. (5) A few chondrites, three in the present study, have a distinct and strong network of fractures making a brickwork or chicken-wire structure. The Chelyabinsk meteorite has the chicken-wire structure of fractures, which explains the very large number of centimeter-sized fragments that showered the Earth. Finally, (6) previous work on Sutter's Mill showed that water-rich meteorites fracture around clasts. To scale the meteorite fractures to the fragmentation behavior of near-Earth asteroids, it has been suggested that the fracturing behavior follows a statistical prediction made in the 1930s, the Weibull distribution, where fractures are assumed to be randomly distributed through the target and the likelihood of encountering a fracture increases with distance. This results in a relationship: σl = σs(ns/nl)α, where σs and σl refers to stress in the small and large object and ns and nl refer to the number of cracks per unit volume of the small and large object. The value for α, the Weibull coefficient, is unclear. Ames meteorite laboratory is working to measure the density and length of fractures observed in these six types of fracture to determine values for the Weibull coefficient for each type of object.

  10. Tribological behavior of near-frictionless carbon coatings in high- and low-sulfur diesel fuels.

    SciTech Connect

    Alzoubi, M. F.; Ajayi, O. O.; Eryilmaz, O. L.; Ozturk, O.; Erdemir, A.; Fenske, G.

    2000-01-19

    The sulfur content in diesel fuel has a significant effect on diesel engine emissions, which are currently subject to environmental regulations. It has been observed that engine particulate and gaseous emissions are directly proportional to fuel sulfur content. With the introduction of low-sulfur fuels, significant reductions in emissions are expected. The process of sulfur reduction in petroleum-based diesel fuels also reduces the lubricity of the fuel, resulting in premature failure of fuel injectors. Thus, another means of preventing injector failures is needed for engines operating with low-sulfur diesel fuels. In this study, the authors evaluated a near-frictionless carbon (NFC) coating (developed at Argonne National Laboratory) as a possible solution to the problems associated with fuel injector failures in low-lubricity fuels. Tribological tests were conducted with NFC-coated and uncoated H13 and 52100 steels lubricated with high- and low- sulfur diesel fuels in a high-frequency reciprocating test machine. The test results showed that the NFC coatings reduced wear rates by a factor of 10 over those of uncoated steel surfaces. In low-sulfur diesel fuel, the reduction in wear rate was even greater (i.e., by a factor of 12 compared to that of uncoated test pairs), indicating that the NFC coating holds promise as a potential solution to wear problems associated with the use of low-lubricity diesel fuels.

  11. Validation of coupled atmosphere-fire behavior models

    SciTech Connect

    Bossert, J.E.; Reisner, J.M.; Linn, R.R.; Winterkamp, J.L.; Schaub, R.; Riggan, P.J.

    1998-12-31

    Recent advances in numerical modeling and computer power have made it feasible to simulate the dynamical interaction and feedback between the heat and turbulence induced by wildfires and the local atmospheric wind and temperature fields. At Los Alamos National Laboratory, the authors have developed a modeling system that includes this interaction by coupling a high resolution atmospheric dynamics model, HIGRAD, with a fire behavior model, BEHAVE, to predict the spread of wildfires. The HIGRAD/BEHAVE model is run at very high resolution to properly resolve the fire/atmosphere interaction. At present, these coupled wildfire model simulations are computationally intensive. The additional complexity of these models require sophisticated methods for assuring their reliability in real world applications. With this in mind, a substantial part of the research effort is directed at model validation. Several instrumented prescribed fires have been conducted with multi-agency support and participation from chaparral, marsh, and scrub environments in coastal areas of Florida and inland California. In this paper, the authors first describe the data required to initialize the components of the wildfire modeling system. Then they present results from one of the Florida fires, and discuss a strategy for further testing and improvement of coupled weather/wildfire models.

  12. The Nonlinear Behaviors in Atmospheric Dielectric Barrier Multi Pulse Discharges

    NASA Astrophysics Data System (ADS)

    Zhang, Dingzong; Wang, Yanhui; Wang, Dezhen

    2016-08-01

    An in-depth and comprehensive understanding of the complex nonlinear behaviors in atmospheric dielectric barrier discharge is significant for the stable operation and effective control of the plasma. In this paper, we study the nonlinear behaviors in argon atmospheric dielectric barrier multi pulse discharges by a one-dimensional fluid model. Under certain conditions, the multi pulse discharge becomes very sensitive with the increase of frequency, and the multi pulse period-doubling bifurcation, inverse period-doubling bifurcation and chaos appear frequently. The discharge can reach a relatively steady state only when the discharges are symmetrical between positive and negative half cycle. In addition, the effects of the voltage on these nonlinear discharges are also studied. It is found that the amplitude of voltage has no effects on the number of discharge pulses in multi-pulse period-doubling bifurcation sequences; however, to a relatively stable periodic discharge, the discharge pulses are proportional to the amplitude of the applied voltage within a certain range. supported by National Natural Science Foundation of China (No. 11447244), the Science Foundation of Hengyang Normal University of China (No. 14B41), the Construct Program of the Key Discipline in Hunan Province, and the Hunan Provincial Applied Basic Research Base of Optoelectronic Information Technology of China (No. GDXX010)

  13. Segregation Behavior of Sulfur and Other Impurities onto the Free Surfaces of ED-NI Deposits

    NASA Technical Reports Server (NTRS)

    Panda, B.; Jerman, G.

    2001-01-01

    Most researchers attribute grain boundary embrittlement in electro-deposited nickel (ED-Ni) to the presence of small quantities of sulfur as an impurity. It occurs in a highly mobile form that segregates to the grain boundaries. Evaluation of sulfur segregation requires that a sample be fractured through the grain boundaries. However, this action may not always be possible. ED-Ni is inherently tough at ambient temperature, especially if a low level of sulfur was intentionally maintained. A new method was developed to study sulfur and other migrant species to the grain boundaries, which also migrate to free surfaces. A test specimen is heated by a quartz lamp within the sample preparation chamber, allowing the mobile species to migrate to polished free surfaces. There the mobile species are analyzed using X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA).

  14. Segregation Behavior of Sulfur and Other Impurities Onto the Free Surfaces of ED-Ni Deposits

    NASA Technical Reports Server (NTRS)

    Panda, Binayak; Jerman, Gregory; Gentz, Steven J. (Technical Monitor)

    2000-01-01

    Most researchers attribute grain boundary embrittlement in electro-deposited Nickel (ED-Ni) to the presence of small quantities of Sulfur as an impurity. It occurs in a highly mobile form that segregates to the grain boundaries. Evaluation of Sulfur segregation requires that a sample be fractured through the grain boundaries. However, this action may not always be possible. ED-Ni is inherently tough at ambient temperature, especially if a low level of Sulfur was intentionally maintained. A new method was developed to study Sulfur and other migrant species to the grain boundaries, which also migrate to free surfaces. A test specimen is heated by a quartz lamp within the sample preparation chamber, allowing the mobile species to migrate to polished free surfaces. There the mobile species are analyzed using X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA).

  15. Freezing behavior of single sulfuric acid aerosols suspended in a quadrupole trap

    NASA Astrophysics Data System (ADS)

    Carleton, K. L.; Sonnenfroh, D. M.; Rawlins, W. T.; Wyslouzil, B. E.; Arnold, S.

    1997-03-01

    The freezing properties of sulfuric acid droplets were studied by suspending single 20- to 30-μm-diameter particles in a quadrupole trap and cooling them to stratospheric temperatures (≥191.5 K). Each particle's dc balance voltage was measured to determine the particle composition as a function of temperature and map out the particle's trajectory relative to the sulfuric acid phase diagram. Angularly resolved optical scattering patterns were monitored to detect freezing events. Particles cooled through the sulfuric acid tetrahydrate region (35-70 wt % H2SO4) did not freeze and remained spherical liquid droplets for several hours. Only particles cooled through the ice-liquid equilibrium region (<35 wt% H2SO4) showed evidence of freezing. This supports previous experimental and field observations that stratospheric sulfuric acid aerosols are likely to remain liquid to within a few degrees of the ice frost point.

  16. Behavioral responses of broilers to different gaseous atmospheres.

    PubMed

    Gerritzen, M A; Lambooij, E; Hillebrand, S J; Lankhaar, J A; Pieterse, C

    2000-06-01

    This study was conducted to determine the differences in behavioral response of broilers when they come into contact for the first time with gas mixtures that can be used for stunning. The six test groups were divided into four experimental groups that were exposed to gas mixtures used for stunning and two control groups that were exposed to atmospheric air. The different gas mixtures and their concentrations were a) air, no flow (control-); b) circulating air, flowing (control+); c) >90% Ar in air; d) 60% CO2 in air; e) 40% CO2 and 30% O2 in air; and f) 70% Ar and 30% CO2 in air. The behavior of the broilers before entering the gas tunnel, the number of birds that moved into the gas mixture, and the behavior in the gas mixture were recorded on video and analyzed afterward. No differences among the groups were observed in the number of broilers that walked into the gas tunnel or in the number of birds that tried to return to the cage. Exposure of broilers to the 70% Ar and 30% CO2 mixture resulted in the fastest loss of posture. The number of broilers exhibiting headshaking and gasping was least in the >90% Ar in air mixture. Convulsions were rarely seen in the 40% CO2 and 30% O2 mixture; the other gas mixtures resulted in severe convulsions. The experiment did not indicate that broilers could detect or avoid increased CO2 or decreased O2 levels when they come into contact with such atmospheres for the first time.

  17. Sulfur mass loading of the atmosphere from volcanic eruptions: Calibration of the ice core record on basis of sulfate aerosol deposition in polar regions from the 1982 El Chichon eruption

    NASA Technical Reports Server (NTRS)

    Sigurdsson, Haraldur; Laj, Paolo

    1990-01-01

    Major volcanic eruptions disperse large quantities of sulfur compound throughout the Earth's atmosphere. The sulfuric acid aerosols resulting from such eruptions are scavenged by snow within the polar regions and appear in polar ice cores as elevated acidity layers. Glacio-chemical studies of ice cores can, thus, provide a record of past volcanism, as well as the means for understanding the fate of volcanic sulfur in the atmosphere. The primary objectives of this project are to study the chemistry and physical properties of volcanic fallout in a Greenland Ice Core in order to evaluate the impact of the volcanic gases on the atmospheric chemistry and the total atmospheric mass of volcanic aerosols emitted by major volcanic eruptions. We propose to compare the ice core record to other atmospheric records performed during the last 10 years to investigate transport and deposition of volcanic materials.

  18. Sulfur mass loading of the atmosphere from volcanic eruptions: Calibration of the ice core record on basis of sulfate aerosol deposition in polar regions from the 1982 El Chichon eruption. Semiannual progress report

    SciTech Connect

    Sigurdsson, H.; Laj, P.

    1990-09-01

    Major volcanic eruptions disperse large quantities of sulfur compound throughout the Earth's atmosphere. The sulfuric acid aerosols resulting from such eruptions are scavenged by snow within the polar regions and appear in polar ice cores as elevated acidity layers. Glacio-chemical studies of ice cores can, thus, provide a record of past volcanism, as well as the means for understanding the fate of volcanic sulfur in the atmosphere. The primary objectives of this project are to study the chemistry and physical properties of volcanic fallout in a Greenland Ice Core in order to evaluate the impact of the volcanic gases on the atmospheric chemistry and the total atmospheric mass of volcanic aerosols emitted by major volcanic eruptions. The authors propose to compare the ice core record to other atmospheric records performed during the last 10 years to investigate transport and deposition of volcanic materials.

  19. Geochemical behavior of sulfur in granitoids during intrusion of the South Mountain batholith, Nova Scotia, Canada

    NASA Astrophysics Data System (ADS)

    Poulson, Simon R.; Kubilius, Walter P.; Ohmoto, Hiroshi

    1991-12-01

    A detailed stable isotope (S, O) and elemental (major, trace, S content) study of peraluminous S-type granites and granodiorites of the South Mountain Batholith and the Meguma Group metasediments into which the batholith was intruded has been conducted on a regional and local scale near Mt. Uniacke. Sulfur contents of the metasediments range from 5 to 2440 ppm, and δ 34S ranges from -3.7 to +26.3%. Sulfur contents of the igneous rocks range from 6 to 570 ppm, with the granites ( ≈20 ppm) having lower sulfur contents than the granodiorites ( ≈300 ppm). Approximately 30 to 60% of the sulfur in the granodiorites is present as pyrrhotite (a late phase), with most of the remainder being present as sulfur substituted into biotite (an early phase). δ 18OQ Quartz values of the Mt. Uniacke granodiorites are heavy (≈a + 12.2%.) indicating formation of the magmas by partial melting of sedimentary rocks. Major element variations suggest that the granites are related to the granodiorites by fractional crystallization of plagioclase, quartz, and biotite. Comparison of the sulfur contents of the granodiorites with experimental determinations of sulfur solubility suggest that the distribution coefficient of sulfur ( Ds) between the cumulate and the magma during fractional crystallization ≈4. The regional granodiorites have a relatively restricted range of δ 34S values (+5.4 to + 8.4%.), while the regional granites have a wide range of δ 34S values ( + 1.6 to + 15.0%.). Granodiorites at Mt. Uniacke with normal magmatic values (+0.76 to +1.42%.) for Δ 18O (Quartz-Feldspar) have δ 34S values between +6.6 and +12.3%., and show good negative correlations between δ 34S and S, FeO, and MgO contents. Some granodiorites at Mt. Uniacke have anomalously low sulfur contents for their major element composition, and Δ 18O (Quartz-Feldspar) values (-0.45 to +0.67%. ) indicate that these samples have undergone hydrothermal alteration, and this alteration event is probably

  20. A study of the total atmospheric sulfur dioxide load using ground-based measurements and the satellite derived Sulfur Dioxide Index

    NASA Astrophysics Data System (ADS)

    Georgoulias, A. K.; Balis, D.; Koukouli, M. E.; Meleti, C.; Bais, A.; Zerefos, C.

    We present characteristics of the sulfur dioxide (SO 2) loading over Thessaloniki, Greece, and seven other selected sites around the world using SO 2 total column measurements from Brewer spectrophotometers together with satellite estimates of the Version 8 TOMS Sulfur Dioxide Index (SOI) over the same locations, retrieved from Nimbus 7 TOMS (1979-1993), Earth Probe TOMS (1996-2003) and OMI/Aura (2004-2006). Traditionally, the SOI has been used to quantify the SO 2 quantities emitted during great volcanic eruptions. Here, we investigate whether the SOI can give an indication of the total SO 2 load for areas and periods away from eruptive volcanic activity by studying its relative changes as a correlative measure to the SO 2 total column. We examined time series from Thessaloniki and another seven urban and non-urban stations, five in the European Union (Arosa, De Bilt, Hohenpeissenberg, Madrid, Rome) and two in India (Kodaikanal, New Delhi). Based on the Brewer data, Thessaloniki shows high SO 2 total columns for a European Union city but values are still low if compared to highly affected regions like those in India. For the time period 1983-2006 the SO 2 levels above Thessaloniki have generally decreased with a rate of 0.028 Dobson Units (DU) per annum, presumably due to the European Union's strict sulfur control policies. The seasonal variability of the SO 2 total column exhibits a double peak structure with two maxima, one during winter and the second during summer. The winter peak can be attributed to central heating while the summer peak is due to synoptic transport from sources west of the city and sources in the north of Greece. A moderate correlation was found between the seasonal levels of Brewer total SO 2 and SOI for Thessaloniki, Greece ( R = 0.710-0.763) and Madrid, Spain ( R = 0.691) which shows that under specific conditions the SOI might act as an indicator of the SO 2 total load.

  1. Behavior of sulfur and chlorine in coal during combustion and boiler corrosion. Technical report, December 1, 1991--February 29, 1992

    SciTech Connect

    Chou, C.L.; Hackley, K.C.; Donnals, G.L.; Cao, J.; Ruch, R.R.; Pan, W.P.; Shao, D.

    1992-08-01

    The goal of this project is to study the evolution of gaseous sulfur and chlorine species during temperature-controlled pyrolysis and combustion and their effect on boiler corrosion. We have been developing two techniques for determining the gas evolution profiles of sulfur and chlorine during coal pyrolysis and combustion. First, using a pyrolysis-combustion system in combination with a quadrupole gas analyzer, the evolution of sulfur dioxide (SO{sub 2}) in combustion gas during temperature-programmed coal pyrolysis-combustion was monitored. When the atmosphere of the combustion chamber was changed to a reducing condition, gaseous COS and H{sub 2}S were also detected in the combustion gas. Detection of hydrogen chloride by QGA has been improved by using a larger-diameter (75 {mu}m) capillary tubing. The HC1 evolution profile during the pyrolysis of coal IBC-109 was determined by QGA and by a chloride ion selective electrode for quantitative purposes. Second, the technique of thermogravimetry (TG) in conjunction with Fourier transform infrared (FTIR) spectroscopy was used to characterize gaseous species during coal pyrolysis. Gas evolution profiles of sulfur (SO{sub 2} and COS), chlorine (HC1), and nitrogen (NH{sub 3} and HCN) species were determined for coal IBC-109. Similar release profiles of HCI and NH{sub 3} supported an interpretation that chlorine gnd nitrogen are closely associated in coal. COS may be formed by reaction of CO with H{sub 2}S in the gas phase. A mass balance study of chlorine evolution from coal IBC-109 in a TG-FTIR experiment was completed; the chloride dissolved in solutions was determined by an ion chromatographic technique.

  2. Hydrogen Sulfide Sequestration and Storage in Geothermal System: New Mitigation Strategy to Reduce H2S from the Atmosphere and Detect its Mineralization with Multiple Sulfur Isotopic Systematics

    NASA Astrophysics Data System (ADS)

    Marieni, C.; Stefansson, A.; Gudbrandsson, S.; Gunnarsson, I.; Aradottir, E. S.; Gunnarsson Robin, J.; Ono, S.

    2015-12-01

    Hydrogen sulfide (H2S) is one of the major components in geothermal fluids and is commonly emitted into the atmosphere from geothermal power plants causing potential environmental problems. Among several mitigation methods proposed to reduce the H2S emissions, is H2S sequestration into geothermal systems. Reykjavík Energy is undertaking a pilot project at Hellisheidi geothermal system (SW Iceland) called Sulfix project where H2S is being injected into the geothermal reservoir for permanent sequestration into pyrite. The SulFix project started its operation in June 2014: the soluble geothermal gases are dissolved in geothermal waste water, and injected at 8 bars into the high temperature reservoir (>200˚C) at 750 m below the wellhead. The reactions involving sulfur in the geothermal reservoir may be traced using sulfur fluid chemistry and multiple sulfur isotope systematics (32S, 33S, 34S and 36S), including mixing between the reservoir geothermal fluid and the injection fluid, sulfide mineralization and oxidation of sulfide to sulfate. In this study we investigated the multiple sulfur isotope systematics upon sulfide mineralization under geothermal conditions. High temperature flow through experiments were carried out in basaltic glass at 200-250°C and ~5 mmol/kg H2S to study the fluid-rock interaction. The results indicate that the sulfide mineralization occurs rapidly under geothermal conditions, highlighting the leaching rate of iron from the basaltic glass as the mineralization rate determining factor. Moreover, the formation of sulfide may be traced using the δ34S-Δ33S relationship in the fluids and pyrite formation - for example to determine if non-reactive mixing between the injection fluids and reservoir fluids occurs at Hellisheidi. The experimental results have been further supported by geochemical modeling involving multiple sulfur isotope fractionation between aqueous sulfide species and rocks upon basalt dissolution and secondary pyrite formation.

  3. Atmospheric evolution of sulfur emissions from Kı̅lauea: real-time measurements of oxidation, dilution, and neutralization within a volcanic plume.

    PubMed

    Kroll, Jesse H; Cross, Eben S; Hunter, James F; Pai, Sidhant; Wallace, Lisa M M; Croteau, Philip L; Jayne, John T; Worsnop, Douglas R; Heald, Colette L; Murphy, Jennifer G; Frankel, Sheila L

    2015-04-07

    The high atmospheric concentrations of toxic gases, particulate matter, and acids in the areas immediately surrounding volcanoes can have negative impacts on human and ecological health. To better understand the atmospheric fate of volcanogenic emissions in the near field (in the first few hours after emission), we have carried out real-time measurements of key chemical components of the volcanic plume from Kı̅lauea on the Island of Hawai'i. Measurements were made at two locations, one ∼ 3 km north-northeast of the vent and the other 31 km to the southwest, with sampling at each site spanning a range of meteorological conditions and volcanic influence. Instrumentation included a sulfur dioxide monitor and an Aerosol Chemical Speciation Monitor, allowing for a measurement of the partitioning between the two major sulfur species (gas-phase SO2 and particulate sulfate) every 5 min. During trade wind conditions, which sent the plume toward the southwest site, sulfur partitioning exhibited a clear diurnal pattern, indicating photochemical oxidation of SO2 to sulfate; this enabled the quantitative determination of plume age (5 h) and instantaneous SO2 oxidation rate (2.4 × 10(-6) s(-1) at solar noon). Under stagnant conditions near the crater, the extent of SO2 oxidation was substantially higher, suggesting faster oxidation. The particles within the plume were extremely acidic, with pH values (controlled largely by ambient relative humidity) as low as -0.8 and strong acidity (controlled largely by absolute sulfate levels) up to 2200 nmol/m(3). The high variability of sulfur partitioning and particle composition underscores the chemically dynamic nature of volcanic plumes, which may have important implications for human and ecological health.

  4. Behavior of self-confined spherical layer of light radiation in the air atmosphere

    NASA Astrophysics Data System (ADS)

    Torchigin, V. P.; Torchigin, A. V.

    2004-07-01

    Behavior of thin spherical layer of intensive light in an inhomogeneous atmosphere is considered. It is shown that the behavior is similar to puzzling and mysterious behavior of ball lightnings. Under assumption that ball lightning moves along the gradient of atmosphere air density process of ball lightning penetration in a salon of a flying airplane is analyzed.

  5. Sulfur Earth

    NASA Astrophysics Data System (ADS)

    de Jong, B. H.

    2007-12-01

    Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

  6. Atmospheric deposition of sulfur and inorganic nitrogen in the Southern Canadian Rocky Mountains from seasonal snowpacks and bulk summer precipitation

    NASA Astrophysics Data System (ADS)

    Wasiuta, Vivian; Lafrenière, Melissa J.; Norman, Ann-Lise

    2015-04-01

    This study quantified atmospheric deposition of sulfur (S) and nitrogen (N) in the alpine of the Southern Canadian Rocky Mountains and evaluated loads relative to critical limits for ecologic effects on alpine ecosystems from N saturation and acidification. Deposition was evaluated by collecting seasonal snowpack and summer bulk precipitation samples along elevational transects in the alpine Haig Valley and given regional context using snowpack samples from six additional glacier sites. S and N deposition were evaluated in terms of two conceptual models. Model 1 representing deposition from emissions that are mainly distant and Model 2 representing deposition from a mixture of distant and local to regional emissions. Annual S and N (including ammonium (NH4+), nitrate (NO3-) and nitrite (NO2-)) deposition in the alpine Haig Valley was 0.74 ± 0.18 kg S ha-1 and 1.10 ± 0.18 kg N ha-1 yr-1, which is sufficiently high for the occurrence of detrimental ecologic effects related to N saturation in the most sensitive alpine ecosystems, but lower than the critical limit for acidification. Snowpack S and N deposition was consistent with well mixed air mainly from distant sources (Model 1), therefore indicating S and N were largely transported within the precipitating air mass and or picked up by the air mass in transit to the alpine Haig Valley. Relatively consistent deposition of S and N in seasonal glacier snowpacks at sites extending 210 km along the Continental Divide and 100 km west of the divide supports the interpretation that Model 1 describes deposition in alpine glacier snowpack. Similar deposition values for the highest site in the Haig Valley and the mean from the regional snowpack study indicate the highest site in the Haig Valley represents regional conditions of S and N deposition. Summer deposition of sulfate (SO42-) and ammonium (NH4+) was also consistent with dominantly distant emission sources (Model 1). In contrast there was enhanced transport and

  7. Behavior of sulfur at high pressures and low temperatures. [transition to high electroconductivity state

    NASA Technical Reports Server (NTRS)

    Golopentia, D. A.; Ruoff, A. L.

    1981-01-01

    A new type of high-pressure apparatus for low-temperature experiments was built, which allows loading and measuring the load in situ at low temperature (1.5 K). It uses the diamond anvil in the flat-indentor configuration. It was used to investigate the high-conductivity state of sulfur at low temperatures. For pressures in the 50-GPa range, sulfur is still a semiconductor or at best a two phase semiconductor-metal system. As the temperature is lowered at 50 GPa, the resistance drops slightly, reaches a minimum around 230 deg K, and then increases dramatically.

  8. Air Quality Criteria for Sulfur Oxides.

    ERIC Educational Resources Information Center

    National Air Pollution Control Administration (DHEW), Washington, DC.

    Included is a literature review which comprehensively discusses knowledge of the sulfur oxides commonly found in the atmosphere. The subject content is represented by the 10 chapter titles: Physical and Chemical Properties and the Atmospheric Reactions of the Oxides of Sulfur; Sources and Methods of Measurements of Sulfur Oxides in the Atmosphere;…

  9. Regeneration and sulfur poisoning behavior of In/H-BEA catalyst for NOx reduction by CH4

    NASA Astrophysics Data System (ADS)

    Pan, Hua; Jian, Yanfei; Yu, Yanke; He, Chi; Shen, Zhenxing; Liu, Hongxia

    2017-04-01

    Sulfur poisoning and regeneration behavior of In/H-BEA catalyst were carried out in NOx reduction by CH4. In/H-BEA catalyst exhibited a poor resistance to sulfur dioxide after addition of 200 ppm SO2 and 10 vol.% H2O into NO reduction with CH4 at 450 °C for 45 h. Sulfur poisoning of In/H-BEA was attributed to the inhibition of NOx adsorption on Brønsted acid sites, suppression of reaction intermediates generation on the active sites, and the formation of surface sulfate species. The formation of surface sulfate reduced the availability of surface active sites, blocked the pore structure and decreased the surface area of catalyst. These changes in chemical and textural properties resulted in a severe loss in the activity of sulfated In/H-BEA catalyst for NO reduction with CH4. H2 reduction is a promising technology for regeneration of In/H-BEA deactivated by SO2 for removing NOx from lean-burn and diesel exhausts. Indium sulfate could be reduced by H2 to InO+ with In2O3 and In(OH)2+ as the intermediates. The optimal parameters of H2 reduction was regeneration temperature of 400 °C and regeneration time of 60 min which completely recovered the catalytic activity of In/H-BEA.

  10. Effects of sulfur-metabolizing bacterial community diversity on H2S emission behavior in landfills with different operation modes.

    PubMed

    Fang, Yuan; Du, Yao; Hu, Lifang; Xu, Jing; Long, Yuyang; Shen, Dongsheng

    2016-11-01

    Hydrogen sulfide (H2S) is one of the major contributors to offensive odors from landfills, and its concentration differs under different operation modes. This study examined the distribution of H2S emission from different landfill depths under different operation modes (anaerobic, semi-aerobic, semi-aerobic transformation, and the three operation modes with additional leachate recirculation). The microbial community (especially the sulfur-metabolizing bacterial community) was investigated using high-throughput sequencing technology. The results showed that the semi-aerobic mode could substantially lower the risks of H2S pollution in landfills, which might be because of the difference in biological processes related to sulfur metabolism driven by functional microbes. A myriad of factors are responsible for mutually shaping the sulfur-metabolizing bacterial community composition in landfills that might subsequently affect the behavior of H2S emission in landfills. The differences in abundance of the genera Acinetobacter and Paracoccus (phylum Proteobacteria) caused by environmental factors might explain the differences in H2S emission. H2S odor control could be realized if the related functional microbe diversity can be influenced by adjustments to landfill operation.

  11. Differentiating atmospheric and mineral sources of sulfur during snowmelt using δ 34S, 35S activity, and δ 18O of sulfate and water as tracers

    NASA Astrophysics Data System (ADS)

    Shanley, J. B.; Mayer, B.; Mitchell, M. J.; Michel, R. L.; Bailey, S.; Kendall, C.

    2003-12-01

    The biogeochemical cycling of sulfur was studied during the 2000 snowmelt at Sleepers River Research Watershed in northeastern Vermont, USA using a combination of isotopic, chemical, and hydrometric measurements. The snowpack and 10 streams of varying size and land use were sampled for sulfate concentrations and isotopic analyses of 35S, δ 34S, and δ 18O of sulfate. Values of δ 18O of water were measured at one of the streams. Apportionment of atmospheric and mineral S sources based on δ 34S was possible at 7 of the 10 streams. Weathering of S-containing minerals was a major contributor to sulfate flux in streamwater, but atmospheric contributions exceeded 50% in several of the streams at peak snowmelt and averaged 41% overall. In contrast, δ 18Osulfate values of streamwater remained significantly lower than those of atmospheric sulfate throughout the melt period, indicating that atmospheric sulfate undergoes microbial redox reactions in the soil that replace the oxygen of atmospheric sulfate with isotopically lighter oxygen from soil water. Streamwater 35S activities were low relative to those of the snowpack; the youngest 35S-ages of the atmospheric S component in each of the 7 streams ranged from 184 to 320 days. Atmospheric S contributions to streamwater, as determined by δ 34S values, co-varied both with 35S activity and new water contributions as determined by δ 18Owater. However, the δ 18Osulfate and 35S ages clearly show that this new water carries very little of the atmospheric sulfate entering with the current snowmelt to the stream. Most incoming atmospheric sulfate first cycles through the organic soil S pool and ultimately reaches the stream as pedogenic sulfate.

  12. Method for preventing sulfur emissions from vessels containing molten sulfur

    SciTech Connect

    Hass, R. H.

    1984-10-23

    Emissions from sulfur pits or other vessels containing molten sulfur are prevented or minimized by use of an air purge drawn into the vessel from the atmosphere and subsequently utilized as a portion of the oxidant required in a process for oxidizing hydrogen sulfide to elemental sulfur.

  13. Atmospheric H2S and SO2 as sulfur source for Brassica juncea and Brassica rapa: impact on the glucosinolate composition.

    PubMed

    Aghajanzadeh, Tahereh; Kopriva, Stanislav; Hawkesford, Malcolm J; Koprivova, Anna; De Kok, Luit J

    2015-01-01

    The impact of sulfate deprivation and atmospheric H2S and SO2 nutrition on the content and composition of glucosinolates was studied in Brassica juncea and B. rapa. Both species contained a number of aliphatic, aromatic and indolic glucosinolates. The total glucosinolate content was more than 5.5-fold higher in B. juncea than in B. rapa, which could solely be attributed to the presence of high levels of sinigrin, which was absent in the latter species. Sulfate deprivation resulted in a strong decrease in the content and an altered composition of the glucosinolates of both species. Despite the differences in patterns in foliarly uptake and metabolism, their exposure hardly affected the glucosinolate composition of the shoot, both at sulfate-sufficient and sulfate-deprived conditions. This indicated that the glucosinolate composition in the shoot was hardly affected by differences in sulfur source (viz., sulfate, sulfite and sulfide). Upon sulfate deprivation, where foliarly absorbed H2S and SO2 were the sole sulfur source for growth, the glucosinolate composition of roots differed from sulfate-sufficient B. juncea and B. rapa, notably the fraction of the indolic glucosinolates was lower than that observed in sulfur-sufficient roots.

  14. Sulfur oxygen processes on Io

    NASA Astrophysics Data System (ADS)

    Nelson, R. M.; Smythe, W. D.

    1985-04-01

    The presence of allotropic sulfur as a possible major constituent of Io's surface and the properties of sulfur in combination with various sulfur-oxygen compounds believed to be present on Io's surface and in its atmosphere are studied by a series of laboratory experiments.

  15. Sulfur Oxygen Processes on Io

    NASA Technical Reports Server (NTRS)

    Nelson, R. M.; Smythe, W. D.

    1985-01-01

    The presence of allotropic sulfur as a possible major constituent of Io's surface and the properties of sulfur in combination with various sulfur-oxygen compounds believed to be present on Io's surface and in its atmosphere are studied by a series of laboratory experiments.

  16. Evaluation of sulfur dioxide-generating pads and modified atmosphere packaging for control of postharvest diseases in blueberries

    USDA-ARS?s Scientific Manuscript database

    Postharvest diseases are a limiting factor of storage and shelf life of blueberries. Gray mold caused by Botrytis cinerea is one of the most important postharvest diseases in blueberries grown in California. In this study, we evaluated the effects of sulfur dioxide (SO2)-generating pads (designated ...

  17. EnviroAtlas - Atmospheric Nitrogen and Sulfur Deposition by 12-digit HUC for the Conterminous United States (2011)

    EPA Pesticide Factsheets

    This EnviroAtlas dataset includes annual nitrogen and sulfur deposition within each 12-digit HUC subwatershed for the year 2011. Values are provided for total oxidized nitrogen (HNO3, NO, NO2, N2O5, NH3, HONO, PAN, organic nitrogen, and particulate NO3), oxidized nitrogen wet deposition, oxidized nitrogen dry deposition, total reduced nitrogen (NH3 and particulate NH4), reduced nitrogen dry deposition, reduced nitrogen wet deposition, total dry nitrogen deposition, total wet nitrogen deposition, total nitrogen deposition (wet+dry), total sulfur (SO2 + particulate SO4) dry deposition, total sulfur wet deposition, and total sulfur deposition. The dataset is based on output from the Community Multiscale Air Quality modeling system (CMAQ) run using the bidirectional flux option for the 12-km grid size for the US, Canada, and Mexico. The CMAQ output has been post-processed to adjust the wet deposition for errors in the location and amount of precipitation and for regional biases in the TNO3 (HNO3 + NO3), NHx (NH4 + NH3), and sulfate wet deposition. Model predicted values of dry deposition were not adjusted. This dataset was produced by the US EPA to support research and online mapping activities related to EnviroAtlas. EnviroAtlas (https://www.epa.gov/enviroatlas) allows the user to interact with a web-based, easy-to-use, mapping application to view and analyze multiple ecosystem services for the contiguous United States. The dataset is available as downloadable data

  18. Behavior of sulfur and chlorine in coal during combustion and boiler corrosion. [Quarterly] technical report, March 1, 1992--May 31, 1992

    SciTech Connect

    Chou, C.L.; Hackley, K.C.; Donnals, G.L.; Cao, J.; Ruch, R.R.; Pan, W.P.; Shao, D.

    1992-10-01

    Four replicate experiments of pyrolysis with quadrupole gas analyzer and ion selective electrode were conducted to monitor the release of chlorine and sulfur from a high-chlorine Illinois coal IBC-109 (0.42% chlorine on dry basis). The chlorine in coal is released solely as HCl, and the HCl release profile shows a broad peak between 250{degree}C and 600{degree}C with a maximum at 445{degree}C. In contrast, the sulfur release profile shows three peaks; the sulfur released around 370{degree}C may be derived from a labile (possibly aliphatic) component of organic sulfur, the main peak at 475{degree}C corresponds to the release of the main component (thiophenic) of organic sulfur, and the third peak at 600{degree} results from the decomposition of pyrite. Sulfur dioxide (SO{sub 2}) is the major sulfur species under an oxidizing condition in the combustion gas; additional gaseous sulfur species (COS and H{sub 2}S) are observed when the atmosphere is changed to a reducing condition. Sodium and chlorine contents in char residues determined by neutron activation analysis showed that 98% of chlorine in coal was volatilized during pyrolysis to 800{degree}C, and all the sodium is retained in the chars. The thermogravimetry-Fourier transform infrared (FTIR) spectroscopy experiments were carried out to characterize gaseous species during pyrolysis of four Illinois coals (IBC-103, -105, -106, and -109). Gas evolution profiles of sulfur (H{sub 2}S, S0{sub 2}, and COS), chlorine (HCl), and nitrogen (NH{sub 3} and HCN) species were determined. Similar release profiles of HCl and NH{sub 3} supported an interpretation that chlorine and nitrogen are closely associated in coal. COS may be formed by reaction of CO with H{sub 2}S in the gas phase.

  19. The formation of acid rain in the atmosphere, adjacent to the TTP with the joint-condensing of sulfur dioxide and water vapor

    NASA Astrophysics Data System (ADS)

    Gvozdyakov, D. V.; Gubin, V. E.; Matveeva, A. A.

    2014-08-01

    Presents the results of mathematical simulation of the condensation process of sulphur dioxide and water vapor on the condensation nuclei surface under the action of natural factors. Numerical investigations were carried out for the summer at a moderate speed of the wind. The influence of the parameter of condensation on the speed of the process of sulfuric acid drops formation in the air space was analyzed. Time ranges, sufficient for the formation of the acid rain sedimentation in the atmosphere, adjacent to the areas of thermal power station work were established. It is shown that the speed of air masses movement effects on the process of acid anthropogenic admixtures dispersion in the atmosphere. Approbation of the obtained results was carried out by checking the difference scheme conservative and solution of test problems.

  20. Behavior of sulfur and chlorine in coal during combustion and boiler corrosion. Technical report, December 1, 1992--February 28, 1993

    SciTech Connect

    Chou, C.L.; Hackley, K.C.; Cao, J.; Frost, R.R.; Ruch, R.R.; Pan, W.P.; Upchurch, M.L.; Cao, H.B.; Shao, D.; Ho, H.H.

    1993-05-01

    The goals of this project is to investigate the behavior of sulfur and chlorine during pyrolysis and combustion of Illinois coals, the chemistry of boiler deposits and the process of ash formation, and remedial measures to reduce the sulfur and chlorine compounds in combustion gases. The chemistry of boiler deposits provides information about the behavior of sulfur, chlorine, and ash particles during coal combustion. We report results obtained during this quarter on mineralogical and chemical compositions of twelve samples of boiler deposits collected from superheater and reheater tubes of an Illinois power plant. Scanning electron microscopy shows microscopic calcium sulfate droplets on cenospheres. There is a considerable variation of chemical composition among the samples. While eight out of twelve samples consist predominantly of quartz, mullite, and glass; the remaining four contain an appreciable amount additional phases (calcium sulfate and alkali iron sulfate) . The chlorine content in the samples is determined by neutron activation analysis. one sample contains 37 ppM chlorine, and the chlorine concentration is below the detection limit in other eleven samples (<15--45 ppM), indicating that most of the chlorine in feed coal is lost during combustion. In a separate set of experiments, the effects of composite gases containing Hcl, SO{sub 2}, and HCl+SO{sub 2} on six metals are determined. Chromium-nickel steel and alloy show higher resistance to corrosion than carbon-manganese steels and chromium-molybdenum steels when metal coupons are exposed to hot gases at 600{degree}C for 24 hours.

  1. Environmental behavior of tritium released to the atmosphere in winter

    SciTech Connect

    Davis, P.A.; Cornett, R.J.; Killey, R.W.D.; Wood, M.J.; Workman, W.J.G. . Chalk River Nuclear Labs.)

    1992-03-01

    An accidental release of HTO to the atmosphere from a reactor at the Chalk River Laboratories was assessed in a timely and efficient manner using a combination of predictive modelling and environmental sampling. A simple Gaussian plume model performed well in predicting the concentration of HTO in air. Doses to workers and to members of the public were well below acceptable levels at all times during the incident. This paper reports that the release was turned to advantage to study tritium behavior in the winter environment. HT concentrations were measured in aid, falling snow, vegetation and the snowpack at many locations during and after the release. The rate of HTO deposition to snow is greatly enhanced when snow is falling. The rate of new snow accumulation exceeded the rate of HTO diffusion in snow, so that the snowpack retained essentially all of the tritium deposited to it until spring melt occurred. Snow core data were therefore used as a surrogate for air concentrations to study the dispersion of the airborne plume, which was strongly affected by the topography of the Ottawa River Valley.

  2. The Corrosion Behavior of Ni3(Si,Nb) Alloys in Boiling 70 wt.% Sulfuric Acid

    NASA Astrophysics Data System (ADS)

    Hsu, Jen-Hsien; Larson, Christopher M.; Newkirk, Joseph W.; Brow, Richard K.; Zhang, San-Hong

    2016-02-01

    Corrosion-resistant Ni3(Si,Nb) alloys are promising materials of construction for hydrogen-production systems based on the sulfur-iodine thermochemical cycle. In this work, the corrosion rates of three different Ni3(Si,Nb) alloys were measured in boiling 70 wt.% sulfuric acid and a three-stage corrosion mechanism was identified, based on the composition and morphology of surface scale that developed. The α(Ni) + β(Ni3Si) eutectic constituent of the alloy microstructure was selectively attacked by acid and, when present, is detrimental to corrosion resistance. The G-phase (Ni16Si17Nb6) is more passive than the β-matrix and seems to contribute to a lower steady-state corrosion rate.

  3. Vapor-liquid phase behavior of the iodine-sulfur water-splitting process : LDRD final report for FY03.

    SciTech Connect

    Bradshaw, Robert W.; Larson, Richard S.; Lutz, Andrew E.

    2004-01-01

    This report summarizes the results of a one-year LDRD project that was undertaken to better understand the equilibrium behavior of the iodine-water-hydriodic acid system at elevated temperature and pressure. We attempted to extend the phase equilibrium database for this system in order to facilitate development of the iodine-sulfur water-splitting process to produce hydrogen to a commercial scale. The iodine-sulfur cycle for thermochemical splitting of water is recognized as the most efficient such process and is particularly well suited to coupling to a high-temperature source of process heat. This study intended to combine experimental measurements of vapor-liquid-liquid equilibrium and equation-of-state modeling of equilibrium solutions using Sandia's Chernkin software. Vapor-liquid equilibrium experiments were conducted to a limited extent. The Liquid Chernkin software that was developed as part of an earlier LDRD project was enhanced and applied to model the non-ideal behavior of the liquid phases.

  4. Zeolites Remove Sulfur From Fuels

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.; Sharma, Pramod K.

    1991-01-01

    Zeolites remove substantial amounts of sulfur compounds from diesel fuel under relatively mild conditions - atmospheric pressure below 300 degrees C. Extracts up to 60 percent of sulfur content of high-sulfur fuel. Applicable to petroleum refineries, natural-gas processors, electric powerplants, and chemical-processing plants. Method simpler and uses considerably lower pressure than current industrial method, hydro-desulfurization. Yields cleaner emissions from combustion of petroleum fuels, and protects catalysts from poisoning by sulfur.

  5. Behavior of sulfur and chlorine in coal during combustion and boiler corrosion. Final technical report, September 1, 1991--August 31, 1992

    SciTech Connect

    Chou, C.L.; Hackley, K.C.; Cao, J.; Donnals, G.L.; Ruch, R.R.; Pan, W.P.; Shao, D.

    1992-12-31

    Using the pyrolysis-QGA system, samples of coal were heated from ambient temperature to 800{degrees}C at a rate of 20{degrees}C/min in the pyrolysis chamber under a nitrogen atmosphere. The volatile products were carried with the nitrogen flow to the combustion chamber which was maintained at 850{degrees}C under a constant flow of oxygen. For Illinois coals (IBC-101, 103, and -109), HCl was the only chlorine species identified by the QGA. The HCl release profiles for the coals showed a broad peak between 250{degrees}C and 600{degrees}C with a maximum at 445{degrees}C. Neutron activation analysis of pyrolysis residues showed that 98 percent of the chlorine in raw coal was volatilized. Thus, it may be inferred that the chlorine in Illinois coals is released rapidly as HCl, not as sodium chloride (NaCl), during combustion in a utility/industrial boiler. In contrast to chlorine, the sulfur release profile for IBC-109 showed three peaks: the first sulfur peak at about 350{degrees}C was probably derived from elemental sulfur, the main peak at 475{degrees}C corresponded to the release of organic sulfur, and the third peak at 600{degrees}C resulted from the decomposition of pyrite. The low-temperature peak was absent for fresh samples. Sulfur dioxide (SO{sub 2}) was the major sulfur species in combustion gases under an oxidizing condition; additional gaseous sulfur species (COS and H{sub 2}S) were observed when the atmosphere was changed to a reducing condition.

  6. Influence of Atmospheric CO2 Variation on Strom Track Behavior

    NASA Astrophysics Data System (ADS)

    Martynova, Yuliya; Krupchatnikov, Vladimir

    2015-04-01

    The storm tracks are the regions of strong baroclinicity where surface cyclones occur. The effect of increase with following decrease of anthropogenic load on storm tracks activity in the Northern Hemisphere was studied. The global climate system model of intermediate complexity ('Planet Simulator', Fraedrich K. et al., 2005) was used in this study. Anthropogenic forcing was set according to climatic scenario RCP8.5 continued till 4000 AD with fixed CO2 concentration till 3000 AD and linear decrease of anthropogenic load to preindustrial value at two different rates: for 100 and 1000 years. Modeling data analysis showed meridional shift of storm tracks due to atmospheric CO2 concentration variation. When CO2 concentration increases storm tracks demonstrate poleward shifting. When CO2 concentration decreases to preindustrial value storm tracks demonstrate a tendency to equator-ward shifting. Storm tracks, however, don't recover their original activity and location to the full. This manifests itself particularly for 'fast' CO2 concentration decrease. Heat and moisture fluxes demonstrate the same behavior. In addition, analysis of eddy length scale (Kidston J. Et al., 2011) showed their increase at mid-latitudes and decrease at tropic latitudes due to intensive CO2 concentration increase. This might cause poleward shift of mid-latitude jets. Acknowledgements. This work is partially supported by SB RAS project VIII.80.2.1, RFBR grant 13-05-12034, 13-05-00480, 14-05-00502 and grant of the President of the Russian Federation. Fraedrich K., Jansen H., Kirk E., Luksch U., and Lunkeit F. The Planet Simulator: Towards a user friendly model // Meteorol. Zeitschrift. 2005, 14, 299-304. Kidston J., Vallis G.K., Dean S.M., Renwick J.A. Can the increase in the eddy length scale ander global warming cause the poleward shift of the jet streams? // J. Climate. 2011, V.24. P. 3764-3780.

  7. Formic acid catalyzed hydrolysis of SO3 in the gas phase: a barrierless mechanism for sulfuric acid production of potential atmospheric importance.

    PubMed

    Hazra, Montu K; Sinha, Amitabha

    2011-11-02

    Computational studies at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels are performed to explore the changes in reaction barrier height for the gas phase hydrolysis of SO(3) to form H(2)SO(4) in the presence of a single formic acid (FA) molecule. For comparison, we have also performed calculations for the reference reaction involving water assisted hydrolysis of SO(3) at the same level. Our results show that the FA assisted hydrolysis of SO(3) to form H(2)SO(4) is effectively a barrierless process. The barrier heights for the isomerization of the SO(3)···H(2)O···FA prereactive collision complex, which is the rate limiting step in the FA assisted hydrolysis, are found to be respectively 0.59 and 0.08 kcal/mol at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels. This is substantially lower than the ~7 kcal/mol barrier for the corresponding step in the hydrolysis of SO(3) by two water molecules--which is currently the accepted mechanism for atmospheric sulfuric acid production. Simple kinetic analysis of the relative rates suggests that the reduction in barrier height facilitated by FA, combined with the greater stability of the prereactive SO(3)···H(2)O···FA collision complex compared to SO(3)···H(2)O···H(2)O and the rather plentiful atmospheric abundance of FA, makes the formic acid mediated hydrolysis reaction a potentially important pathway for atmospheric sulfuric acid production.

  8. Retention behavior of isomeric polycyclic aromatic sulfur heterocycles in reversed-phase liquid chromatography.

    PubMed

    Wilson, Walter B; Sander, Lane C; de Alda, Miren Lopez; Lee, Milton L; Wise, Stephen A

    2016-08-26

    Retention indices for 70 polycyclic aromatic sulfur heterocycles (PASHs) were determined using reversed-phase liquid chromatography (LC) on a monomeric and a polymeric C18 stationary phase. Molecular shape parameters [length, breadth, thickness (T), and length-to-breadth ratio (L/B)] were calculated for all the compounds studied. Correlations between the retention on the polymeric C18 phase and PASH geometry (L/B and T) were investigated for six specific PASH isomer groups with molecular mass (MM) 184Da, 234Da, 258Da, 284Da, 334Da, and 384Da. Similar to previous studies for polycyclic aromatic hydrocarbons (PAHs), PASH elution order on the polymeric C18 phase was generally found to follow increasing L/B values. Correlation coefficients for retention vs L/B ranged from r=0.45 (MM 184Da) to r=0.89 (MM 284Da). In the case of smaller PASHs (MM≤258Da), the location of the sulfur atom in the bay-region of the structure resulted in later than expected elution of these isomers based on L/B. In the case of the larger PASHs (MM≥284Da), nonplanarity had a significant influence on earlier than predicted elution based on L/B values.

  9. Retention behavior of alkyl-substituted polycyclic aromatic sulfur heterocycles in reversed-phase liquid chromatography.

    PubMed

    Wilson, Walter B; Sander, Lane C; de Alda, Miren Lopez; Lee, Milton L; Wise, Stephen A

    2016-08-26

    Retention indices for 79 alkyl-substituted polycyclic aromatic sulfur heterocycles (PASHs) were determined by using reversed-phase liquid chromatography (LC) on a monomeric and polymeric octadecylsilane (C18) stationary phase. Molecular shape parameters [length, breadth, thickness (T), and length-to-breadth ratio (L/B)] were calculated for all the compounds studied. Based on separations of isomeric methylated polycyclic aromatic hydrocarbons on polymeric C18 phases, alkyl-substituted PASHs are expected to elute based on increasing L/B ratios. However, the correlation coefficients had a wide range of values from r=0.43 to r=0.93. Several structural features besides L/B ratios were identified to play an important role in the separation mechanism of PASHs on polymeric C18 phases. First, the location of the sulfur atom in a bay-like-region results in alkylated-PASHs being more retentive than non-bay-like-region alkylated-PASHs, and they elute later than expected based on L/B value. Second, the placement of the alkyl group in the k region of the structure resulted in a later elution than predicted by L/B. Third, highly nonplanar methyl-PASHs (i.e., 1-Me and 11-MeBbN12T) elute prior to the parent PASH (BbN12T).

  10. Relationship of liquefaction behavior of a set of high-sulfur coals to chemical structural characteristics

    SciTech Connect

    Neill, P.H.

    1985-01-01

    The aim of this research project was to use empirical mathematical relationships to formulate a better understanding of the processes involved in the liquefaction of a set of medium rank high sulfur coals. These coals were chosen because previous work had shown that similar samples tended to exhibit high liquefaction yields. Additionally it appeared that rank, organic and pyritic sulfur were important structural parameters in the liquefaction process. About 50 structural parameters and yields of product classes were determined. The structural parameters included distribution of acids produced by oxidation with trifluoroperoxyacetic acid, aromaticity as determined by CP/MAS TC nmr spectroscopy, intensity of aliphatic and aromatic C-H absorptions measured by FTIR, infrared absorption due to carbonyl in acetylated coals, and the high and low temperature ash yields. The product classes determined included total conversion, conversion to asphaltenes, oils, and gases. The gases were further analyzed by gas chromatography for hydrocarbons, CO, CO2, H2S and hydrocarbons, and the hexane-soluble oils were separated into saturate, aromatic and polar fractions by HPLC.

  11. Effects of the atmospheric chemistry and dynamics on the distributions of Venusian sulfuric acid clouds in low- and mid-latitudes simulated by a general circulation model

    NASA Astrophysics Data System (ADS)

    Aizawa, S.; Kasaba, Y.; Kuroda, T.; Ikeda, K.; Terada, N.; Takahashi, M.; Medvedev, A. S.; Hartogh, P.

    2016-12-01

    Sulfuric acid clouds reflect and affect Venusian atmospheric dynamics and climate changes through their radiative processes. It is the main observational target of JAXA Venus Orbiter Akatsuki. We have implemented the sulfuric acid cloud formations with related chemical processes into a Venusian General Circulation Model (VGCM) developed by Ikeda (2011), and investigated the cloud formation and circulation systems. We implemented the chemical processes which determine the abundances of H2SO4 vapor, SO3, SO2 and H2O. They are critical in the reproduction of the realistic cloud maintenance processes. With those chemical processes, we could reproduce the latitudinal distributions of the cloud thickness and the vertical profiles of H2SO4 vapor. It qualitatively agrees with the observational results by the Visible and InfraRed Thermal Imaging Spectrometer (VIRTIS) onboard Venus Express (VEX) and the Magellan radio occultation data, respectively, in low- and mid- latitudes (0-60 deg.). With this model, we investigated the maintenance and circulation processes of the sulfuric acid clouds and vapor in the latitude regions. In the upper cloud region (60-80 km), the production of clouds by the condensation of H2SO4 is the largest at 65 km in altitude. Those clouds flow upward and poleward by the meridional circulation and vertical diffusion. Meanwhile, in the lower cloud region (50-60 km), H2SO4 vapor is transported to the equatorial region at 50-54 km in altitude by the meridional circulation and vertical diffusion. There the vapor condenses into the clouds, and the formed clouds are transported poleward along with the meridional circulation. Although these cycles have been indicated by a 2-D latitude-altitude model by Imamura and Hashimoto (1998), we first succeeded to reproduce this cloud cycles in a VGCM.

  12. Laboratory measurements of the 3.7-20 cm wavelength opacity of sulfur dioxide and carbon dioxide under simulated conditions for the deep atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Steffes, Paul G.; Shahan, Patrick; Christopher Barisich, G.; Bellotti, Amadeo

    2015-01-01

    In the past two decades, multiple observations of Venus have been made at X-Band (3.6 cm) using the Jansky Very Large Array (VLA), and maps have been created of the 3.6 cm emission from Venus (see, e.g., Devaraj, K. [2011]. The Centimeter- and Millimeter-Wavelength Ammonia Absorption Spectra under Jovian Conditions. PhD Thesis, Georgia Institute of Technology, Atlanta, GA). Since the emission morphology is related both to surface features and to deep atmospheric absorption from CO2 and SO2 (see, e.g., Butler, B.J., Steffes, P.G., Suleiman, S.H., Kolodner, M.A., Jenkins, J.M. [2001]. Icarus 154, 226-238), knowledge of the microwave absorption properties of sulfur dioxide in a carbon dioxide atmosphere under conditions for the deep atmosphere of Venus is required for proper interpretation. Except for a single measurement campaign conducted at a single wavelength (3.2 cm) over 40 years ago (Ho, W., Kaufman, I.A., Thaddeus, P. [1966]. J. Geophys. Res. 71, 5091-5108), no measurements of the centimeter-wavelength properties of any Venus atmospheric constituent have been conducted under conditions characteristic of the deep atmosphere (pressures from 10 to 92 bars and temperatures from 400 to 700 K). New measurements of the microwave properties of SO2 and CO2 at wavelengths from 3.7 to 20 cm have been conducted under simulated conditions for the deep atmosphere of Venus, using a new high-pressure system. Results from this measurement campaign conducted at temperatures from 430 K to 560 K and at pressures up to 92 bars are presented. Results indicate that the model for the centimeter-wavelength opacity from pure CO2 (Ho, W., Kaufman, I.A., Thaddeus, P. [1966]. J. Geophys. Res. 71, 5091-5108), is valid over the entire centimeter-wavelength range under simulated conditions for the deep atmosphere of Venus. Additionally, the laboratory results indicate that both of the models for the centimeter-wavelength opacity of SO2 in a CO2 atmosphere from Suleiman et al. (Suleiman, S

  13. Long-term variations in abundance and distribution of sulfuric acid vapor in the Venus atmosphere inferred from Pioneer Venus and Magellan radio occultation studies

    NASA Technical Reports Server (NTRS)

    Jenkins, J. M.; Steffes, P. G.

    1992-01-01

    Radio occultation experiments have been used to study various properties of planetary atmospheres, including pressure and temperature profiles, and the abundance profiles of absorbing constituents in those planetary atmospheres. However, the reduction of amplitude data from such experiments to determine abundance profiles requires the application of the inverse Abel transform (IAT) and numerical differentiation of experimental data. These two operations preferentially amplify measurement errors above the true signal underlying the data. A new technique for processing radio occultation data has been developed that greatly reduces the errors in the derived absorptivity and abundance profiles. This technique has been applied to datasets acquired from Pioneer Venus Orbiter radio occultation studies and more recently to experiments conducted with the Magellan spacecraft. While primarily designed for radar studies of the Venus surface, the high radiated power (EIRP) from the Magellan spacecraft makes it an ideal transmitter for measuring the refractivity and absorptivity of the Venus atmosphere by such experiments. The longevity of the Pioneer Venus Orbiter has made it possible to study long-term changes in the abundance and distribution of sulfuric acid vapor, H2SO4(g), in the Venus atmosphere between 1979 and 1992. The abundance of H2SO4(g) can be inferred from vertical profiles of 13-cm absorptivity profiles retrieved from radio occultation experiments. Data from 1979 and 1986-87 suggest that the abundance of H2SO4(g) at latitudes northward of 70 deg decreased over this time period. This change may be due to a period of active volcanism in the late 1970s followed by a relative quiescent period, or some other dynamic process in the Venus atmosphere. While the cause is not certain, such changes must be incorporated into dynamic models of the Venus atmosphere. Potentially, the Magellan spacecraft will extend the results of Pioneer Venus Orbiter and allow the continued

  14. Medusa: a sample preconcentration and GC/MS detector system for in situ measurements of atmospheric trace halocarbons, hydrocarbons, and sulfur compounds.

    PubMed

    Miller, Benjamin R; Weiss, Ray F; Salameh, Peter K; Tanhua, Toste; Greally, Brian R; Mühle, Jens; Simmonds, Peter G

    2008-03-01

    Significant changes have occurred in the anthropogenic emissions of many compounds related to the Kyoto and Montreal Protocols within the past 20 years and many of their atmospheric abundances have responded dramatically. Additionally, there are a number of related natural compounds with underdetermined source or sink budgets. A new instrument, Medusa, was developed to make the high frequency in situ measurements required for the determination of the atmospheric lifetimes and emissions of these compounds. This automated system measures a wide range of halocarbons, hydrocarbons, and sulfur compounds involved in ozone depletion and/or climate forcing, from the very volatile perfluorocarbons (PFCs, e.g., CF(4) and CH(3)CF(3)) and hydrofluorocarbons (HFCs, e.g., CH(3)CF(3)) to the higher-boiling point solvents (such as CH(3)Cl(3) and CCl(2)=CCl(2)) and CHBr(3). A network of Medusa systems worldwide provides 12 in situ ambient air measurements per day of more than 38 compounds of part per trillion mole fractions and precisions up to 0.1% RSD at the five remote field stations operated by the Advanced Global Atmospheric Gases Experiment (AGAGE). This custom system couples gas chromatography/mass spectrometry (GC/MSD) with a novel scheme for cryogen-free low-temperature preconcentration (-165 degrees C) of analytes from 2 L samples in a two-trap process using HayeSep D adsorbent.

  15. Strain effects on the behavior of isolated and paired sulfur vacancy defects in monolayer MoS2

    NASA Astrophysics Data System (ADS)

    Sensoy, Mehmet Gokhan; Vinichenko, Dmitry; Chen, Wei; Friend, Cynthia M.; Kaxiras, Efthimios

    2017-01-01

    We investigate the behavior of sulfur vacancy defects, the most abundant type of intrinsic defect in monolayer MoS2, using first-principles calculations based on density functional theory. We consider the dependence of the isolated defect formation energy on the charge state and on uniaxial tensile and compressive strain up to 5%. We also consider the possibility of defect clustering by examining the formation energies of pairs of vacancies at various relative positions, and their dependence on charge state and strain. We find that there is no driving force for vacancy clustering, independent of strain in the material. The barrier for diffusion of S vacancies is larger than 1.9 eV in both charged and neutral states regardless of the presence of other nearby vacancies. We conclude that the formation of extended defects from S vacancies in planar monolayer MoS2 is hindered both thermodynamically and kinetically.

  16. Thermodynamic modeling of REE behavior in oxidized hydrothermal fluids of high sulfate sulfur concentrations

    NASA Astrophysics Data System (ADS)

    Shironosova, G. P.; Kolonin, G. R.; Borovikov, A. A.; Borisenko, A. S.

    2016-08-01

    Thermodynamic calculations using the HCh software were made for mineral equilibriums including REEs in the fluoride-sulfide-chloride-carbonate-sulfate-system in the presence of Na, Ca, and P with fluids of various acidities-alkalinities [11]. The obtained thermodynamic characteristics of thenardite allowed us to carry out the calculations for this phase under complicated hydrothermal conditions simulating the presence of oxidized fluids at 500-100°C and 2000-125 bar. Among other solid phases, REEs-fluorite, monazite, and REE-F-apatite were formed as CaF2-(Ln,Y)F3, LnPO4, and Ca5(PO4)3F-(Ln,Y)3(PO4)3 ideal solid solutions, respectively, where Ln is La, Ce, Pr, Nd, Sm, Eu, and Gd. Xenotime, anhydrite, elemental sulfur, and calcite were found as well.

  17. Multi-model Mean Nitrogen and Sulfur Deposition from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): Evaluation Historical and Projected Changes

    NASA Technical Reports Server (NTRS)

    Lamarque, J.-F.; Dentener, F.; McConnell, J.; Ro, C.-U.; Shaw, M.; Vet, R.; Bergmann, D.; Cameron-Smith, P.; Doherty, R.; Faluvegi, G.; hide

    2013-01-01

    We present multi-model global datasets of nitrogen and sulfate deposition covering time periods from 1850 to 2100, calculated within the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). The computed deposition fluxes are compared to surface wet deposition and ice-core measurements. We use a new dataset of wet deposition for 2000-2002 based on critical assessment of the quality of existing regional network data. We show that for present-day (year 2000 ACCMIP time-slice), the ACCMIP results perform similarly to previously published multi-model assessments. For this time slice, we find a multi-model mean deposition of 50 Tg(N) yr1 from nitrogen oxide emissions, 60 Tg(N) yr1 from ammonia emissions, and 83 Tg(S) yr1 from sulfur emissions. The analysis of changes between 1980 and 2000 indicates significant differences between model and measurements over the United States but less so over Europe. This difference points towards misrepresentation of 1980 NH3 emissions over North America. Based on ice-core records, the 1850 deposition fluxes agree well with Greenland ice cores but the change between 1850 and 2000 seems to be overestimated in the Northern Hemisphere for both nitrogen and sulfur species. Using the Representative Concentration Pathways to define the projected climate and atmospheric chemistry related emissions and concentrations, we find large regional nitrogen deposition increases in 2100 in Latin America, Africa and parts of Asia under some of the scenarios considered. Increases in South Asia are especially large, and are seen in all scenarios, with 2100 values more than double 2000 in some scenarios and reaching 1300 mg(N) m2 yr1 averaged over regional to continental scale regions in RCP 2.6 and 8.5, 3050 larger than the values in any region currently (2000). The new ACCMIP deposition dataset provides novel, consistent and evaluated global gridded deposition fields for use in a wide range of climate and ecological studies.

  18. Atmosphere Behavior in Gas-Closed Mouse-Algal Systems: An Experimental and Modelling Study

    NASA Technical Reports Server (NTRS)

    Averner, M. M.; Moore, B., III; Bartholomew, I.; Wharton, R.

    1985-01-01

    A dual approach of mathematical modelling and laboratory experimentation aimed at examining the gas exchange characteristics of artificial animal/plant systems closed to the ambient atmosphere was initiated. The development of control techniques and management strategies for maintaining the atmospheric levels of carbon dioxide and oxygen at physiological levels is examined. A mathematical model simulating the atmospheric behavior in these systems was developed and an experimental gas closed system was constructed. These systems are described and preliminary results are presented.

  19. An Investigation on Teacher Candidates' Perspectives about Behaviors Positively Affecting Classroom Atmosphere

    ERIC Educational Resources Information Center

    Bulut Ozsezer, M. Spencer; Iflazoglu Saban, Ayten

    2016-01-01

    Problem Statement: A revision of literature shows that there are studies focusing on student and teacher perceptions of classroom atmosphere; however, no research has been found to be related to teacher candidates' perspectives on their behaviors in terms of positive classroom atmosphere. As teacher candidates are the main subject and the future…

  20. Sulfur Isotopic Composition and Behavior in Granitoid Intrusions, southwestern New Brunswick, Canada

    NASA Astrophysics Data System (ADS)

    Yang, X.; Lentz, D. R.

    2004-05-01

    Bulk sulfur isotopic composition and sulfur content were determined for 12 granitoid intrusions (48 samples) associated with various types of mineralization (e.g., Au, Sb-W-Mo-Au, W-Sn-In-Zn-Pb-Cu) and the pertinent wallrocks (7 samples), in southwestern New Brunswick, Canada. This data together with data from field relations, magnetic susceptibility, sulfide mineralogy, petrology, and geochemistry, were used to characterize these intrusions. Two distinct groups can be established, although both show some features of I-type grantiods: (1) a Late Devonian granitic series (GS) including the Mount Pleasant, True Hill, Beech Hill, Pleasant Ridge, Kedron, Sorrel Ridge granites, and (2) a Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS) including the Magaguadavic, Bocabec, Utopia, Tower Hill, Evandale, and Lake George intrusions. The former occur along the northwestern flank of the Saint George Batholith as satellite plutons, and the later form parts of this batholith and the Pokiok Batholith to the north. The GS rocks show the attributes of evolved I-type with some A-type features, whereas the GMS rocks are either reduced I-type (ilmenite-series), or normal I-type (magnetite-series). Strong assimilation and contamination by local metasedimentary rocks lead to the Tower Hill granite resembling S-type, e.g., the presence of muscovite and garnet. The GS type rocks have δ 34S values between -7.1 and +13 per mil with bulk-S content ranging from 33 to 3434 ppm. The GMS type rocks have relatively narrower variation in δ 34S values (-4.4 to +7.3 per mil), but with larger ranges of bulk-S content (45 to 11100 ppm). The granite samples with S contents much higher than its solubility in felsic melts are interpreted to be affected either by local metasedimentary rocks or by late stage hydrothermal alteration. The metasedimentary rocks contain variable S contents (707 to 14000 ppm) with δ 34S values of -10.6 to 0.1 per mil. In terms of mass balance, a

  1. Mass independent oxygen and sulfur isotopic compositions of environmental sulfate and nitrate. A new probe of atmospheric, hydrospheric and geological processes

    NASA Astrophysics Data System (ADS)

    Thiemens, M.; Michalski, G.; Romero, A.; McCabe, J.

    2003-04-01

    Aerosol sulfate is well known to exert a significant influence on the Earth’s atmosphere and surface. They mediate climate in its capacity as a cloud condensation nuclei (CCN) and as a visible light scattering agent. These particles are respirable, with severe cardiovascular disease consequences. Removal by wet and dry depositions is well known to cause surficial damage to biota, biodiversity, and structures. Despite decades of high precision global concentration measurements, single isotope ratio measurements (d18O, d34S) and high quality modeling efforts, there remain unresolved issues with respect to resolution of relative oxidative processes (homogenous vs. heterogeneous), transformation mechanisms, and identification of sources, proximal and distal. Mass independent oxygen isotopic compositions have added new insights un attainable by other techniques. These observations ideally complement other measurements in an effort to improve parameters used in modeling aerosols and climate. Recent sulfur mass independent compositions have potentially added a new means to recognize upper atmospheric photolytic processes. Aerosol nitrate is estimated to nearly double in the next half century, with potentially severe consequences which include soil acidification, loss of biodiversity, eutrophication of coastal and freshwaters, and, human cardiovascular disease. Loss of fresh water lake clarity, e.g. Lake Tahoe is also believed to occur due to increased nitrogen levels. As in the case of atmospheric sulfate, mass independent oxygen isotopic signatures have been observed in nitrate. The D17O is one of the largest mass independent isotopic signatures observed in any environmental species with the exception of ozone. These measurements have demonstrated the ability to provide new insight into the nitrogen cycle, including atmospheric, hydrospheric and geologic processes.

  2. Depletions of sulfur and/or zinc in IDPs: Are they reliable indicators of atmospheric entry heating?

    NASA Technical Reports Server (NTRS)

    Flynn, G. J.; Sutton, S. R.; Bajt, S.; Kloeck, W.; Thomas, K. L.; Keller, L. P.

    1993-01-01

    The degree of heating of interplanetary dust particles (IDP's) on Earth atmospheric entry is important in distinguishing cometary particles from main-belt asteroidal particles. Depletions in the volatile elements S and Zn were proposed as chemical indicators of significant entry heating. The S and Zn contents of cosmic dust particles were correlated with physical indicators of atmospheric entry heating, such as the production of magnetite and the loss of solar wind implanted He. The results indicate that the Zn content of IDP's is a useful indicator of entry heating, but the S content seems to be less useful.

  3. PREDICTION OF MULTICOMPONENT INORGANIC ATMOSPHERIC AEROSOL BEHAVIOR. (R824793)

    EPA Science Inventory

    Many existing models calculate the composition of the atmospheric aerosol system by solving a set of algebraic equations based on reversible reactions derived from thermodynamic equilibrium. Some models rely on an a priori knowledge of the presence of components in certain relati...

  4. PREDICTION OF MULTICOMPONENT INORGANIC ATMOSPHERIC AEROSOL BEHAVIOR. (R824793)

    EPA Science Inventory

    Many existing models calculate the composition of the atmospheric aerosol system by solving a set of algebraic equations based on reversible reactions derived from thermodynamic equilibrium. Some models rely on an a priori knowledge of the presence of components in certain relati...

  5. The seasonal behavior of water vapor in the Mars atmosphere

    NASA Astrophysics Data System (ADS)

    Jakosky, B. M.

    Understanding the evolution of volatiles on Mars requires understanding the processes which are currently acting to cause exchange between the various reservoirs on annual and longer timescales. On the seasonal timescale, exchange of water can occur between the atmosphere and reservoirs of ice in the polar caps and of adsorbed water in the near-surface regolith covering the remainder of the planet. The water vapor content of the Mars atmosphere was measured from the Viking Orbiter Mars Atmospheric Water Detectors (MAWD) for a period of more than one Martian year, from June, 1976, through April, 1979, and the results are presented. The strong annual gradient of vapor from north to south implies a net annual flow of vapor toward the south. The perennially-cold nature of the south-polar residual cap, along with the relatively large summertime vapor abundances over the cap, implies a net annual condensation of vapor onto the cap. Estimates are made of the southward transport, and are consistent with the movement of ice being important in the formation and evolution of the polar layered terrain, and with the formation of the individual layers at the rate of one per obliquity cycle (105 years). Models were constructed which include regolith exchange, polar cap formation, and atmospheric transport.

  6. Sulfur-rich Sediments

    NASA Astrophysics Data System (ADS)

    Goldhaber, M. B.

    2003-12-01

    Marine sediments with more than a few tenths of a percent of organic carbon, as well as organic-matter-bearing, nonmarine sediments with significant concentrations of sulfate in the depositional waters contain the mineral pyrite (FeS2). Pyrite, along with sulfur-bearing organic compounds, form indirectly through the metabolic activities of sulfate-reducing microorganisms. The geochemical transformations of sulfur in sediments leading to these products significantly impact the pathway of early sedimentary diagenesis, conditions for the localization of mineral deposits (Ohmoto and Goldhaber, 1997), the global cycling of sulfur and carbon, the abundance of oxygen in the Earth's atmosphere, and perhaps even the emergence of life on Earth (e.g., Russell and Hall, 1997). This chapter provides an overview of sedimentary-sulfur geochemistry from its microbial and abiologic pathways to the global consequences of these processes.The geochemistry of sulfur is complicated by its wide range of oxidation states (Table 1). Under oxidizing conditions (e.g., in the presence of atmospheric oxygen) sulfate, with sulfur in the +6 valence state, is the stable form of sulfur. Under reducing conditions (e.g., in the presence of H2), sulfide (S=-2 valent) is the stable oxidation state. However, a range of additional aqueous and solid-phase sulfur species exist with valences between these two end-members. What makes the study of sulfur geochemistry so exciting and challenging is that many of these intermediate-valent forms play key roles in sedimentary-sulfur transformations. Furthermore, many of these reactions are microbially mediated. As detailed below, these complex biogeochemical pathways are now yielding to research whose scope ranges from molecular to global level. Table 1. Forms of sulfur in marine sediments and their oxidation states Aqueous species or mineralFormulaOxidation state(s) of sulfur SulfideH2S(aq), HS-(aq)-2 Iron sulfideaFeS(s)-2 GreigiteFe3S4(s)-2, 0 PyriteFeS2(s)-2

  7. Corrosion resistance and behavior of construction materials exposed to dilute sulfuric acid at elevated temperatures under static conditions

    SciTech Connect

    Nguyen, D.T.

    1994-10-01

    Laboratory investigation has been undertaken to determine the electrochemical behavior and corrosion resistance of various construction materials in a simulated hydrolysis environment (5 wt % sulfuric acid) at temperatures ranging from 90 to 220C. Tests were performed in an autoclave-type electrochemical cell. The corrosion behavior of the test materials was determined using computer-controlled DC potentiodynamic polarization. Corrosion rates of the test materials were determined using AC impedance techniques. Among the stainless steels tested, only alloy N08026 (Carpenter 20Mo-6) performed satisfactory up to a temperature of 100C. The alloy passivated spontaneously in the environment and corroded at a rate of less than 2 mpy. None of the stainless steels tested could be used at 120{degrees}C or above. A number of nickel-based alloys tested had good corrosion resistance up to 100C, but their corrosion rate exceeded 2 mpy at higher temperatures. Zirconium alloys were satisfactory up to 180C. Only tantalum and a tantalum-niobium alloy were satisfactory up to 220C.

  8. Effect of Aging Temperature on Corrosion Behavior of Sintered 17-4 PH Stainless Steel in Dilute Sulfuric Acid Solution

    NASA Astrophysics Data System (ADS)

    Szewczyk-Nykiel, Aneta; Kazior, Jan

    2017-07-01

    The general corrosion behavior of sintered 17-4 PH stainless steel processed under different processing conditions in dilute sulfuric acid solution at 25 °C was studied by open-circuit potential measurement and potentiodynamic polarization technique. The corrosion resistance was evaluated based on electrochemical parameters, such as polarization resistance, corrosion potential, corrosion current density as well as corrosion rate. The results showed that the precipitation-hardening treatment could significantly improve the corrosion resistance of the sintered 17-4 PH stainless steel in studied environment. As far as the influence of aging temperature on corrosion behavior of the sintered 17-4 PH stainless steel is concerned, polarization resistance and corrosion rate are reduced with increasing aging temperature from 480 up to 500 °C regardless of the temperature of solution treatment. It can be concluded that the highest corrosion resistance in 0.5 M H2SO4 solution exhibits 17-4 PH after solution treatment at 1040 °C followed by aging at 480 °C.

  9. Statistical prediction of the atmospheric behavior for free space optical link

    NASA Astrophysics Data System (ADS)

    Hajek, Lukas; Vitasek, Jan; Vanderka, Ales; Latal, Jan; Perecar, Frantisek; Vasinek, Vladimir

    2015-09-01

    The atmosphere is unstable and unpredictable environment, where are continual changes of the air refractive index. These changes cause fluctuation of optical power at the receiver site. The prediction of behavior of the atmosphere and effect of this behavior on the FSO link is very complicated or even impossible. Aim of this article is focused on statistical analysis of measured level signal RSSI of the FSO link and atmospheric properties measured by hydro-meteorological station. For measured data the statistical analysis tools were used. Next part of article is focused on determination of the linear regression model to calculate level of RSSI depending on the atmospheric properties. Two empirical equations are result for day and night time. These equations describe behavior of signal RSSI in 30 days interval. Finally, comparison of the obtained mathematical model with real measured data of RSSI was introduced for one week before and one week after the analyzed time interval.

  10. Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth’s atmosphere

    PubMed Central

    Whitehill, Andrew R.; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei

    2013-01-01

    Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen (16O,17O,18O) and sulfur (32S, 33S, 34S, 36S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ33S up to 78‰ and Δ36S up to 110‰, from the broadband excitation of SO2 in the 250–350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 (3B1), which results from intersystem crossing from the excited singlet (1A2/1B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin–orbit interaction between the singlet (1A2/1B1) and triplet (3B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for 33SO2 and 36SO2 for the low vibrational levels of the 1A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems. PMID:23836655

  11. Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth's atmosphere.

    PubMed

    Whitehill, Andrew R; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei

    2013-10-29

    Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen ((16)O,(17)O,(18)O) and sulfur ((32)S, (33)S, (34)S, (36)S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ(33)S up to 78‰ and Δ(36)S up to 110‰, from the broadband excitation of SO2 in the 250-350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 ( (3)B1), which results from intersystem crossing from the excited singlet ( (1)A2/ (1)B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin-orbit interaction between the singlet ( (1)A2/ (1)B1) and triplet ( (3)B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for (33)SO2 and (36)SO2 for the low vibrational levels of the (1)A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems.

  12. Dynamical Behavior of Meteor in AN Atmosphere: Theory vs Observations

    NASA Astrophysics Data System (ADS)

    Gritsevich, Maria

    Up to now the only quantities which directly follow from the available meteor observations are its brightness, the height above sea level, the length along the trajectory, and as a consequence its velocity as a function of time. Other important parameters like meteoroid's mass, its shape, bulk and grain density, temperature remain unknown and should be found based on physical theories and special experiments. In this study I will consider modern methods for evaluating meteoroid parameters from observational data, and some of their applications. The study in particular takes an approach in modelling the meteoroids' mass and other properties from the aerodynamical point of view, e.g. from the rate of body deceleration in the atmosphere as opposed to conventionally used luminosity [1]. An analytical model of the atmospheric entry is calculated for registered meteors using published observational data and evaluating parameters describing drag, ablation and rotation rate of meteoroid along the luminous segment of the trajectory. One of the special features of this approach is the possibility of considering a change in body shape during its motion in the atmosphere. The correct mathematical modelling of meteor events is necessary for further studies of consequences for collisions of cosmic bodies with the Earth [2]. It also helps us to estimate the key parameters of the meteoroids, including deceleration, pre-entry mass, terminal mass, ablation coefficient, effective destruction enthalpy, and heat-transfer coefficient. With this information, one can use models for the dust influx onto Earth to estimate the number of meteors detected by a camera of a given sensitivity. References 1. Gritsevich M. I. Determination of Parameters of Meteor Bodies based on Flight Obser-vational Data // Advances in Space Research, 44, p. 323-334, 2009. 2. Gritsevich M. I., Stulov V. P. and Turchak L. I. Classification of Consequences for Col-lisions of Natural Cosmic Bodies with the Earth

  13. Thermodynamic Properties of Sulfatian Apatite: Constraints on the Behavior of Sulfur in Calc-Alkaline Magmas

    NASA Astrophysics Data System (ADS)

    Core, D.; Essene, E. J.; Luhr, J. F.; Kesler, S. E.

    2004-12-01

    The Gibbs free energy of hydroxyellestadite [Ca10(SiO4)3(SO4)3(OH)2] was estimated using mineral equilibria applied to analyzed assemblages from the experimental charges of Luhr (1990). The apatite analyses of Peng et al. (1997) were used in conjunction with new analyses of the oxides and silicates in this study. An ideal mixing model was employed for apatite combined with mixing models from MELTS (Ghiorso & Sack, 1994) and Gibbs free energy data from Robie & Hemingway (1995) for the other crystalline phases. The resultant equation of the Gibbs free energy vs. T for hydroxyellestadite is as follows: DG°T(elem) = [2.817(T - 273) - 11831]/1000 kJ/mol, T in K. The calculated entropy for hydroxyellestadite is 1944 J/mol.K at 1073 K and 2151 J/mol.K at 1227 K. Independent estimates of the entropy of hydroxyellestadite obtained with the method of Robinson & Haas (1983) are within 5% of these values. The thermodynamic data on hydroxyellestadite were used to calculate the locus of the reactions: 2Ca10(SiO4)3(SO4)3(OH)2 + 7S2 + 21O2 = 20CaSO4 + 6SiO2 + 2H2O 6Ca10(SiO4)3(SO4)3(OH)2 + 102SiO2 + 20Fe3O4 = 60CaFeSi2O6 + 6H2O + 9S2 + 37O2 2Ca10(SiO4)3(SO4)3(OH)2 + 10Mg2Si2O6 + 14SiO2 = 20CaMgSi2O6 + 2H2O + 3S2 + 9O2 in fO2-fS2 space at fixed P-T. Application of these equilibria to apatite zoned in sulfate from oxidized granitoids reflects a drop in fS2 by more than 1 log unit during its growth. The zoning is interpreted to represent the removal of a magmatic vapor phase during crystallization of these plutons. Removal of sulfur from magmas by hydrothermal fluids is important to the ore-forming process and to the production of acid sulfate aerosols during eruption of oxidized magmas. Preservation of sulfatian apatite may yield data on the sulfidation states of ancient flood basalts such as the Deccan Traps of India and the Parana basalts of Brazil to address the environmental impact of these giant eruptions.

  14. Perrhenate and Pertechnetate Behavior on Iron and Sulfur-Bearing Compounds

    SciTech Connect

    Anderson, B.E.; Becker, U.; Helean, K.B.; Ewing, R.C.

    2007-07-01

    Investigations of the behavior of the element {sup 99}Tc frequently use a stable isotope of rhenium as an analogue. This is based on the elements? similar radii, major oxidation states of +7 and +4, and analogous eH-pH diagrams. However, recent studies [1] have shown this analogy to be imperfect. Therefore, one goal of this study is to compare the behavior of these elements, with an emphasis on the adsorption of perrhenate and pertechnetate (the major forms of Re and Tc in natural waters) onto mineral surfaces. Quantum mechanical calculations were performed for the adsorption of these two anions onto relaxed clusters of the well-characterized sulfide galena (PbS). With these calculations, we have gained insight into differences between the anions adsorption behavior, including geometry, adsorption energies, and electronic structure. Differences between interactions on terraces and step edges, the effects of co-adsorbates such as Na{sup +} and Cl{sup -}, and chloride complexation were also explored. The influence of water was calculated using homogeneous dielectric fluids.As a complement to the calculations, batch sorption tests are in progress involving ReO{sub 4}{sup -}/TcO{sub 4}{sup -} solution in contact with Fe metal, 10% Fe-doped hydroxyapatite, goethite, hematite, magnetite, pyrite, galena, pyrrhotite, and sphalerite. (authors)

  15. Perrhenate and Pertechnetate Behavior on Iron and Sulfur-Bearing Compounds.

    SciTech Connect

    B.E. Anderson; U. Becker; K.B. Helean; R.C. Ewing

    2006-09-15

    Investigations on the behavior of the radioactive element technetium frequently use a stable isotope of rhenium as an analogue. This is justified by citing the elements similar radii and major oxidation states of +7 and +4. However, at least one study [1] has shown this analogy to be imperfect. Therefore, one goal of our study is to compare the adsorption behavior of perrhenate and pertechnetate (the major forms of Re and Tc in natural waters) on a number of different mineral surfaces. Quantum mechanical calculations were performed on the adsorption of these two anions on a series of iron oxides and sulfides. With these calculations, we gain insight into any differences between the anions adsorption behavior, including geometry, adsorption energies, and electronic structure such as density of states and orbital shapes and energies at the adsorption site. Differences between interactions on terraces and step edges, the effects of co-adsorbates such as Na{sup +} or H{sup +}, and possible reduction mechanisms are also explored. The influence of water was calculated using homogeneous dielectric fluids and explicit water molecules. As a complement to the calculations, batch sorption tests are in progress involving ReO{sub 4}{sup -}/TcO{sub 4}{sup -} solution in contact with Fe metal, 10% Fe-doped hydroxyapatite, goethite, hematite, magnetite, pyrite, galena, and sphalerite.

  16. An Aerosol Condensation Model for Sulfur Trioxide

    SciTech Connect

    Grant, K E

    2008-02-07

    This document describes a model for condensation of sulfuric acid aerosol given an initial concentration and/or source of gaseous sulfur trioxide (e.g. fuming from oleum). The model includes the thermochemical effects on aerosol condensation and air parcel buoyancy. Condensation is assumed to occur heterogeneously onto a preexisting background aerosol distribution. The model development is both a revisiting of research initially presented at the Fall 2001 American Geophysical Union Meeting [1] and a further extension to provide new capabilities for current atmospheric dispersion modeling efforts [2]. Sulfuric acid is one of the most widely used of all industrial chemicals. In 1992, world consumption of sulfuric acid was 145 million metric tons, with 42.4 Mt (mega-tons) consumed in the United States [10]. In 2001, of 37.5 Mt consumed in the U.S., 74% went into producing phosphate fertilizers [11]. Another significant use is in mining industries. Lawuyi and Fingas [7] estimate that, in 1996, 68% of use was for fertilizers and 5.8% was for mining. They note that H{sub 2}SO{sub 4} use has been and should continue to be very stable. In the United States, the elimination of MTBE (methyl tertiary-butyl ether) and the use of ethanol for gasoline production are further increasing the demand for petroleum alkylate. Alkylate producers have a choice of either a hydrofluoric acid or sulfuric acid process. Both processes are widely used today. Concerns, however, over the safety or potential regulation of hydrofluoric acid are likely to result in most of the growth being for the sulfuric acid process, further increasing demand [11]. The implication of sulfuric acid being a pervasive industrial chemical is that transport is also pervasive. Often, this is in the form of oleum tankers, having around 30% free sulfur trioxide. Although sulfuric acid itself is not a volatile substance, fuming sulfuric acid (referred to as oleum) is [7], the volatile product being sulfur trioxide

  17. Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium–Sulfur Batteries

    PubMed Central

    2017-01-01

    Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium–sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development. PMID:28573201

  18. Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

    DOE PAGES

    Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun; ...

    2017-04-27

    Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

  19. Sulfur, Chlorine and Fluorine Degassing and Atmospheric Loading by the Roza eruption, Columbia River Basalt Group, Washington

    NASA Technical Reports Server (NTRS)

    Thordarson, Th.; Self, S

    1996-01-01

    In this study we attempt to quantify the amount of S, Cl and F released by the 1300 cu km Roza member (approximately 14.7 Ma) of the Columbia River Basalt Group, which was produced by a moderate-size flood basalt eruption in the mid-Miocene. Our results are the first indication of the potential atmospheric SO2 yield from a flood basalt eruption, and indicate the mechanism by which flood basalt eruptions may have seriously affected the environment. Glass inclusions in phenocrysts and quenched glass in products from various stages of the eruption were analyzed for concentrations of S, Cl and F and major elements. Glass inclusions contain 1965 +/- 110 ppm S, 295 +/- 65 ppm Cl and 1310 +/- 110 ppm F. Groundmass glass of Roza dike selvages contains considerably lower concentrations: 1110 +/- 90 ppm S, 245 +/- 30 ppm Cl and 1020 +/- 25 ppm F. Scoria clasts from near vent deposits contain 665 +/- 75 ppm S, 175 +/- 5 ppm Cl and 950 +/- 20 ppm F, and the groundmass glass of lava selvages contains 520 +/- 30 ppm S, 190 +/- 30 ppm Cl and 890 +/- 55 ppm F. In crystalline lava, the concentrations are 195 ppm S, 100 ppm Cl and 830 ppm F. Volatile element concentrations in these samples represent the progress of degassing through the eruption and can be used to estimate the potential amount of the volatiles S, Cl and F released by the magma into the atmosphere, as well as to evaluate the amount liberated by various phases of the eruption. The total amount of volatiles released by the Roza eruption is estimated to have been approximately 12,420 MtSO2, approximately 710 MtHCI and approximately 1780 MtHF. The Roza magma liberated approximately 9620 MtSO, (77% of the total volatile mass released), approximately 400 MtHCI (56%) and approximately 1450 MtHF (81%) at the vents and lofted by the eruption columns to altitudes of 7-13 km. Degassing of the lava is estimated to have released an additional approximately 2810 MtSO2, approximately 310 MtHCI and approximately 330 MtHF. The Roza

  20. Spatial patterns of atmospheric deposition of nitrogen and sulfur using ion-exchange resin collectors in Rocky Mountain National Park, USA

    USGS Publications Warehouse

    Clow, David W.; Roop, Heidi; Nanus, Leora; Fenn, Mark; Sexstone, Graham A.

    2015-01-01

    Lakes and streams in Class 1 wilderness areas in the western United States (U.S.) are at risk from atmospheric deposition of nitrogen (N) and sulfur (S), and protection of these resources is mandated under the Federal Clean Air Act and amendments. Assessment of critical loads, which are the maximum exposure to pollution an area can receive without adverse effects on sensitive ecosystems, requires accurate deposition estimates. However, deposition is difficult and expensive to measure in high-elevation wilderness, and spatial patterns in N and S deposition in these areas remain poorly quantified. In this study, ion-exchange resin (IER) collectors were used to measure dissolved inorganic N (DIN) and S deposition during June 2006–September 2007 at approximately 20 alpine/subalpine sites spanning the Continental Divide in Rocky Mountain National Park. Results indicated good agreement between deposition estimated from IER collectors and commonly used wet + dry methods during summer, but poor agreement during winter. Snowpack sampling was found to be a more accurate way of quantifying DIN and S deposition during winter. Summer DIN deposition was significantly greater on the east side of the park than on the west side (25–50%; p ≤ 0.03), consistent with transport of pollutants to the park from urban and agricultural areas to the east. Sources of atmospheric nitrate (NO3−) were examined using N isotopes. The average δ15N of NO3− from IER collectors was 3.5‰ higher during winter than during summer (p < 0.001), indicating a seasonal shift in the relative importance of regional NOxsources, such as coal combustion and vehicular sources of atmospheric NO3−. There were no significant differences in δ15N of NO3− between east and west sides of the park during summer or winter (p = 0.83), indicating that the two areas may have similar sources of atmospheric NO3−. Results from this study indicate that a combination of IER collectors and snowpack

  1. Spatial patterns of atmospheric deposition of nitrogen and sulfur using ion-exchange resin collectors in Rocky Mountain National Park, USA

    NASA Astrophysics Data System (ADS)

    Clow, David W.; Roop, Heidi A.; Nanus, Leora; Fenn, Mark E.; Sexstone, Graham A.

    2015-01-01

    Lakes and streams in Class 1 wilderness areas in the western United States (U.S.) are at risk from atmospheric deposition of nitrogen (N) and sulfur (S), and protection of these resources is mandated under the Federal Clean Air Act and amendments. Assessment of critical loads, which are the maximum exposure to pollution an area can receive without adverse effects on sensitive ecosystems, requires accurate deposition estimates. However, deposition is difficult and expensive to measure in high-elevation wilderness, and spatial patterns in N and S deposition in these areas remain poorly quantified. In this study, ion-exchange resin (IER) collectors were used to measure dissolved inorganic N (DIN) and S deposition during June 2006-September 2007 at approximately 20 alpine/subalpine sites spanning the Continental Divide in Rocky Mountain National Park. Results indicated good agreement between deposition estimated from IER collectors and commonly used wet + dry methods during summer, but poor agreement during winter. Snowpack sampling was found to be a more accurate way of quantifying DIN and S deposition during winter. Summer DIN deposition was significantly greater on the east side of the park than on the west side (25-50%; p ≤ 0.03), consistent with transport of pollutants to the park from urban and agricultural areas to the east. Sources of atmospheric nitrate (NO3-) were examined using N isotopes. The average δ15N of NO3- from IER collectors was 3.5‰ higher during winter than during summer (p < 0.001), indicating a seasonal shift in the relative importance of regional NOx sources, such as coal combustion and vehicular sources of atmospheric NO3-. There were no significant differences in δ15N of NO3- between east and west sides of the park during summer or winter (p = 0.83), indicating that the two areas may have similar sources of atmospheric NO3-. Results from this study indicate that a combination of IER collectors and snowpack sampling can be used to

  2. Multi-model Mean Nitrogen and Sulfur Deposition from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): Evaluation of Historical and Projected Future Changes

    SciTech Connect

    Lamarque, Jean-Francois; Dentener, Frank; McConnell, J.R.; Ro, C-U; Shaw, Mark; Vet, Robert; Bergmann, D.; Cameron-Smith, Philip; Dalsoren, S.; Doherty, R.; Faluvegi, G.; Ghan, Steven J.; Josse, B.; Lee, Y. H.; MacKenzie, I. A.; Plummer, David; Shindell, Drew; Skeie, R. B.; Stevenson, D. S.; Strode, S.; Zeng, G.; Curran, M.; Dahl-Jensen, D.; Das, S.; Fritzsche, D.; Nolan, M.

    2013-08-20

    We present multi-model global datasets of nitrogen and sulfate deposition covering time periods from 1850 to 2100, calculated within the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). The computed deposition fluxes are compared to surface wet deposition and ice-core measurements. We use a new dataset of wet deposition for 2000-2002 based on critical assessment of the quality of existing regional network data. We show that for present-day (year 2000 ACCMIP time-slice), the ACCMIP results perform similarly to previously published multi-model assessments. The analysis of changes between 1980 and 2000 indicates significant differences between model and measurements over the United States, but less so over Europe. This difference points towards misrepresentation of 1980 NH3 emissions over North America. Based on ice-core records, the 1850 deposition fluxes agree well with Greenland ice cores but the change between 1850 and 2000 seems to be overestimated in the Northern Hemisphere for both nitrogen and sulfur species. Using the Representative Concentration Pathways to define the projected climate and atmospheric chemistry related emissions and concentrations, we find large regional nitrogen deposition increases in 2100 in Latin America, Africa and parts of Asia under some of the scenarios considered. Increases in South Asia are especially large, and are seen in all scenarios, with 2100 values more than double 2000 in some scenarios and reaching >1300 mgN/m2/yr averaged over regional to continental scale regions in RCP 2.6 and 8.5, ~30-50% larger than the values in any region currently (2000). Despite known issues, the new ACCMIP deposition dataset provides novel, consistent and evaluated global gridded deposition fields for use in a wide range of climate and ecological studies.

  3. Observation of vanadyl porphyrins and sulfur-containing vanadyl porphyrins in a petroleum asphaltene by atmospheric pressure photonionization Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Qian, Kuangnan; Mennito, Anthony S; Edwards, Kathleen E; Ferrughelli, Dave T

    2008-07-01

    Vanadyl (VO) porphyrins and sulfur-containing vanadyl (VOS) porphyrins of a wide carbon number range (C(26) to C(52)) and Z-number range (-28 to -54) were detected and identified in a petroleum asphaltene by atmospheric pressure photonionization (APPI) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). APPI provides soft ionization of asphaltene molecules (including VO and VOS porphyrins), generating primarily molecular ions (M(+.)). The ultra-high mass resolving power (m/Delta m(FWHM) approximately 500 K) of FTICR-MS enabled resolution and positive identification of elemental formulae for the entire family of VO and VOS porphyrins in a complicated asphaltene matrix. Deocophylerythro-etioporphyrin (DPEP) is found to be the most prevalent structure, followed by etioporphyrins (etio)- and rhodo (benzo)-DPEP. The characteristic Z-distribution of VO porphyrins suggests benzene and naphthene increment in the growth of porphyrin ring structures. Bimodal carbon number distributions of VO porphyrins suggest possible different origins of low and high molecular weight species. To our knowledge, the observation of VOS porphyrins in a petroleum product has not previously been reported. The work is also the first direct identification of the entire vanadyl porphyrin family by ultra-high resolution mass spectrometry without chromatographic separation or demetallation.

  4. A case study of the relative effects of power plant nitrogen oxides and sulfur dioxide emission reductions on atmospheric nitrogen deposition.

    PubMed

    Vijayaraghavan, Krish; Seigneur, Christian; Bronson, Rochelle; Chen, Shu-Yun; Karamchandani, Prakash; Walters, Justin T; Jansen, John J; Brandmeyer, Jo Ellen; Knipping, Eladio M

    2010-03-01

    The contrasting effects of point source nitrogen oxides (NOx) and sulfur dioxide (SO2) air emission reductions on regional atmospheric nitrogen deposition are analyzed for the case study of a coal-fired power plant in the southeastern United States. The effect of potential emission reductions at the plant on nitrogen deposition to Escambia Bay and its watershed on the Florida-Alabama border is simulated using the three-dimensional Eulerian Community Multiscale Air Quality (CMAQ) model. A method to quantify the relative and individual effects of NOx versus SO2 controls on nitrogen deposition using air quality modeling results obtained from the simultaneous application of NOx and SO2 emission controls is presented and discussed using the results from CMAQ simulations conducted with NOx-only and SO2-only emission reductions; the method applies only to cases in which ambient inorganic nitrate is present mostly in the gas phase; that is, in the form of gaseous nitric acid (HNO3). In such instances, the individual effects of NOx and SO2 controls on nitrogen deposition can be approximated by the effects of combined NOx + SO2 controls on the deposition of NOy, (the sum of oxidized nitrogen species) and reduced nitrogen species (NHx), respectively. The benefit of controls at the plant in terms of the decrease in nitrogen deposition to Escambia Bay and watershed is less than 6% of the overall benefit due to regional Clean Air Interstate Rule (CAIR) controls.

  5. Atmospheric wet deposition of nitrogen and sulfur to a typical red soil agroecosystem in Southeast China during the ten-year monsoon seasons (2003-2012)

    NASA Astrophysics Data System (ADS)

    Cui, Jian; Zhou, Jing; Peng, Ying; He, Yuanqiu; Yang, Hao; Mao, Jingdong

    2014-01-01

    Biological processes in agroecosystems have been affected by atmospheric nitrogen (N) and sulfur (S) deposition, but there is uncertainty about their deposition characteristics in the monsoon season. We collected rain samples using an ASP-2 sampler, recorded rainfall and rain frequency by an auto-meteorological experiment sub-station, and determined total N, NO3--N and NH4+-N levels in precipitation with an AutoAnalyzer 3 and SO42--S with a chromatography, in order to characterize the wet deposition of N and S to a typical red soil agroecosystem by a ten-year monitoring experiment in Southeast China. The results indicated that N and S wet deposition had an increased trend with the flux of total N (3.34-65.17 kg ha-1 N) and total S (SO42--S) (7.17-23.44 kg ha-1 S) during the monsoon seasons. The additional applications of pig mature in 2006 and 2007 led to the peaks of DON (dissolved organic nitrogen) and total N wet deposition. On average, NH4+-N was the major N form, accounting for 48.5% of total N wet deposition and DON was not a negligible N form, accounting for 20.8% during the ten-year monsoon seasons (except 2006 and 2007). Wet deposition of N and S has been intensively influenced by human activities in the monsoon season, and would increase the potential ecological risk in the red soil agricultural ecosystem.

  6. The importance of sulfur for the behavior of highly-siderophile elements during Earth's differentiation

    NASA Astrophysics Data System (ADS)

    Laurenz, Vera; Rubie, David C.; Frost, Daniel J.; Vogel, Antje K.

    2016-12-01

    The highly siderophile elements (HSEs) are widely used as geochemical tracers for Earth's accretion and core formation history. It is generally considered that core formation strongly depleted the Earth's mantle in HSEs, which were subsequently replenished by a chondritic late veneer. However, open questions remain regarding the origin of suprachondritic Ru/Ir and Pd/Ir ratios that are thought to be characteristic for the primitive upper mantle. In most core-formation models that address the behavior of the HSEs, light elements such as S entering the core have not been taken into account and high P-T experimental data for S-bearing compositions are scarce. Here we present a comprehensive experimental study to investigate the effect of increasing S concentration in the metal on HSE metal-silicate partitioning at 2473 K and 11 GPa. We show that the HSEs become less siderophile with increasing S concentrations in the metal, rendering core-forming metal less efficient in removing the HSEs from the mantle if S is present. Furthermore, we investigated the FeS sulfide-silicate partitioning of the HSEs as a function of pressure (7-21 GPa) and temperature (2373-2673 K). The sulfide-silicate partition coefficient for Pt increases strongly with P, whereas those for Pd, Ru and Ir all decrease. The combined effect is such that above ∼20 GPa Ru becomes less chalcophile than Pt, which is opposite to their behavior in the metal-silicate system where Ru is always more siderophile than Pt. The newly determined experimental results are used in a simple 2-stage core formation model that takes into account the effect of S on the behavior of the HSEs during core formation. Results of this model show that segregation of a sulfide liquid to the core from a mantle with substantial HSE concentrations plays a key role in reproducing Earth's mantle HSE abundances. As Ru and Pd are less chalcophile than Pt and Ir at high P-T, some Ru and Pd remain in the mantle after sulfide segregation

  7. Effects of sulfur dioxide emissions on stream chemistry in the western United States

    USGS Publications Warehouse

    Campbell, D.H.; Turk, J.T.

    1988-01-01

    A 20-year record of water chemistry for seven headwater streams in the Rocky Mountain region of the western United States is compared to estimates of local and regional sulfur dioxide emissions. Emissions from smelters comprise a significant part of sulfur dioxide emissions for the 11 states upwind of acid-sensitive watersheds in the Rocky Mountains, but smelter emissions have steadily decreased since 1970. Analysis of stream chemistry indicates conservative behavior of watershed sulfate, with atmospheric deposition as the dominant source. No relation between regional stream chemistry and smelter or regional sulfur dioxide emissions is detected. Local emissions trends, however, do appear to affect sulfate concentrations in the streams. -from Authors

  8. Effect of Elemental Sulfur and Sulfide on the Corrosion Behavior of Cr-Mo Low Alloy Steel for Tubing and Tubular Components in Oil and Gas Industry

    PubMed Central

    Khaksar, Ladan; Shirokoff, John

    2017-01-01

    The chemical degradation of alloy components in sulfur-containing environments is a major concern in oil and gas production. This paper discusses the effect of elemental sulfur and its simplest anion, sulfide, on the corrosion of Cr-Mo alloy steel at pH 2 and 5 during 10, 20 and 30 h immersion in two different solutions. 4130 Cr-Mo alloy steel is widely used as tubing and tubular components in sour services. According to the previous research in aqueous conditions, contact of solid sulfur with alloy steel can initiate catastrophic corrosion problems. The corrosion behavior was monitored by the potentiodynamic polarization technique during the experiments. Energy dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM) have been applied to characterize the corrosion product layers after each experiment. The results show that under the same experimental conditions, the corrosion resistance of Cr-Mo alloy in the presence of elemental sulfur is significantly lower than its resistance in the presence of sulfide ions. PMID:28772790

  9. Biogenic sulfur emissions and aerosols over the tropical South Atlantic: 3. Atmospheric dimethylsulfide, aerosols and cloud condensation nuclei

    NASA Astrophysics Data System (ADS)

    Andreae, Meinrat O.; Elbert, Wolfgang; de Mora, Stephen J.

    1995-06-01

    We measured dimethylsulfide in air (DMSa) and the number concentration, size distribution, and chemical composition of atmospheric aerosols, including the concentration of cloud condensation nuclei (CCN), during February-March 1991 over the tropical South Atlantic along 19°S (F/S Meteor, cruise 15/3). Aerosol number/size distributions were determined with a laser-optical particle counter, condensation nuclei (CN) concentrations with a TSI 3020, and cloud condensation nuclei (CCN) with a Hudson-type supersaturation chamber. Aerosol samples were collected on two-stage stacked filters and analyzed by ion chromatography for soluble ion concentrations. Black carbon in aerosols was measured by visible light absorption and used to identify and eliminate periods with anthropogenic pollution from the data set. Meteorological analysis shows that most of the air masses sampled had spent extended periods over remote marine areas in the tropical and subtropical region. DMSa was closely correlated with the sea-to- air DMS flux calculated from DMS concentrations in seawater and meteorological data. Sea salt made the largest contribution to aerosol mass and volume but provided only a small fraction of the aerosol number concentration. The submicron aerosol had a mean composition close to ammonium bisulfate, with the addition of some methanesulfonate. Aerosol (CN and CCN) number and non-sea-salt sulfate concentrations were significantly correlated with DMS concentration and flux. This suggests that DMS oxidation followed by aerosol nucleation and growth in the marine boundary layer is an important, if not dominating, source of CN and possibly CCN. The degree of correlation between DMS and particle concentrations in the marine boundary layer may be strongly influenced by the different time scales of the processes regulating these concentrations. Our results provide strong support for several aspects of the CLAW hypothesis, which proposes the existence of a feedback loop linking DMS

  10. Investigations on the Electrochemical Reduction Behaviors of Cu-Se Compound in Sulfuric Acid Solutions

    NASA Astrophysics Data System (ADS)

    Li, Yuan-yuan; Yang, Meng-qian; Yang, Wei-fang; Liu, Xiao-qing; Shen, Zheng-wu; Yi, Yun; Wang, Wei

    2017-05-01

    The electrochemical reduction behaviors of a Cu unitary system, Se unitary system and Cu-Se binary system were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy in solutions containing H2SO4, K2SO4, CuSO4 (Cu unitary system) or H2SeO3 (Se unitary system) or both CuSO4 and H2SeO3 (Cu-Se binary system). The effects of CuSO4 concentration, H2SeO3 concentration, H2SO4 concentration and K2SO4 concentration were also considered. In the Cu unitary system, the electrochemical reduction of Cu2+ to Cu0 experiences a two-step reaction process. Cu2+ in the solutions was first reduced to Cu+ and then to Cu0 on the surface of the electrode. A four-step electrochemical reduction process takes place in the Se unitary system. Se4+ existing in the form of H2SeO3 is first reduced to Se2+ by a two-electron reaction step and then to Se0 at a more negative potential. With the potential moving negatively, the electrodeposited Se0 on the surface of the electrode is further reduced to Se2-. There is also a chemical reaction taking place between the reduced Se2- and H2SeO3 existing in the solution to form Se0. In the Cu-Se binary system, there are three major processes taking place which form CuSe, Cu3Se2 and Cu2Se. X-ray diffraction and energy-dispersive spectroscopy were used in combination to verify their formation.

  11. Investigations on the Electrochemical Reduction Behaviors of Cu-Se Compound in Sulfuric Acid Solutions

    NASA Astrophysics Data System (ADS)

    Li, Yuan-yuan; Yang, Meng-qian; Yang, Wei-fang; Liu, Xiao-qing; Shen, Zheng-wu; Yi, Yun; Wang, Wei

    2017-03-01

    The electrochemical reduction behaviors of a Cu unitary system, Se unitary system and Cu-Se binary system were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy in solutions containing H2SO4, K2SO4, CuSO4 (Cu unitary system) or H2SeO3 (Se unitary system) or both CuSO4 and H2SeO3 (Cu-Se binary system). The effects of CuSO4 concentration, H2SeO3 concentration, H2SO4 concentration and K2SO4 concentration were also considered. In the Cu unitary system, the electrochemical reduction of Cu2+ to Cu0 experiences a two-step reaction process. Cu2+ in the solutions was first reduced to Cu+ and then to Cu0 on the surface of the electrode. A four-step electrochemical reduction process takes place in the Se unitary system. Se4+ existing in the form of H2SeO3 is first reduced to Se2+ by a two-electron reaction step and then to Se0 at a more negative potential. With the potential moving negatively, the electrodeposited Se0 on the surface of the electrode is further reduced to Se2-. There is also a chemical reaction taking place between the reduced Se2- and H2SeO3 existing in the solution to form Se0. In the Cu-Se binary system, there are three major processes taking place which form CuSe, Cu3Se2 and Cu2Se. X-ray diffraction and energy-dispersive spectroscopy were used in combination to verify their formation.

  12. Analysis of the free-fall behavior of liquid-metal drops in a gaseous atmosphere

    NASA Technical Reports Server (NTRS)

    Mccoy, J. Kevin; Markworth, Alan J.; Collings, E. W.; Brodkey, Robert S.

    1987-01-01

    The free-fall of a liquid-metal drop and heat transfer from the drop to its environment are described for both a gaseous atmosphere and vacuum. A simple model, in which the drop is assumed to fall rectilinearly with behavior like that of a rigid particle, is developed first, then possible causes of deviation from this behavior are discussed. The model is applied to describe solidification of drops in a drop tube. Possible future developments of the model are suggested.

  13. Analysis of the free-fall behavior of liquid-metal drops in a gaseous atmosphere

    NASA Technical Reports Server (NTRS)

    Mccoy, J. Kevin; Markworth, Alan J.; Collings, E. W.; Brodkey, Robert S.

    1987-01-01

    The free-fall of a liquid-metal drop and heat transfer from the drop to its environment are described for both a gaseous atmosphere and vacuum. A simple model, in which the drop is assumed to fall rectilinearly with behavior like that of a rigid particle, is developed first, then possible causes of deviation from this behavior are discussed. The model is applied to describe solidification of drops in a drop tube. Possible future developments of the model are suggested.

  14. A preliminary study on sulfate reduction bacteria behaviors in groundwater by sulfur and carbon isotopes: a case study in Jiaozuo City, China.

    PubMed

    Zhang, Dong; Liu, Congqiang

    2014-12-01

    Inorganic pollutants in groundwater, such as sulfate and nitrate, have been a serious problem in China for decades. These pollutants are difficult to be removed because of their high solubility and ease of transport in subsurface environment. It had been found that microorganism could be one of the most feasible methods for inorganic pollutant elimination. During the process of degradation, some microorganisms can utilize sulfur and nitrogen in sulfate and nitrate forms, respectively, as energy sources. Meanwhile, significant variations of sulfur stable isotope ratios happened. Therefore sulfur isotope can be used as a good indicator for pollutant degradation and microbial activities. Shallow groundwater (SGW), deep groundwater (DGW), and surface water (SFW) were investigated in alluvial plain in Jiaozuo City, China. The results of hydrochemical analysis indicated that K(+), Na(+), and HCO3(-) were dominant ions in DGW, Mg(2+) and HCO3(-) were dominant ions in SGW, and Ca(2+) and HCO3 (-) were dominant in SFW except for LR sample. A wide variation of δ (34)SSO4 values ranging from + 7.3 to +23.6‰ had been observed for all water samples, with a mean value of +20.7, +12.6 and +10.0‰ for DGW, SGW, and SFW respectively. At the same time, δ(13)C values of dissolved inorganic carbon (DIC) ranged from -12.4 to -5.7‰, with a mean value of -7.5, -9.0, and -9.6‰ for DGW, SGW, and SFW, respectively. The microbial degradation processes resulted in significant sulfur isotope fractionations in DGW. Organic carbon was utilized by bacteria and transferred into inorganic carbon, leading to negative fractionation of carbon isotopes. Thus the variations in stable isotope ratios of sulfur and carbon in groundwater can be used as good indicators for understanding of the relationship between bacteria behaviors and sulfate degradation.

  15. Sulfur revisited.

    PubMed

    Lin, A N; Reimer, R J; Carter, D M

    1988-03-01

    Sulfur is a time-honored therapeutic agent useful in a variety of dermatologic disorders. Its keratolytic action is due to formation of hydrogen sulfide through a reaction that depends upon direct interaction between sulfur particles and keratinocytes. The smaller the particle size, the greater the degree of such interaction and the greater the therapeutic efficacy. When applied topically, sulfur induces various histologic changes, including hyperkeratosis, acanthosis, and dilatation of dermal vasculature. One study showed that sulfur was comedogenic when applied onto human and rabbit skin, findings that were not reproduced in other studies. About 1% of topically applied sulfur is systemically absorbed. Adverse effects from topically applied sulfur are uncommon and are mainly limited to the skin. In infants, however, fatal outcome after extensive application has been reported.

  16. Sulfur Cycle

    NASA Technical Reports Server (NTRS)

    Hariss, R.; Niki, H.

    1985-01-01

    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.

  17. Target loads of atmospheric sulfur deposition for the protection and recovery of acid-sensitive streams in the Southern Blue Ridge Province.

    PubMed

    Sullivan, Timothy J; Cosby, Bernard J; Jackson, William A

    2011-11-01

    An important tool in the evaluation of acidification damage to aquatic and terrestrial ecosystems is the critical load (CL), which represents the steady-state level of acidic deposition below which ecological damage would not be expected to occur, according to current scientific understanding. A deposition load intended to be protective of a specified resource condition at a particular point in time is generally called a target load (TL). The CL or TL for protection of aquatic biota is generally based on maintaining surface water acid neutralizing capacity (ANC) at an acceptable level. This study included calibration and application of the watershed model MAGIC (Model of Acidification of Groundwater in Catchments) to estimate the target sulfur (S) deposition load for the protection of aquatic resources at several future points in time in 66 generally acid-sensitive watersheds in the southern Blue Ridge province of North Carolina and two adjoining states. Potential future change in nitrogen leaching is not considered. Estimated TLs for S deposition ranged from zero (ecological objective not attainable by the specified point in time) to values many times greater than current S deposition depending on the selected site, ANC endpoint, and evaluation year. For some sites, one or more of the selected target ANC critical levels (0, 20, 50, 100μeq/L) could not be achieved by the year 2100 even if S deposition was reduced to zero and maintained at that level throughout the simulation. Many of these highly sensitive streams were simulated by the model to have had preindustrial ANC below some of these target values. For other sites, the watershed soils contained sufficiently large buffering capacity that even very high sustained levels of atmospheric S deposition would not reduce stream ANC below common damage thresholds.

  18. Spatial variation of biogenic sulfur in the south Yellow Sea and the East China Sea during summer and its contribution to atmospheric sulfate aerosol.

    PubMed

    Zhang, Sheng-Hui; Yang, Gui-Peng; Zhang, Hong-Hai; Yang, Jian

    2014-08-01

    Spatial distributions of biogenic sulfur compounds including dimethylsulfide (DMS), dissolved and particulate dimethylsulfoniopropionate (DMSPd and DMSPp) were investigated in the South Yellow Sea (SYS) and the East China Sea (ECS) in July 2011. The concentrations of DMS and DMSPp were significantly correlated with the levels of chlorophyll a in the surface water. Simultaneously, relatively high ratio values of DMSP/chlorophyll a and DMS/chlorophyll a occurred in the areas where the phytoplankton community was dominated by dinoflagellates. The DMSPp and chlorophyll a size-fractionation showed that larger nanoplankton (5-20 μm) was the most important producer of DMSPp in the study area. The vertical profiles of DMS and DMSP were characterized by a maximum at the upper layer and the bottom concentrations were also relatively higher compared with the overlying layer of the bottom. In addition, a positive linear correlation was observed between dissolved dimethylsulfoxide (DMSOd) and DMS concentrations in the surface waters. The sea-to-air fluxes of DMS in the study area were estimated to be from 0.03 to 102.35 μmol m(-2) d(-1) with a mean of 16.73 μmol m(-2) d(-1) and the contribution of biogenic non-sea-salt SO4(2-) (nss-SO4(2-)) to the measured total nss-SO4(2-) in the atmospheric aerosol over the study area varied from 1.42% to 30.98%, with an average of 8.2%.

  19. Resolving the Strange Behavior of Extraterrestrial Potassium in the Upper Atmosphere

    NASA Technical Reports Server (NTRS)

    Plane, J. M. C.; Feng, W.; Dawkins, E.; Chipperfield, M. P.; Hoeffner, J.; Janches, D.; Marsh, D. R.

    2014-01-01

    It has been known since the 1960s that the layers of Na and K atoms, which occur between 80 and 105km in the Earth's atmosphere as a result of meteoric ablation, exhibit completely different seasonal behavior. In the extratropics Na varies annually, with a pronounced wintertime maximum and summertime minimum. However, K varies semiannually with a small summertime maximum and minima at the equinoxes. This contrasting behavior has never been satisfactorily explained. Here we use a combination of electronic structure and chemical kinetic rate theory to determine two key differences in the chemistries of K and Na. First, the neutralization of K+ ions is only favored at low temperatures during summer. Second, cycling between K and its major neutral reservoir KHCO3 is essentially temperature independent. A whole atmosphere model incorporating this new chemistry, together with a meteor input function, now correctly predicts the seasonal behavior of the K layer.

  20. Sulfur cycling, retention, and mobility in soils: A review

    Treesearch

    Pamela J. Edwards

    1998-01-01

    Sulfur inputs to forests originate from mineral weathering, atmospheric deposition, and organic matter decomposition. In the soil, sulfur occurs in organic and inorganic forms and is cycled within and between those forms via mobilization, immobilization, mineralization, oxidation, and reduction processes. Organic sulfur compounds are largely immobile. Inorganic sulfur...

  1. The Role of Family Atmosphere in the Relapse Behavior of Iranian Opiate Users: a Qualitative Study

    PubMed Central

    Peyrovi, Hamid; Seyedfatemi, Naiemeh; Jalali, Amir

    2015-01-01

    Introduction Many Iranian opiate users live with family members and family atmosphere can be influential on reducing such social behaviors of opiate users as substance use and relapses. This paper reports the impact of family atmosphere on relapse behavior as a part of the findings of a larger study that explored the relapse process among Iranian opiate users. Methods: In this qualitative research, we selected 17 participants (5 women and 12 men). The questions were been asked through semi-structured interviews. The researchers analyzed the verbatim transcripts using content analysis method. Results: "Family atmosphere" with three sub-themes (family and tribes' interaction, family challenges and family structure) was been found as determinants of relapse behavior. The quality of the family atmosphere could be in harmony with or against the willingness or motivation of the opiate user towards the relapse. Conclusion Health care providers should reinforce involvement of the family members in the treatment and rehabilitation of opiate users. The opiate user's family and even relatives may benefit from learning how to manage their own feelings and attitude towards the client and being supportive during interactions. PMID:26464835

  2. Atmosphere behavior in gas-closed mouse-algal systems - An experimental and modelling study

    NASA Technical Reports Server (NTRS)

    Averner, M. M.; Moore, B., III; Bartholomew, I.; Wharton, R.

    1984-01-01

    A NASA-sponsored research program initiated using mathematical modelling and laboratory experimentation aimed at examining the gas-exchange characteristics of artificial animal/plant systems closed to the ambient atmosphere is studied. The development of control techniques and management strategies for maintaining the atmospheric levels of carbon dioxide and oxygen at physiological levels is considered. A mathematical model simulating the behavior of a gas-closed mouse-algal system under varying environmental conditions is described. To verify and validate the model simulations, an analytical system with which algal growth and gas exchange characteristics can be manipulated and measured is designed, fabricated, and tested. The preliminary results are presented.

  3. Atmosphere behavior in gas-closed mouse-algal systems - An experimental and modelling study

    NASA Technical Reports Server (NTRS)

    Averner, M. M.; Moore, B., III; Bartholomew, I.; Wharton, R.

    1984-01-01

    A NASA-sponsored research program initiated using mathematical modelling and laboratory experimentation aimed at examining the gas-exchange characteristics of artificial animal/plant systems closed to the ambient atmosphere is studied. The development of control techniques and management strategies for maintaining the atmospheric levels of carbon dioxide and oxygen at physiological levels is considered. A mathematical model simulating the behavior of a gas-closed mouse-algal system under varying environmental conditions is described. To verify and validate the model simulations, an analytical system with which algal growth and gas exchange characteristics can be manipulated and measured is designed, fabricated, and tested. The preliminary results are presented.

  4. An Analytic Approach to Modeling Land-Atmosphere Interaction: 1. Construct and Equilibrium Behavior

    NASA Astrophysics Data System (ADS)

    Brubaker, Kaye L.; Entekhabi, Dara

    1995-03-01

    A four-variable land-atmosphere model is developed to investigate the coupled exchanges of water and energy between the land surface and atmosphere and the role of these exchanges in the statistical behavior of continental climates. The land-atmosphere system is substantially simplified and formulated as a set of ordinary differential equations that, with the addition of random noise, are suitable for analysis in the form of the multivariate Îto equation. The model treats the soil layer and the near-surface atmosphere as reservoirs with storage capacities for heat and water. The transfers between these reservoirs are regulated by four states: soil saturation, soil temperature, air specific humidity, and air potential temperature. The atmospheric reservoir is treated as a turbulently mixed boundary layer of fixed depth. Heat and moisture advection, precipitation, and layer-top air entrainment are parameterized. The system is forced externally by solar radiation and the lateral advection of air and water mass. The remaining energy and water mass exchanges are expressed in terms of the state variables. The model development and equilibrium solutions are presented. Although comparisons between observed data and steady state model results re inexact, the model appears to do a reasonable job of partitioning net radiation into sensible and latent heat flux in appropriate proportions for bare-soil midlatitude summer conditions. Subsequent work will introduce randomness into the forcing terms to investigate the effect of water-energy coupling and land-atmosphere interaction on variability and persistence in the climatic system.

  5. 40 CFR 60.104 - Standards for sulfur oxides.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... atmosphere from any Claus sulfur recovery plant containing in excess of: (i) For an oxidation control system... emissions to the atmosphere by 90 percent or maintain SO2 emissions to the atmosphere less than or equal to... device to reduce SO2 emission, maintain sulfur oxides emissions calculated as SO2 to the atmosphere...

  6. The seasonal and global behavior of water vapor in the Mars atmosphere - Complete global results of the Viking atmospheric water detector experiment

    NASA Technical Reports Server (NTRS)

    Jakosky, B. M.; Farmer, C. B.

    1982-01-01

    A key question regarding the evolution of Mars is related to the behavior of its volatiles. The present investigation is concerned with the global and seasonal abundances of water vapor in the Mars atmosphere as mapped by the Viking Mars Atmospheric Water Detector (MAWD) instrument for almost 1-1/2 Martian years from June 1976 to April 1979. Attention is given to the implications of the observed variations for determining the relative importance of those processes which may be controlling the vapor cycle on a seasonal basis. The processes considered include buffering of the atmosphere water by a surface or subsurface reservior of ground ice, physically adsorbed water, or chemically bound water. Other processes are related to the supply of water from the residual or seasonal north polar ice cap, the redistribution of the vapor resulting from atmospheric circulation, and control of the vapor holding capacity of the atmosphere by the local atmospheric temperatures.

  7. The seasonal and global behavior of water vapor in the Mars atmosphere - Complete global results of the Viking atmospheric water detector experiment

    NASA Technical Reports Server (NTRS)

    Jakosky, B. M.; Farmer, C. B.

    1982-01-01

    A key question regarding the evolution of Mars is related to the behavior of its volatiles. The present investigation is concerned with the global and seasonal abundances of water vapor in the Mars atmosphere as mapped by the Viking Mars Atmospheric Water Detector (MAWD) instrument for almost 1-1/2 Martian years from June 1976 to April 1979. Attention is given to the implications of the observed variations for determining the relative importance of those processes which may be controlling the vapor cycle on a seasonal basis. The processes considered include buffering of the atmosphere water by a surface or subsurface reservior of ground ice, physically adsorbed water, or chemically bound water. Other processes are related to the supply of water from the residual or seasonal north polar ice cap, the redistribution of the vapor resulting from atmospheric circulation, and control of the vapor holding capacity of the atmosphere by the local atmospheric temperatures.

  8. Experimental Behavior of Sulfur Under Primitive Planetary Differentiation Processes, the Sulfide Formations in Enstatite Meteorites and Implications for Mercury.

    NASA Technical Reports Server (NTRS)

    Malavergne, V.; Brunet, F.; Righter, K.; Zanda, B.; Avril, C.; Borensztajn, S.; Berthet, S.

    2012-01-01

    Enstatite meteorites are the most reduced naturally-occuring materials of the solar system. The cubic monosulfide series with the general formula (Mg,Mn,Ca,Fe)S are common phases in these meteorite groups. The importance of such minerals, their formation, composition and textural relationships for understanding the genesis of enstatite chondrites (EC) and aubrites, has long been recognized (e.g. [1]). However, the mechanisms of formation of these sulfides is still not well constrained certainly because of possible multiple ways to produce them. We propose to simulate different models of formation in order to check their mineralogical, chemical and textural relevancies. The solubility of sulfur in silicate melts is of primary interest for planetary mantles, particularly for the Earth and Mercury. Indeed, these two planets could have formed, at least partly, from EC materials (e.g. [2, 3, 4]). The sulfur content in silicate melts depends on the melt composition but also on pressure (P), temperature (T) and oxygen fugacity fO2. Unfortunately, there is no model of general validity in a wide range of P-T-fO2-composition which describes precisely the evolution of sulfur content in silicate melts, even if the main trends are now known. The second goal of this study is to constrain the sulfur content in silicate melts under reducing conditions and different temperatures.

  9. Transient Scaling Behavior and Predictability of Atmospheric Moisture, Clouds and Precipitation

    NASA Astrophysics Data System (ADS)

    Barros, Ana; Nogueira, Miguel; Sun, Xiaoming

    2015-04-01

    The stochastic scaling behavior of clouds and rainfall observations exhibits transient behavior consistent with the temporal and spatial evolution of atmospheric dynamics at all scales. In mountainous regions, and regions of well-defined, spatially stationary modes of land-atmosphere interactions, analysis of remote-sensing and ground-based observations shows ubiquitous co-organization of landform, clouds and precipitation with seasonal and inter-annual variability consistent with regional climate. Recent work using both idealized and realistic model simulations of atmospheric dynamics (Nogueira and Barros, 2014; Nogueira et al., 2013) shows that transient scaling behavior at regional scales can be strictly interpreted in the light of moist processes, and in particular atmospheric stability regimes as defined by CAPE, Richardson number and normalized Brunt-Vaisala frequency among others. Furthermore, a sharp transition scaling parameters between non-convective and convective conditions is found that explains different scaling regimes reported in the literature for atmospheric wind, temperature and moisture observations. Spectral slopes around 2-2.3 arise under non-convective or very weak convective conditions, tightly related to the scaling behavior of the underlying topography. In convective situations the transient scaling exponents remain under 5/3 in agreement with the Kolmogorov turbulent regime accounting for the intermittency correction. The non-convective/convective transition is also unambiguously captured by the temporal evolution of the multifractal intermittency parameter. These findings indicate that the transient stochastic scaling of clouds and precipitation is an emergent property of complex moist processes with important implications for predictability: predictability in space conditional on landform and land-atmosphere interactions at local to regional scales, and predictability in time conditional on atmospheric dynamics, and convective activity

  10. Monitoring and ANN modeling of coal stockpile behavior under different atmospheric conditions

    SciTech Connect

    Ozdeniz, A.H.; Ozbay, Y.; Yilmaz, N.; Sensogut, C.

    2008-07-01

    In this study, an industrial-sized stockpile of 5 m width, 4 m height, and 10 m length was built in a coal stock area to investigate coal stockpile behavior under different atmospheric conditions. The effective parameters on the coal stockpile that were time, weather temperature, atmospheric pressure, air humidity, velocity, and direction of wind values were automatically measured by means of a computer-aided measurement system to obtain Artificial Neural Network (ANN) input data. The coal stockpiles, which should be continuously observed, are capable of spontaneous combustion and then causing serious economical losses due to the mentioned parameters. Afterwards, these measurement values were used for training and testing of the ANN model. Comparison of the experimental and ANN results, accuracy rates of training, and testing were found as 98.6% and 98.7%, respectively. It is shown that possible coal stockpile behavior with this ANN model is powerfully estimated.

  11. Lunar sulfur

    NASA Technical Reports Server (NTRS)

    Kuck, David L.

    1991-01-01

    Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

  12. Lunar sulfur

    NASA Astrophysics Data System (ADS)

    Kuck, David L.

    Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

  13. Correlations between the behavior of recreational horses, the physiological parameters and summer atmospheric conditions.

    PubMed

    Janczarek, Iwona; Wilk, Izabela; Zalewska, Edyta; Bocian, Krzysztof

    2015-07-01

    The aim of this paper was to select atmospheric factors and their values, which may disrupt the correct behavior and physiological condition of recreational horses. The studies were carried out from 1 July until 1 September on 16 Anglo-Arabian geldings. Each day, from 09.00 to 10.00 hours, the horses worked under saddle. The riders and the authors gave a qualitative behavioral assessment for each horse. Mood and willingness to work were evaluated. The quantitative assessment was called 'incorrect behavior of the horse while riding' (IBHR). The percentage time of duration and the number of occurrences of the features while riding were calculated. Heart rate, body temperature and respiratory rate were taken at 08.00 hours (resting measurement) and at 10.05 hours (post-exercise measurement). Air temperature, relative air humidity, wind speed and atmospheric pressure were measured at 08.00 and 10.00 hours. The results showed that adverse changes in the behavior of recreational horses can occur if the horse is ridden when the air temperature is above 26°C and when wind speeds exceed 5.5 m/s. Such conditions may cause a reduction in the mood and willingness to work in horses. Physiological parameters like heart rate and body temperature seem to be more sensitive indicators of the horse body reaction to the weather than behavioral reactions.

  14. The influence of diesel-truck exhaust particles on the kinetics of the atmospheric oxidation of dissolved sulfur dioxide by oxygen.

    PubMed

    Meena, Vimlesh Kumar; Dhayal, Yogpal; Saxena, Deepa; Rani, Ashu; Chandel, C P Singh; Gupta, K S

    2016-09-01

    The automobile exhausts are one of the major sources of particulate matter in urban areas and these particles are known to influence the atmospheric chemistry in a variety of ways. Because of this, the oxidation of dissolved sulfur dioxide by oxygen was studied in aqueous suspensions of particulates, obtained by scraping the particles deposited inside a diesel truck exhaust pipe (DEP). A variation in pH showed the rate to increase with increase in pH from 5.22 to about ∼6.3 and to decrease thereafter becoming very slow at pH = 8.2. In acetate-buffered medium, the reaction rate was higher than the rate in unbuffered medium at the same pH. Further, the rate was found to be higher in suspension than in the leachate under otherwise identical conditions. And, the reaction rate in the blank reaction was the slowest. This appears to be due to catalysis by leached metal ions in leachate and due to catalysis by leached metal ions and particulate surface both in suspensions. The kinetics of dissolved SO2 oxidation in acetate-buffered medium as well as in unbuffered medium at pH = 5.22 were defined by rate law: k obs  = k 0 + k cat [DEP], where k obs and k 0 are observed rate constants in the presence and the absence of DEP and k cat is the rate constant for DEP-catalyzed pathway. At pH = 8.2, the reaction rate was strongly inhibited by DEP in buffered and unbuffered media. Results suggest that the DEP would have an inhibiting effect in those areas where rainwater pH is 7 or more. These results at high pH are of particular significance to the Indian subcontinent, because of high rainwater pH. Conversely, it indicates the DEP to retard the oxidation of dissolved SO2 and control rainwater acidification.

  15. Are the clouds of Venus sulfuric acid.

    NASA Technical Reports Server (NTRS)

    Young, A. T.

    1973-01-01

    It is shown that strong aqueous sulfuric acid solutions have the right refractive index and freeze at Venusian cloud temperature, explain the dryness of the Venusian stratosphere, are consistent with some features of the Venusian IR spectrum, and do not absorb in highly reflecting areas of Venus. It is also indicated that such solutions should be produced by reactions between known atmospheric constituents and most sulfur-bearing rock at the Venusian surface temperature, and require only small amounts of sulfur consistent with its cosmic abundance and with the amounts of other volatile elements present in the atmosphere. It is believed therefore that the clouds of Venus consist of sulfuric acid solutions.

  16. Sulfuric acid as autocatalyst in the formation of sulfuric acid.

    PubMed

    Torrent-Sucarrat, Miquel; Francisco, Joseph S; Anglada, Josep M

    2012-12-26

    Sulfuric acid can act as a catalyst of its own formation. We have carried out a computational investigation on the gas-phase formation of H(2)SO(4) by hydrolysis of SO(3) involving one and two water molecules, and also in the presence of sulfuric acid and its complexes with one and two water molecules. The hydrolysis of SO(3) requires the concurrence of two water molecules, one of them acting as a catalyzer, and our results predict an important catalytic effect, ranging between 3 and 11 kcal·mol(-1) when the catalytic water molecule is substituted by a sulfuric acid molecule or one of its hydrates. In these cases, the reaction products are either bare sulfuric acid dimer or sulfuric acid dimer complexed with a water molecule. There are broad implications from these new findings. The results of the present investigation show that the catalytic effect of sulfuric acid in the SO(3) hydrolysis can be important in the Earth's stratosphere, in the heterogeneous formation of sulfuric acid and in the formation of aerosols, in H(2)SO(4) formation by aircraft engines, and also in understanding the formation of sulfuric acid in the atmosphere of Venus.

  17. Investigating connections between local-remote atmospheric variability and Greenland outlet glacier behavior

    NASA Astrophysics Data System (ADS)

    Sobolowski, Stefan; Chen, Linling; Miles, Victoria

    2016-04-01

    The outlet glaciers along the margins of the Greenland Ice Sheet (GrIS) exhibit a range of behaviors, which are crucial for understanding GrIS mass changes from a dynamical point of view. However, the drivers of this behavior are still poorly understood. Arguments (counter-arguments) have been made for a strong (weak) local oceanic influence on marine terminating outlet glaciers while decadal-scale drivers linked to fluctuations in the Ice sheet itself and the North Atlantic ocean (e.g. Atlantic Multidecadal Variability) have also been posited as drivers. Recently there have also been studies linking (e.g. seasonal to interannual) atmospheric variability, synoptic activity and the Ice Sheet variability. But these studies typically investigate atmospheric links to the large-scale behavior of the Ice Sheet itself and do not go down to the scale of the outlet glaciers. Conversely, investigations of the outlet glaciers often do not include potential links to non-local atmospheric dynamics. Here the authors attempt to bridge the gap and investigate the relationship between atmospheric variability across a range of scales and the behavior of three outlet glaciers on Greenland's southeast coast over a 33-year period (1980-2012). The glaciers - Helheim, Midgard and Fenris - are near Tasiilaq, are marine terminating and exhibit varying degree of connection to the GrIS. ERA-Interim reanalysis, sea-ice data and glacier observations are used for the investigation. Long records of mass balance are unavailable for these glaciers and front position is employed as a measure of glacier atmosphere interactions across multiple scales, as it exhibits robust relationships to atmospheric variability on time scales of seasons to many years, with the strongest relationships seen at seasonal - interannual time scales. The authors do not make the argument that front position is a suitable proxy for mass balance, only that it is indicative of the role of local and remote atmospheric

  18. Improving the electrochemical behavior of lithium-sulfur batteries through silica-coated nickel-foam cathode collector

    NASA Astrophysics Data System (ADS)

    Cho, Sung Ho; Cho, Sung Man; Bae, Ki Yoon; Kim, Byung Hyuk; Yoon, Woo Young

    2017-02-01

    A facile method that improves the initial specific capacity and capacity retention rate of lithium-sulfur (Li-S) batteries, using silica-back-coated nickel foam has been studied. A new cathode collector in which silica is back-coated onto the nickel foam is fabricated by a facile method that utilizes an ultrasonicator for reducing the electrolyte viscosity at the surface of the sulfur electrode using a polysulfide absorbent. The nickel foam provides more reaction sites than an aluminum current collector does, thus allowing the back-coated silica to absorb the polysulfides. This synergetic effect of nickel foam and silica suppresses the increasing viscosity of the electrolyte and leads to a higher initial specific capacity (1341 mAh/g) at a 0.2-C rate and a higher capacity retention rate after 150 cycles (85%), relative to pristine Li-S batteries (951 mAh/g and 79%, respectively).

  19. Corrosion inhibition and adsorption behavior of methionine on mild steel in sulfuric acid and synergistic effect of iodide ion.

    PubMed

    Oguzie, E E; Li, Y; Wang, F H

    2007-06-01

    The corrosion inhibition of mild steel in sulfuric acid by methionine (MTI) was investigated using electrochemical techniques. The effect of KI additives on corrosion inhibition efficiency was also studied. The results reveal that MTI inhibited the corrosion reaction by adsorption onto the metal/solution interface. Inhibition efficiency increased with MTI concentration and synergistically increased in the presence of KI, with an optimum [KI]/[MTI] ratio of 5/5, due to stabilization of adsorbed MTI cations as revealed by AFM surface morphological images. Potentiodynamic polarization data suggest that the compound functioned via a mixed-inhibition mechanism. This observation was further corroborated by the fit of the experimental adsorption data to the Temkin and Langmuir isotherms. The inhibition mechanism has been discussed vis-à-vis the presence of both nitrogen and sulfur atoms in the MTI molecule.

  20. Sulfur behavior in chemical looping combustion with NiO/Al{sub 2}O{sub 3} oxygen carrier

    SciTech Connect

    Shen, Laihong; Gao, Zhengping; Wu, Jiahua; Xiao, Jun

    2010-05-15

    Chemical looping combustion (CLC) is a novel technology where CO{sub 2} is inherently separated during combustion. Due to the existence of sulfur contaminants in the fossil fuels, the gaseous products of sulfur species and the interaction of sulfur contaminants with oxygen carrier are a big concern in the CLC practice. The reactivity of NiO/Al{sub 2}O{sub 3} oxygen carrier reduction with a gas mixture of CO/H{sub 2} and H{sub 2}S is investigated by means of a thermogravimetric analyzer (TGA) and Fourier Transform Infrared spectrum analyzer in this study. An X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM) are used to evaluate the phase characterization of reacted oxygen carrier, and the formation mechanisms of the gaseous products of sulfur species are elucidated in the process of chemical looping combustion with a gaseous fuel containing hydrogen sulfide. The results show that the rate of NiO reduction with H{sub 2}S is higher than the one with CO. There are only Ni and Ni{sub 3}S{sub 2} phases of nickel species in the fully reduced oxygen carrier, and no evidence for the existence of NiS or NiS{sub 2}. The formation of Ni{sub 3}S{sub 2} is completely reversible during the process of oxygen carrier redox. A liquid phase sintering on the external surface of reduced oxygen carriers is mainly attributed to the production of the low melting of Ni{sub 3}S{sub 2} in the nickel-based oxygen carrier reduction with a gaseous fuel containing H{sub 2}S. Due to the sintering of metallic nickel grains on the external surface of the reduced oxygen carrier, further reaction of the oxygen carrier with H{sub 2}S is constrained, and there is no increase of the sulfidation index of the reduced oxygen carrier with the cyclical reduction number. Also, a continuous operation with a syngas of carbon monoxide and hydrogen containing H{sub 2}S is carried out in a 1 kW{sub th} CLC prototype based on the nickel-based oxygen carrier, and

  1. (abstract) Line Mixing Behavior of Hydrogen-Broadened Ammonia Under Jovian Atmospheric Conditions

    NASA Technical Reports Server (NTRS)

    Spilker, Thomas R.

    1994-01-01

    Laboratory spectral data reported last year have been used to investigate the line mixing behavior of hydrogen-broadened ammonia inversion lines. The data show that broadening parameters appearing in the modified Ben-Reuven opacity formalism of Berge and Gulkis (1976) cannot maintain constant values over pressure ranges that include low to moderate pressures and high pressures. Also, they cannot change drastically in value, as in the Spilker (1990) revision of the Berge and Gulkis formalism. It has long been recognized that at low pressures, less than about 1 bar of a Jovian atmospheric mixture, a VVW formalism yields more accurate predictions of ammonia opacity than Ben-Reuven formalisms. At higher pressures the Ben-Reuven formalisms are more accurate. Since the Ben-Reuven lineshape collapses to a VVW lineshape in the low pressure limit, this low pressure inaccuracy of the Ben-Reuven formalisms is surprising. By incorporating various behavior, a new formalism is produced that is more accurate than previous formalisms, particularly in the critical 'transition region' from 0.5 to 2 bars, and that can be used without discontinuity from pressures of zero to hundreds of bars. The new formalism will be useful in such applications as interpretation of radio astronomical and radio occultation data on giant planet atmospheres, and radiative transfer modeling of those atmospheres.

  2. Comparison of the Reaction Behavior of Hexagonal Silicon Carbide Powder in Different Atmospheres

    NASA Astrophysics Data System (ADS)

    Wang, Enhui; Hou, Xinmei; Chen, Junhong; Chou, Kuo-Chih

    2017-07-01

    The reaction behavior of hexagonal silicon carbide (h-SiC) powder under different atmospheres including dry air, air containing 20 vol pct water vapor, and Ar containing 20 vol pct water vapor at 1373 K to 1773 K (1100 °C to 1500 °C) for 10 hours has been investigated and compared. The SiC powder exhibits good oxidation resistance up to 1373 K (1100 °C) and its reaction behavior depends on both the temperature and atmosphere. Below 1773 K (1500 °C), water vapor can promote the formation of pores and enhance the oxidation of SiC powder. However, it tends to aggravate the surface sintering and intensify the volatilization reaction at 1773 K (1500 °C). This phenomenon is further verified with the increasing water vapor content. Based on this, a gas-solid model is adopted to deal with the corresponding reaction kinetics, and especially both oxidation and volatilization reactions are considered when dealing with the reaction kinetics of SiC powder in water-containing atmospheres.

  3. Comparison of the Reaction Behavior of Hexagonal Silicon Carbide Powder in Different Atmospheres

    NASA Astrophysics Data System (ADS)

    Wang, Enhui; Hou, Xinmei; Chen, Junhong; Chou, Kuo-Chih

    2017-10-01

    The reaction behavior of hexagonal silicon carbide (h-SiC) powder under different atmospheres including dry air, air containing 20 vol pct water vapor, and Ar containing 20 vol pct water vapor at 1373 K to 1773 K (1100 °C to 1500 °C) for 10 hours has been investigated and compared. The SiC powder exhibits good oxidation resistance up to 1373 K (1100 °C) and its reaction behavior depends on both the temperature and atmosphere. Below 1773 K (1500 °C), water vapor can promote the formation of pores and enhance the oxidation of SiC powder. However, it tends to aggravate the surface sintering and intensify the volatilization reaction at 1773 K (1500 °C). This phenomenon is further verified with the increasing water vapor content. Based on this, a gas-solid model is adopted to deal with the corresponding reaction kinetics, and especially both oxidation and volatilization reactions are considered when dealing with the reaction kinetics of SiC powder in water-containing atmospheres.

  4. Atmosphere behavior in gas-closed mouse-algal systems: An experimental and modelling study

    NASA Astrophysics Data System (ADS)

    Averner, Maurice M.; Moore, Berrien; Bartholomew, Irene; Wharton, Robert

    Concepts of biologically-based regenerative life support systems anticipate the use of photosynthetic organisms for air revitalization. However, mismatches in the rates of production and uptake of oxygen or carbon dioxide between the crew and the plants will lead to an accumulation or depletion of these gases beyond tolerable limits. One method for correcting these atmospheric changes is to use physicochemical devices. This would conflict with the constraint of minimal size and weight imposed upon the successful development of a competitive bioregenerative system. An alternate control strategy is based upon reducing the gas exchange mismatch by manipulation of those environmental parameters known to affect plant or algae gas exchange ratios. We have initiated a research program using a dual approach of mathematical modelling and laboratory experimentation aimed at examining the gas exchange characteristics of artificial animal/plant systems closed to the ambient atmosphere. Our goal is to develop control techniques and management strategies for maintaining the atmospheric levels of carbon dioxide and oxygen at physiological levels. A mathematical model simulating the atmospheric behavior in these systems has been developed and an experimental gas-closed system has been constructed. These will be described and preliminary results will be presented.

  5. The impact of Mount Etna sulfur emissions on the atmospheric composition and aerosol properties in the central Mediterranean: A statistical analysis over the period 2000-2013 based on observations and Lagrangian modelling

    NASA Astrophysics Data System (ADS)

    Sellitto, Pasquale; Zanetel, Claudia; di Sarra, Alcide; Salerno, Giuseppe; Tapparo, Andrea; Meloni, Daniela; Pace, Giandomenico; Caltabiano, Tommaso; Briole, Pierre; Legras, Bernard

    2017-01-01

    The emission of gases and aerosols due to volcanic activity may impact significantly atmospheric composition, cloud occurrence and properties, and the regional and global climate. While the effects of strong explosive (stratospheric) eruptions are relatively well known, limited information on the impacts of small to moderate volcanic activities, including passive degassing, is available. In this paper, the downwind impact of Mount Etna's sulfur emissions on the central Mediterranean is investigated on a statistical basis over the period 2000-2013 using: (a) daily sulfur dioxide emission rates measured near crater at Mount Etna with ground-based ultraviolet spectrophotometers, (b) Lagrangian trajectories and simulated plume dispersion obtained with the FLEXPART (FLEXible PARTicle dispersion) model, and (c) long-term observations of column SO2 concentration and aerosol Ångström exponent α at Lampedusa (35.5° N, 12.6° E). This statistical analysis has allowed, for the first time, the characterization of decadal impact of Mount Etna's sulfur emissions on the sulfur dioxide and the aerosol microphysical/optical properties in the central Mediterranean. On average, statistically significant higher SO2 concentrations and smaller aerosol sizes are present when air masses from Mount Etna overpass Lampedusa. Despite being upwind of Lampedusa for only 5% of the time, Mount Etna is potentially responsible for up to 40% and 20% of the SO2 and α extreme values (exceedances of a fixed threshold), respectively, at this location. The most important factor determining this perturbation is the prevailing dynamics, while the magnitude of the SO2 emission rates from Mount Etna appears to be likely important only for relatively strong emissions. The observed perturbations to the aerosol size distribution are expected to produce a direct regional radiative effect in this area.

  6. Behavior of UO2 and fissium in sodium vapor atmosphere at temperatures up to 2800 C

    NASA Astrophysics Data System (ADS)

    Feuerstein, H.; Oschinski, J.

    1986-11-01

    An experimental technique was developed to study the behavior of fuel and fission products in out-of-pile tests in a sodium vapor atmosphere. Evaporation rates of UO2 were measured up to 2800 C. The evaporation is found to depend on temperature and the active surface. Evaporation restructures the surface of the samples, however no new active surface is formed; UO2 can form well shaped crystals and curious erosion products. The efficiency of the used condenser/filter lines is 99.99%. In an HCDA, all the evaporated substances condense in the sodium pool. Thermal reduction of the UO2 reduces the oxygen potential of the system. The final composition at 2500 C is UO1.95. The only influence of the sodium vapor is found for the diffusion of UO2 into the thoria of the crucible. Compared with experiments in an atmosphere of pure argon, the diffusion rate is reduced.

  7. Divergent behavior of hydrogen sulfide pools and of the sulfur metabolite lanthionine, a novel uremic toxin, in dialysis patients.

    PubMed

    Perna, Alessandra F; Di Nunzio, Annarita; Amoresano, Angela; Pane, Francesca; Fontanarosa, Carolina; Pucci, Piero; Vigorito, Carmela; Cirillo, Giovanni; Zacchia, Miriam; Trepiccione, Francesco; Ingrosso, Diego

    2016-07-01

    Dialysis patients display a high cardiovascular mortality, the causes of which are still not completely explained, but are related to uremic toxicity. Among uremic toxins, homocysteine and cysteine are both substrates of cystathionine β-synthase and cystathionine γ-lyase in hydrogen sulfide biosynthesis, leading to the formation of two sulfur metabolites, lanthionine and homolanthionine, considered stable indirect biomarkers of its production. Hydrogen sulfide is involved in the modulation of multiple pathophysiological responses. In uremia, we have demonstrated low plasma total hydrogen sulfide levels, due to reduced cystathionine γ-lyase expression. Plasma hydrogen sulfide levels were measured in hemodialysis patients and healthy controls with three different techniques in comparison, allowing to discern the different pools of this gas. The protein-bound (the one thought to be the most active) and acid-labile forms are significantly decreased, while homolanthionine, but especially lanthionine, accumulate in the blood of uremic patients. The hemodialysis regimen plays a role in determining sulfur compounds levels, and lanthionine is partially removed by a single dialysis session. Lanthionine inhibits hydrogen sulfide production in cell cultures under conditions comparable to in vivo ones. We therefore propose that lanthionine is a novel uremic toxin. The possible role of high lanthionine as a contributor to the genesis of hyperhomocysteinemia in uremia is discussed.

  8. Statistical modelling of discharge behavior of atmospheric pressure dielectric barrier discharge

    SciTech Connect

    Tay, W. H.; Kausik, S. S.; Wong, C. S. Yap, S. L.; Muniandy, S. V.

    2014-11-15

    In this work, stochastic behavior of atmospheric pressure dielectric barrier discharge (DBD) has been investigated. The experiment is performed in a DBD reactor consisting of a pair of stainless steel parallel plate electrodes powered by a 50 Hz ac high voltage source. Current pulse amplitude distributions for different space gaps and the time separation between consecutive current pulses are studied. A probability distribution function is proposed to predict the experimental distribution function for the current pulse amplitudes and the occurrence of the transition regime of the pulse distribution. Breakdown voltage at different positions on the dielectric surface is suggested to be stochastic in nature. The simulated results based on the proposed distribution function agreed well with the experimental results and able to predict the regime of transition voltage. This model would be useful for the understanding of stochastic behaviors of DBD and the design of DBD device for effective operation and applications.

  9. Sulfur concentration of martian basalts at sulfide saturation at high pressures and temperatures - Implications for deep sulfur cycle on Mars

    NASA Astrophysics Data System (ADS)

    Ding, Shuo; Dasgupta, Rajdeep; Tsuno, Kyusei

    2014-04-01

    To constrain sulfur concentration at sulfide saturation (SCSS) of martian magmas at mantle conditions, we simulated basalt-sulfide melt equilibria using two synthesized meteorite compositions, i.e., Yamato980459 and NWA2990 in both anhydrous and hydrous conditions at 1-5 GPa and 1500-1700 °C. Our experimental results show that SCSS decreases with increasing pressure and increases with increasing temperature. Based on our experimental SCSS and those from previous low-pressure experiments on high-FeO∗ martian basalts, we developed a parameterization to predict martian basalt SCSS as a function of depth, temperature, and melt composition. Our model suggests that sulfur contents as high as 3500-4300 ppm can be transferred from the martian mantle to the martian exogenic system, and sulfur-rich gases might have caused the greenhouse conditions during the late Noachian. However, modeling of the behavior of sulfur along the liquid line of descent of a primitive martian basalt suggests that a fraction of the magmatic sulfur could precipitate as sulfides in the cumulates during cooling and fractional crystallization of basaltic magmas. Furthermore, the latter case is consistent with the S concentration of martian meteorites, which reflect variable amount of trapped liquid in cumulus mineral assemblage. Furthermore, our model predicts an average S storage capacity of 5700 ppm for the martian magma ocean, whereas the same for Earth is only ∼860 ppm. Lastly, high SCSS of martian magma ocean and its inverse correlation with depth along the mantle liquidus could have triggered a sulfur pump where the post-core-formation magma ocean of Mars would gain sulfur through interaction with SO2/H2S rich nascent atmosphere.

  10. Atmosphere

    NASA Astrophysics Data System (ADS)

    Ghosh, D.; Mitra, S. K.

    2014-05-01

    This paper investigates the high-temperature corrosion behavior of microstructurally different regions of the weldment of 9 Cr-1 Mo steel used in thermal power plant boiler in SO2 + O2 environment. The weldment is produced by tungsten inert gas welding method, and the different regions of the weldment (weld metal, heat-affected zone, and base metal) are exposed in SO2 + O2 (ratio 2:1) environment at 973 K for 120 h. The reaction kinetics and corrosion growth rate of different regions of weldment in isothermal condition are evaluated. The post corroded scales of the different specimens are studied in SEM, EDS, and XRD. The results indicate that the weld metal shows higher corrosion rate followed by HAZ and base metal. The higher rate of corrosion of weldmetal is mainly attributed to the least protective inner scale of Cr2O3 with minimum Cr Content. This is due to the formation of delta ferrite, which leads to the precipitation of the Cr-based secondary phases and depletes the free Cr from the matrix. The thermal cycles during welding at high temperature are favorable for the formation of delta ferrite. On the other hand, in absence of delta ferrite, the base metal and HAZ regions of the weldment show lower corrosion rate than weld metal. The difference in corrosion rate in the three regions of the weldment is supplemented by post-corroded scale characterizations.

  11. Analysis of organic sulfur compounds in atmospheric aerosols at the HKUST supersite in Hong Kong using HR-ToF-AMS.

    PubMed

    Huang, Dan Dan; Li, Yong Jie; Lee, Berto P; Chan, Chak K

    2015-03-17

    Organic sulfur compounds have been identified in ambient secondary organic aerosols, but their contribution to organic mass is not well quantified. In this study, using a high-resolution time-of-flight aerosol mass spectrometer (AMS), concentrations of organic sulfur compounds were estimated based on the high-resolution fragmentation patterns of methanesulfonic acid (MSA), and organosulfates (OS), including alkyl, phenyl, and cycloalkyl sulfates, obtained in laboratory experiments. Mass concentrations of MSA and minimum mass concentrations of OS were determined in a field campaign conducted at a coastal site of Hong Kong in September 2011. MSA and OS together accounted for at least 5% of AMS detected organics. MSA is of marine origin with its formation dominated by local photochemical activities and enhanced by aqueous phase processing. OS concentrations are better correlated with particle liquid water content (LWC) than with particle acidity. High-molecular-weight OS were detected in the continental influenced period probably because they had grown into larger molecules during long-range transport or they were formed from large anthropogenic precursors. This study highlights the importance of both aqueous-phase processing and regional influence, i.e., different air mass origins, on organic sulfur compound formation in coastal cities like Hong Kong.

  12. The study of azaarene behavior over atmosphere of subtropical city(Keelung)

    NASA Astrophysics Data System (ADS)

    Liu, Chih Yun

    2017-04-01

    In this study, we collected the Total Suspended Particulates (TSP) from July 2014 to February 2016 in the subtropical city (Keelung), and researched azaarene behavior over atmosphere. Polycyclic Aromatic Compounds (PAHs) are ubiquitous pollutants in the environment; they have known carcinogens and/or mutagens, mainly produce from incomplete combustion. Azaarenes are polycyclic aromatic hydrocarbon derivative compounds in which a carbon atom in one of the aromatic rings is substituted by a nitrogen atom. Organism exposure to azaarenes occurs through inhalation of polluted air and by ingestion of food and/or water containing combustion products and accumulate in the body. Total azaarene concentration (16 individual compound concentration of the aggregate) is between 0.92 to 3.76 μg/m3, results showed that the concentration of azaarenes have significant seasonal variation, they have higher concentration in the cold month. In molecular weight, the highest proportion is the molecular weight equal to 143(ΣMQ) and then the molecular weight equal to 179(BAP), ΣMQ would rise from 30% 40% to 40% 50% during the cold month and warm months. Compared to ring number, 2-rings are biggest part, the smallest is 4-rings, its ratio has slight variation, but primary species is 2-rings. Emissions from transportation, local housing heating, factories burning fossil fuels and dust from Mainland south air mass are pollutant, their sources and climate conditions can affect concentration and composition of compound. There are highly significant correlation between 3-rings and 4-rings, which suggests that there are similar source strengths and transport mechanisms for these compounds. Correlation between concentration of azaarenes and ambient temperature is negative moderation, with concentration of atmospheric suspended particles is positive moderate correlation. Finally, we establish the relationship between the three parameters to predict concentration of azaarenes over atmosphere of

  13. Effects of sintering atmospheres on phase transformation, oxygen vacancy and photoabsorption behaviors of highly Fe-doped titania crystals

    NASA Astrophysics Data System (ADS)

    Wang, Xiaohuan; Shi, Zhiming; Wang, Lina

    2017-02-01

    Fe-doped TiO2 crystals were successfully prepared using a sol-gel technique in reducing and oxidizing atmospheres. The effects of sintering atmosphere on phase transformation, oxygen vacancy concentration and photoabsorption behaviors were investigated. The results indicate that upon sintering in reducing atmosphere, Ti and Fe ion valences were decreased and highly Fe ions (12 mol%) were entirely dissolved into titania crystals, increasing oxygen vacancy concentration and leading to increased photoabsorption capability. In contrast, sintering in oxidizing atmosphere causes precipitation of the Fe2O3 phase, which is detrimental to the photoabsorption capability. The best photoabsorption performance is obtained by sintering 12 mol% Fe-doped TiO2 in reducing atmosphere, resulting in an absorption edge of approximately 435 nm, which is much higher than that of undoped TiO2 in the oxidizing atmospheres with the absorption edge 352 nm.

  14. Meteoritic Sulfur Isotopic Analysis

    NASA Technical Reports Server (NTRS)

    Thiemens, Mark H.

    1996-01-01

    Funds were requested to continue our program in meteoritic sulfur isotopic analysis. We have recently detected a potential nucleosynthetic sulfur isotopic anomaly. We will search for potential carriers. The documentation of bulk systematics and the possible relation to nebular chemistry and oxygen isotopes will be explored. Analytical techniques for delta(sup 33), delta(sup 34)S, delta(sup 36)S isotopic analysis were improved. Analysis of sub milligram samples is now possible. A possible relation between sulfur isotopes and oxygen was detected, with similar group systematics noted, particularly in the case of aubrites, ureilites and entstatite chondrites. A possible nucleosynthetic excess S-33 has been noted in bulk ureilites and an oldhamite separate from Norton County. High energy proton (approximately 1 GeV) bombardments of iron foils were done to experimentally determine S-33, S-36 spallogenic yields for quantitation of isotopic measurements in iron meteorites. Techniques for measurement of mineral separates were perfected and an analysis program initiated. The systematic behavior of bulk sulfur isotopes will continue to be explored.

  15. Effect of Immersion Time and Cooling Mode on the Electrochemical Behavior of Hot-Dip Galvanized Steel in Sulfuric Acid Medium

    NASA Astrophysics Data System (ADS)

    Lekbir, Choukri; Dahoun, Nessrine; Guetitech, Asma; Hacid, Abdenour; Ziouche, Aicha; Ouaad, Kamel; Djadoun, Amar

    2017-04-01

    In this work, we investigated the influence of galvanizing immersion time and cooling modes environments on the electrochemical corrosion behavior of hot-dip galvanized steel, in 1 M sulfuric acid electrolyte at room temperature using potentiodynamic polarization technique. In addition, the evolution of thickness, structure and microstructure of zinc coatings for different immersion times and two cooling modes (air and water) is characterized, respectively, by using of Elcometer scan probe, x-ray diffraction and metallography analysis. The analysis of the behavior of steel and galvanized steel, vis-a-vis corrosion, by means of corrosion characteristic parameters as anodic (β a) and cathodic (β c) Tafel slopes, corrosion potential (E corr), corrosion current density (i corr), corrosion rate (CR) and polarization resistance (R p), reveals that the galvanized steel has anticorrosion properties much better than that of steel. More the immersion time increases, more the zinc coatings thickness increases, and more these properties become better. The comparison between the two cooling modes shows that the coatings of zinc produced by hot-dip galvanization and air-cooled provides a much better protection to steel against corrosion than those cooled by quenching in water which exhibit a brittle corrosive behavior due to the presence of cracks.

  16. TRENDS IN RURAL SULFUR CONCENTRATIONS

    EPA Science Inventory

    This paper presents an analysis of regional trends in atmospheric concentrations in sulfur dioxide (502) and particulate sulfate (50~- ) at rural monitoring sites in the Clean Air Act Status and Trends Monitoring Network (CAsTNet) from 1990 to 1999. A two-stage approach is used t...

  17. TRENDS IN RURAL SULFUR CONCENTRATIONS

    EPA Science Inventory

    This paper presents an analysis of regional trends in atmospheric concentrations in sulfur dioxide (502) and particulate sulfate (50~- ) at rural monitoring sites in the Clean Air Act Status and Trends Monitoring Network (CAsTNet) from 1990 to 1999. A two-stage approach is used t...

  18. Active microbial sulfur disproportionation in the Mesoproterozoic.

    PubMed

    Johnston, David T; Wing, Boswell A; Farquhar, James; Kaufman, Alan J; Strauss, Harald; Lyons, Timothy W; Kah, Linda C; Canfield, Donald E

    2005-12-02

    The environmental expression of sulfur compound disproportionation has been placed between 640 and 1050 million years ago (Ma) and linked to increases in atmospheric oxygen. These arguments have their basis in temporal changes in the magnitude of 34S/32S fractionations between sulfate and sulfide. Here, we present a Proterozoic seawater sulfate isotope record that includes the less abundant sulfur isotope 33S. These measurements imply that sulfur compound disproportionation was an active part of the sulfur cycle by 1300 Ma and that progressive Earth surface oxygenation may have characterized the Mesoproterozoic.

  19. An evaluation of possible mechanisms for conversion of sulfur dioxide to sulfuric acid and sulfate aerosols in the troposphere

    Treesearch

    Jack G. Calvert

    1976-01-01

    The mechanisms and rates of conversion of sulfur dioxide to sulfur trioxide, sulfuric acid, and other "sulfate" aerosol precursors are considered in view of current knowledge related to atmospheric reactions and chemical kinetics. Several heterogeneous pathways exist for SO2 oxidation promoted on solid catalyst particles and in aqueous...

  20. Bisulfite and sulfite as derivatives of sulfur dioxide alters biomechanical behaviors of airway smooth muscle cells in culture.

    PubMed

    Song, Aijing; Lin, Feng; Li, Jianming; Liao, Qingfeng; Liu, Enmei; Jiang, Xuemei; Deng, Linhong

    2014-02-01

    Sulfur dioxide (SO2) is a common air pollutant that triggers asthmatic symptoms, but its toxicological mechanisms are not fully understood. Specifically, it is unclear how SO2 in vivo affects airway smooth muscle (ASM) cells of which the mechanics is known to ultimately mediate airway hyperresponsiveness (AHR) - a hallmark feature of asthma. To this end, we investigated the effects of bisulfite/sulfite (1:3 M/M in neutral fluid to simulate the in vivo derivatives of inhaled SO2 in the airways), on the viability, migration, stiffness and contractility of ASM cells cultured in vitro. The results showed that bisulfite/sulfite consistently increased viability, migration, F-actin intensity and stiffness of ASM cells in similar fashion as concentration increasing from 10(-4) to 10(-1) mmol/L. However, bisulfite/sulfite increased the ASM cell contractility induced by KCl only at the concentration between 10(-4) and 10(-3) mmol/L (p < 0.05), while having no consistent effect on that induced by histamine. At the concentration of 10(0) mmol/L, bisulfite/sulfite became acutely toxic to the ASM cells. Taken together, the data suggest that SO2 derivatives at low levels in vivo may directly increase the mass, stiffness and contractility of ASM cells, which may help understand the mechanism in which specific air pollutants contribute in vivo to the pathogenesis of asthma.

  1. Mass-independent sulfur of inclusions in diamond and sulfur recycling on early Earth.

    PubMed

    Farquhar, J; Wing, B A; McKeegan, K D; Harris, J W; Cartigny, P; Thiemens, M H

    2002-12-20

    Populations of sulfide inclusions in diamonds from the Orapa kimberlite pipe in the Kaapvaal-Zimbabwe craton, Botswana, preserve mass-independent sulfur isotope fractionations. The data indicate that material was transferred from the atmosphere to the mantle in the Archean. The data also imply that sulfur is not well mixed in the diamond source regions, allowing for reconstruction of the Archean sulfur cycle and possibly offering insight into the nature of mantle convection through time.

  2. Advanced Sulfur Control Processing

    SciTech Connect

    Gangwal, S.K.; Portzer, J.W.; Turk, B.S.; Gupta, R.

    1996-12-31

    The primary objective of this project is to determine the feasibility of an alternate concept for the regeneration of high temperature desulfurization sorbents in which elemental sulfur, instead of SO{sub 2}, is produced. If successful, this concept will eliminate or alleviate problems caused by the highly exothermic nature of the regeneration reaction, the tendency for metal sulfate formation, and the need to treat the regeneration off-gas to prevent atmospheric SO{sub 2}, emissions. Iron and cerium-based sorbents were chosen on the basis of thermodynamic analysis to determine the feasibility of elemental sulfur production. The ability of both to remove H{sub 2}S during the sulfidation phase is less than that of zinc-based sorbents, and a two-stage desulfurization process will likely be required. Preliminary experimental work used electrobalance reactors to compare the relative rates of reaction of O{sub 2} and H{sub 2}O with FeS. More detailed studies of the regeneration of FeS as well as the sulfidation of CeO{sub 2} and regeneration of Ce{sub 2}O{sub 2}S are being carried out in a laboratory-scale fixed-bed reactor equipped with a unique analytical system which permits semi-continuous analysis of the distribution of elemental sulfur, H{sub 2}S, and SO{sub 2} in the reaction product gas.

  3. Isothermal Oxidation Behavior of Supersonic Atmospheric Plasma-Sprayed Thermal Barrier Coating System

    NASA Astrophysics Data System (ADS)

    Bai, Yu; Ding, Chunhua; Li, Hongqiang; Han, Zhihai; Ding, Bingjun; Wang, Tiejun; Yu, Lie

    2013-10-01

    In this work, Y2O3 stabilized zirconia-based thermal barrier coatings (TBCs) were deposited by conventional atmospheric plasma spraying (APS) and high efficiency supersonic atmospheric plasma spraying (SAPS), respectively. The effect of Al2O3 layer stability on the isothermal growth behavior of thermally grown oxides (TGOs) was studied. The results revealed that the Al2O3 layer experienced a three-stage change process, i.e., (1) instantaneous growth stage, (2) steady-state growth stage, and (3) depletion stage. The thickness of Al2O3 scale was proved to be an important factor for the growth rate of TGOs. The SAPS-TBCs exhibited a higher Al2O3 stability and better oxidation resistance as compared with the APS-TBCs. Additionally, it was found that inner oxides, especially nucleated on the top of the crest, continually grew and swallowed the previously formed Al2O3 layer, leading to the granulation and disappearance of continuous Al2O3 scale, which was finally replaced by the mixed oxides and spinel.

  4. Initial corrosion behavior of a copper-clad plate in typical outdoor atmospheric environments

    NASA Astrophysics Data System (ADS)

    Yi, Pan; Xiao, Kui; Ding, Kangkang; Yan, Lidan; Dong, Chaofang; Li, Xiaogang

    2016-01-01

    A copper-clad printed circuit board (PCB-Cu) was subjected to long-term exposure test under typical Chinese atmospheric environments to study corrosion failure mechanisms. The corrosion behavior was investigated by analyzing electrochemical impedance, scanning Kelvin probes, stereo and scanning electron microscopes, and energy-dispersive spectra. Results showed that the initial surface potential was unevenly distributed. The outdoor PCB-Cu samples suffered severe corrosion caused by dust particles, contaminated media, and microorganisms after long-term atmospheric exposure. The initial localized corrosion was exacerbated and progressed to general corrosion for samples in Turpan, Beijing, and Wuhan under prolonged exposure, whereas PCB-Cu in Xishuangbanna was only slightly corroded. The tendency for electrochemical migration (ECM) of PCB-Cu was relatively low when applied with a bias voltage of 12 V. ECM was only observed in the PCB-Cu samples in Beijing. Contaminated medium and high humidity synergistically affected ECM corrosion in PCB-Cu materials. [Figure not available: see fulltext.

  5. [Comparisons of sulfur contents and isotopes between mosses and surface soils in Jiangxi Province].

    PubMed

    Li, Nan; Xiao, Hua-Yun; Chen, Yong-Zhong; Zhou, Dan; Luo, Li; Wu, Dai-She

    2013-10-01

    In order to study the influence of atmospheric sulfur on soil sulfur, the forest surface soil samples and moss samples were collected in north areas of Jiangxi province. Contents and isotopes of sulfur in different forms (total sulfur, water-soluble sulfur, absorbed sulfur and organic sulfur) were determined. The average sulfur content of mosses was 0. 34% +/- 0. 20%. All of the delta34S values except at Fengcheng (-3. 31 per thousand) were positive, the average was 5.64 per thousand +/- 2. 23 per thousand. The average contents of soil total sulfur were between 189.0 mg.kg-1 and 793.5 mg.kg-1. The organic sulfur was the main sulfur form in surface soils and the contents of water-soluble sulfur were the lowest. The delta34S values of total sulfur were in the range of 4. 45 per thousand +/-10. 28 per thousand. The highest soil delta34S values were determined for organic sulfur and the delta34S values of water-soluble and absorbed sulfur were similar. The contents of soil total sulfur were much lower than those of the mosses. Except for organic sulfur (R = 0. 50, P >0. 05) , the delta34S values of total sulfur, water-soluble sulfur and absorbed sulfur were all significantly correlated with those of moss sulfur (R >0.7, P <0. 01). These results indicated that atmospheric sulfur directly affected the total sulfur, water-soluble sulfur and absorbed sulfur, but not the organic sulfur.

  6. Application of electrochemical investigation methods in high sulfur coal flotation

    SciTech Connect

    Zhu Hong; Ou Zeshen; Shi Xiuping; Shen Yanchun

    1997-12-31

    More and more attention has been paid to sulfur dioxide pollution caused by coal burning. It is important that sulfur in coal should be reduced before combustion. Flotation is an important method for the removal of pyrite from high sulfur coal. Many chemicals have been tested as a pyrite depressant. In recent years many tests have been done in the laboratory on the flotation behavior of pyrite, and the results have confirmed that the hydrophobicity of the pyrite surface is dependent on the redox potential of the pulp. The mechanism and the reaction products on the pyrite surface are discussed under various conditions. And pyrite depression in coal flotation by electrochemical control are further studied on the basis of what has been achieved. There are two methods in electrochemical control: chemical reagent and control potential by electrochemical instrument (``control potential`` for short). This paper studies pyrite depression in coal flotation by electrochemical control. The influence of sulfur removal in coal flotation has been probed by chemical reagent and control potential. Experiment shows that at low pulp potential the pyrite flotation is generally suppressed. This is new, efficient and simple method of pyrite depression without environmental pollution. The following main conclusions can be drawn from this study: (1) The control of pulp potential can regulate and lead to electrochemical reaction of the hydrophobicity or hydrophilicity on the pyrite surface; and (2) The characteristics of electrochemical methods are normal atmospheric temperature, simple technological process and strong selection.

  7. Theoretical studies of the marine sulfur cycle

    NASA Technical Reports Server (NTRS)

    Toon, Owen B.; Kasting, James B.; Liu, May S.

    1985-01-01

    Several reduced sulfur compounds are produced by marine organisms and then enter the atmosphere, where they are oxidized and ultimately returned to the ocean or the land. The oceanic dimethyl sulfide (DMS) flux, in particular, represents a significant fraction of the annual global sulfur input to the atmosphere. In the atmosphere, this gas is converted to sulfur dioxide (SO2), methane sulfonic acid, and other organic acids which are relatively stable and about which little is known. SO2 is a short lived gas which, in turn, is converted to sulfuric acid and other sulfate compounds which contribute significantly to acid rain. Because of the complexity of the sulfur system, it is not well understood even in the unperturbed atmosphere. However, a number of new observations and experiments have led to a significant increase in the understanding of this system. A number of one dimensional model experiments were conducted on the gas phase part of the marine sulfur cycle. The results indicate the measured concentration of DMS and the amplitude of its diurnal cycle are in agreement with estimates of its global flux. It was also found that DMS can make a large contribution to the background SO2 concentration in the free troposphere. Estimates of CS2 concentrations in the atmosphere are inconsistent with estimated fluxes; however, measured reaction rates are consistent with the observed steep tropospheric gradient in CS2. Observations of CS2 are extremely sparse. Further study is planned.

  8. Biogeochemistry of sulfur in the Vienna Woods: Study of sulfur stable isotope ratios by MC-ICP-MS as indicator of biogeochemical S cycling

    NASA Astrophysics Data System (ADS)

    Hanousek, Ondrej; Berger, Torsten W.; Prohaska, Thomas

    2014-05-01

    Sulfur entering forest ecosystems originates mainly from combustion of fossil fuels. This source of sulfur has been strongly (by more than 95 %) reduced in last decades and recently, higher sulfur output (in soil solution or stream water) than sulfur input (in rain water) in an ecosystem was registered in many monitored forest ecosystems. This unbalance may be caused by weathering of sulfur-bearing rocks, desorption of sulfur adsorbed in soil in the past or (re)mineralization of organic sulfur compounds. This 'negative' balance leads to mobilization of base cations along with SO42- and as such to an acidification of soils. As hypothesis, δ34S/32S depletion in stream water will be observed if a considerable proportion of atmospherically deposited sulfate is cycled through the organic S pool. Rain water and soil solutions samples were collected for this study at 3 sites (beech stands) in the Vienna Woods, Austria twice a month from May 2010 to April 2012. Due to the expected sulfate concentration gradient with respect to the distance from a tree, sampling was carried out at 5 intervals from a stem. The sulfur concentration in the samples was determined by ion chromatography. Sulfur isotope ratios (δ34S/32SV CDT) were analyzed by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in edge-resolution mode. The method was validated using IAEA-S-1 and IAEA-S-2 isotopic certified reference materials. The combined standard uncertainty of the measurement (uc = 0.10 %, k = 1) proves the suitability of the developed method. The concentration of sulfur in rain water showed expected behavior, with a seasonal maximum in winter months, in contrast to the corresponding δ34S/32SV CDT isotope ratios, where no or low seasonal trends were observed. The sulfur isotope ratios in soil solution samples show a dependence on the distance from a tree stem and the sampling depth with lower δ34S/32SV CDT ratios as compared to the precipitation. The measured isotopic

  9. Laboratory measurements of the microwave and millimeter-wave opacity of gaseous sulfur dioxide (SO2) under simulated conditions for the Venus atmosphere

    NASA Technical Reports Server (NTRS)

    Fahd, Antoine K.; Steffes, Paul G.

    1992-01-01

    Laboratory measurements have been conducted of the opacity of gaseous SO2 in a CO2 atmosphere at 12.3 cm, 1.32 cm, and 0.32 cm, with a view to the effects of this gas on the mm-wave emission of the Venus atmosphere. Close agreement is noted between the results obtained and the absorptivity predicted from a Van Vleck-Weisskopf formalism at the two shortest wavelengths, but not at the longest. These results have been incorporated into a radiative transfer model in order to infer an abundance profile for gaseous SO2 in Venus' middle atmosphere, and are also used to ascertain the effects of a SO2/CO2 gaseous mixture on the mm-wavelength spectrum of Venus.

  10. Laboratory measurements of the microwave opacity and vapor pressure of sulfuric acid vapor under simulated conditions for the middle atmosphere of Venus

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.

    1985-01-01

    Microwave absorption measurements at wavelengths of 13.4 and 3.6 cm were made in gaseous H2SO4 in a CO2 atmosphere under simulated conditions for the Venus middle atmosphere. The results suggest that abundances of gaseous H2SO4 on the order of 15-30 ppm could account for the absorption observed by radio occultation measurements at these wavelengths. They also imply that such abundances would correspond to saturation vapor pressure existing at or above the 46-48-km range, which correlates with the observed cloud base.

  11. Optimizing stratospheric sulfur geoengineering by seasonally changing sulfur injections

    NASA Astrophysics Data System (ADS)

    Laakso, Anton; Partanen, Antti-Ilari; Kokkola, Harri; Lehtinen, Kari; Korhonen, Hannele

    2015-04-01

    Solar radiation management (SRM) by stratospheric sulfur injection has been shown to have potential in counteracting global warming if reducing of greenhouse gases has not been achieved fast enough and if climate warming will continue. Injecting large amounts of sulfate particles to the stratosphere would increase the reflectivity of the atmosphere and less sunlight would reach the surface. However, the effectivity (per injected sulphur mass unit) of this kind of geoengineering would decrease when amount of injected sulfur is increased. When sulfur concentration increases, stratospheric particles would grow to larger sizes which have larger gravitational settling velocity and which do not reflect radiation as efficiently as smaller particles. In many previous studies, sulfur has been assumed to be injected along the equator where yearly mean solar intensity is the highest and from where sulfur is spread equally to both hemispheres. However, the solar intensity will change locally during the year and sulfate has been assumed to be injected and spread to the hemisphere also during winter time, when the solar intensity is low. Thus sulfate injection could be expected to be more effective, if sulfur injection area is changed seasonally. Here we study effects of the different SRM injection scenarios by using two versions of the MPI climate models. First, aerosol spatial and temporal distributions as well as the resulting radiative properties from the SRM are defined by using the global aerosol-climate model ECHAM6.1-HAM2.2-SALSA. After that, the global and regional climate effects from different injection scenarios are predicted by using the Max Planck Institute's Earth System Model (MPI-ESM). We carried out simulations, where 8 Tg of sulfur is injected as SO2 to the stratosphere at height of 20-22 km in an area ranging over a 20 degree wide latitude band. Results show that changing the sulfur injection area seasonally would lead to similar global mean shortwave

  12. Uses of lunar sulfur

    NASA Technical Reports Server (NTRS)

    Vaniman, D.; Pettit, D.; Heiken, G.

    1992-01-01

    Sulfur and sulfur compounds have a wide range of applications for their fluid, electrical, chemical, and biochemical properties. Although known abundances on the Moon are limited (approximately 0.1 percent in mare soils), sulfur is relatively extractable by heating. Coproduction of sulfur during oxygen extraction from ilmenite-rich mare soils could yield sulfur in masses up to 10 percent of the mass of oxygen produced. Sulfur deserves serious consideration as a lunar resource.

  13. Uses of lunar sulfur

    SciTech Connect

    Vaniman, D.T.; Pettit, D.R.; Heiken, G.

    1988-01-01

    Sulfur and sulfur compounds have a wide range of applications for their fluid, electrical, chemical and biochemical properties. Although low in abundance on the Moon (/approximately/0.1% in mare soils), sulfur is surface-correlated and relatively extractable. Co-production of sulfur during oxygen extraction from ilmenite-rich soils could yield sulfur in masses up to 10% of the mass of oxygen produced. Sulfur deserves serious consideration as a lunar resource. 29 refs., 3 figs.

  14. Thermal infrared properties of the Martian atmosphere. I - Global behavior at 7, 9, 11, and 20 microns

    NASA Technical Reports Server (NTRS)

    Martin, T. Z.; Peterfreund, A. R.; Miner, E. D.; Kieffer, H. H.; Hunt, G. E.

    1979-01-01

    Infrared observations of Mars by the Viking infrared thermal mapper (IRTM) are presented for conditions of both a relatively clear and a dust-laden atmosphere. The 7-, 9-, 11-, and 20-micron bands of the IRTM respond differently to radiation emitted through and by a dusty atmosphere, permitting characterization of the global atmospheric state, monitoring of secular changes, and derivation of optical depth information. Surface temperature behavior is found to be greatly modified by the diminution of insolation and thermal blanketing resulting from global dust storms. Brightness temperature at 7 microns is employed to estimate surface temperatures in the presence of dust absorption. The difference (T7) is indicative of airborne dust when thermal contrast exists between the surface and atmosphere. The diurnal behavior of T7-T9 reveals changes in the contrast; the sign of the differential reverses as the surface, warmer than the atmosphere in daytime, becomes cooler than the atmosphere at night. IRTM observations of local areas at varying emission angle yield optical depths indicative of global trends. Two global dust storms in 1977 produced large optical depth changes: at 9 microns the optical depth became as large as 2.0.

  15. Ultrafine aerosol size distributions and sulfuric acid vapor pressures: Implications for new particle formation in the atmosphere. Year 2 progress report

    SciTech Connect

    McMurry, P.H.

    1993-07-01

    This project has two components: (1) measurement of H{sub 2}SO{sub 4} vapor pressures in air under temperature/relative humidity conditions similar to atmospheric, and (2) measurement of ultrafine aerosol size distributions. During Year 2, more effort was put on size distribution measurements. 4 figs.

  16. Reliability of Undergraduate Student in a Research on the Relations between Behavior and Days of the Week or Atmospheric Conditions.

    ERIC Educational Resources Information Center

    Vachon, Jean

    The influence of atmospheric conditions and the day of the week on school children's behavior was investigated by undergraduates. The college students were told either that their participation in the research was compulsory and would be graded, or that their participation was voluntary and ungraded. Fifty teachers observed their pupils' behavior…

  17. Reliability of Undergraduate Student in a Research on the Relations between Behavior and Days of the Week or Atmospheric Conditions.

    ERIC Educational Resources Information Center

    Vachon, Jean

    The influence of atmospheric conditions and the day of the week on school children's behavior was investigated by undergraduates. The college students were told either that their participation in the research was compulsory and would be graded, or that their participation was voluntary and ungraded. Fifty teachers observed their pupils' behavior…

  18. Linking neutral and charged sulfuric acid-ammonia and sulfuric acid-dimethylamine clusters

    NASA Astrophysics Data System (ADS)

    Ortega, Ismael K.; Kupiainen, Oona; Olenius, Tinja; Loukonen, Ville; Kurtén, Theo; Vehkamäki, Hanna

    2013-05-01

    We have used a quantum chemical method to calculate the formation free energies of negatively charged sulfuric acid - ammonia and sulfuric acid - dimethylamine clusters. Using the calculated formation free energies we have estimated the evaporation rates of the clusters. We have compared the evaporation rate of the charged clusters with the corresponding neutral clusters. We found that, although small clusters of sulfuric acid with ammonia and dimethylamine are stable and should be present in the atmosphere, they can not be detected using mass spectroscopy techniques. Charging the cluster will result in the fast evaporation of the base molecules, and they will be detected as pure sulfuric acid cluster.

  19. Effects of sulfur impurity on the scale adhesion behavior of a desulfurized Ni-based superalloy aluminized by chemical vapor deposition

    SciTech Connect

    Lee, W.Y.; Wright, I.G.; Pint, B.A.; Liwa, P.K.

    1998-03-01

    The surface of a single-crystal Ni-based superalloy, which contained a bulk sulfur content of {approximately} 0.4 ppmw, was aluminized in a hot-wall chemical vapor deposition (CVD) reactor, using AlCl{sub 3} and H{sub 2} as gaseous precursors, at 1,100 C. The chemical composition and microstructure of the resulting aluminide coating were characterized with particular emphasis on sulfur incorporation as an impurity during aluminizing. Depth profiling by glow-discharge mass spectroscopy (GDMS) was used as a qualitative means of assessing the level of sulfur in the coating structure. Sulfur contamination, which was initially observed at the coating surface and the substrate-coating interface, could be reduced by some minor reactor modifications. With the reduced sulfur content, scale adhesion on the surface of the aluminide grains of the coating was significantly improved during cyclic oxidation, whereas scale spallation at the coating`s grain boundaries became more apparent.

  20. Spectral studies on sulfur poisoning of Pd/Mg6Ni by NEXAFS and XPS

    NASA Astrophysics Data System (ADS)

    Yagi, S.; Nambu, M.; Tsukada, C.; Ogawa, S.; Kutluk, G.; Namatame, H.; Taniguchi, M.

    2013-02-01

    We have studied on the hydrogen storage materials based on Mg-Ni alloy and fabricated the sample constructed with the Pd thin layer (TL) on Mg6Ni alloy substrate. The adsorption behavior of the dimethyl disulfide (DMS) molecules on the sample has been measured to reveal the sulfur poisoning of the Pd TL/Mg6Ni by means of XPS and Sulfur K-edge NEXAFS techniques. The chemisorbed DMS, methanethiolate (MT) and atomic S have been observed on the surface. Especially, it is clear that some atomic S has been oxidized by air and detected the adsorbate of the SO32- and SO42- species. During exposure to the atmosphere, most of the adsorbed DMS and MT adsorbates desorb from the Pd TL surface. We thus conclude the Pd TL might be able to prevent the hydrogen storage materials from the sulfur poisoning.

  1. Influences of temperature, H2SO4 concentration and Sn content on corrosion behaviors of PbSn alloy in sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Li, D. G.; Chen, D. R.; Wang, J. D.; Chen, H. S.

    2011-10-01

    The influences of temperature, H2SO4 concentration and Sn content on corrosion behaviors of PbSn alloys in sulfuric acid solution were investigated by potentiodynamic curve, cyclic voltammetry (CV), linear sweeping voltage (LSV), electrochemical impedance spectra (EIS), a.c. voltammetry (ACV) and Mott-Schottky analysis. The microstructure of the corrosion layer on PbSn alloy was analyzed by scanning electron microscopy (SEM). The results showed that the corrosion resistance of PbSn alloy increased with ascending Sn content and H2SO4 concentration, the increment of temperature can decrease the corrosion resistance of PbSn alloy in H2SO4 solution. The conductivity of the anodic film on PbSn alloy was enhanced with increasing temperature, ascending Sn content and descending H2SO4 concentration. SEM result revealed that the corrosion film after cyclic voltammetry was consisted of tetragonal crystal, the porosity enlarged with decreasing temperature, Sn content and H2SO4 concentration.

  2. Sulfuric acid-sulfur heat storage cycle

    DOEpatents

    Norman, John H.

    1983-12-20

    A method of storing heat is provided utilizing a chemical cycle which interconverts sulfuric acid and sulfur. The method can be used to levelize the energy obtained from intermittent heat sources, such as solar collectors. Dilute sulfuric acid is concentrated by evaporation of water, and the concentrated sulfuric acid is boiled and decomposed using intense heat from the heat source, forming sulfur dioxide and oxygen. The sulfur dioxide is reacted with water in a disproportionation reaction yielding dilute sulfuric acid, which is recycled, and elemental sulfur. The sulfur has substantial potential chemical energy and represents the storage of a significant portion of the energy obtained from the heat source. The sulfur is burned whenever required to release the stored energy. A particularly advantageous use of the heat storage method is in conjunction with a solar-powered facility which uses the Bunsen reaction in a water-splitting process. The energy storage method is used to levelize the availability of solar energy while some of the sulfur dioxide produced in the heat storage reactions is converted to sulfuric acid in the Bunsen reaction.

  3. Does low-frequency atmospheric variability exhibit regime-like behavior?

    NASA Astrophysics Data System (ADS)

    Wallace, John M.; Cheng, Xinhua; Sun, Dezheng

    1991-09-01

    If the general circulation exhibits nonlinear, regime-like behavior, it should be reflected in the frequency distributions of the state of the atmospheric in phase space either in the form of bi- (or multi) modality or skewness. In order to determine whether the Northern Hemisphere winter circulation exhibits these characteristics, we examine frequency distributions of (1) the inner product or spatial covariance (2) the (spatial) "anomaly correlation", and (3) the root mean squared difference or "distance" between each map and each other map in phase space. Our distributions are based on a sample of 702 10-day lowpass filtered, hemispheric 500mb height anomaly maps (18 maps at 5-day intervals for the equivalent of 39 winter seasons). Excluding pairs of maps from the same winter season, the sample size for the distributions is 240,156. All the frequency distributions of (1) and (2) for the hemispheric maps exhibit a close fit to the corresponding randomly generated distributions based on 20 spatial degrees of freedom. There is no evidence of bimodality. However, the numbers of large positive spatial covariances and anomaly correlations greatly exceed the numbers of their counterparts in the negative tails of the frequency distributions (i.e. "analogues" outnumber "antilogues" of comparable quality). Using a simple form of cluster analysis we show that three rather distinctive blocking patterns account for a disproportionate share of the largest positive values in the frequency distributions. The asymmetries in our frequency distributions may be a reflection of regime-like behavior, but it is also conceivable that they could be the signature of more subtle forms of nonlinearity in the low frequency dynamics.

  4. Organic Sulfur Gas Production in Sulfidic Caves

    NASA Astrophysics Data System (ADS)

    Stern, L. A.; Engel, A. S.; Bennett, P. C.

    2001-12-01

    Lower Kane Cave, Big Horn Basin, WY, permits access to an environment where anaerobic sulfide-rich groundwater meets the aerobic vadose zone. At this interface microorganisms thrive on diverse metabolic pathways including autotrophic sulfur oxidation, sulfate reduction, and aerobic heterotrophy. Springs introduce groundwater rich in H2S to the cave where it both degasses into the cave atmosphere and is used by chemautotrophic sulfur oxidizing bacteria in the cave spring and stream habitat. The cave atmosphere in the immediate vicinity of the springs has elevated levels of CO2, H2S and methane, mirroring the higher concentration of H2S and methane in the spring water. The high CO2 concentrations are attenuated toward the two main sources of fresh air, the cave entrance and breathing holes at the rear of the cave. Conventional toxic gas monitors permit estimations of H2S concentrations, but they have severe cross sensitivity with other reduced sulfur gases, and thus are inadequate for characterization of sulfur cave gases. However employment of a field-based GC revealed elevated concentrations of carbonyl sulfide in cave atmosphere. Cultures of microorganisms collected from the cave optimized for enriching fermenters and autotrophic and heterophic sulfate reducing bacteria each produced carbonyl sulfide suggesting a biogenic in origin of the COS in addition to H2S. Enrichment cultures also produced methanethiol (methyl mercaptan) and an additional as yet undetermined volatile organic sulfur compound. In culture, the organo-sulfur compounds were less abundant than H2S, whereas in the cave atmosphere the organo-sulfur compounds were the dominant sulfur gases. Thus, these organo-sulfur gases may prove to be important sources of both reduced sulfur and organic carbon to microorganisms living on the cave wall in a subaerial habitat. Moreover groundwater has not yet been recognized as a source of sulfur gases to the atmosphere, but with the abundance of sulfidic

  5. Oxidation Behavior of Titanium Carbonitride Coating Deposited by Atmospheric Plasma Spray Synthesis

    NASA Astrophysics Data System (ADS)

    Zhu, Lin; He, Jining; Yan, Dianran; Liao, Hanlin; Zhang, Nannan

    2017-08-01

    Abstract: As a high-hardness and anti-frictional material, titanium carbonitride (TiCN) thick coatings or thin films are increasingly being used in many industrial fields. In the present study, TiCN coatings were obtained by atmospheric plasma spray synthesis or reactive plasma spray. In order to promote the reaction between the Ti particles and reactive gases, a home-made gas tunnel was mounted on a conventional plasma gun to perform the spray process. The oxidation behavior of the TiCN coatings under different temperatures in static air was carefully investigated. As a result, when the temperature was over 700 °C, the coatings suffered from serious oxidation, and finally they were entirely oxidized to the TiO2 phase at 1100 °C. The principal oxidation mechanism was clarified, indicating that the oxygen can permeate into the defects and react with TiCN at high temperatures. In addition, concerning the use of a TiCN coating in high-temperature conditions, the microhardness of the oxidized coatings at different treatment temperatures was also evaluated.

  6. Oxidation Behavior of Titanium Carbonitride Coating Deposited by Atmospheric Plasma Spray Synthesis

    NASA Astrophysics Data System (ADS)

    Zhu, Lin; He, Jining; Yan, Dianran; Liao, Hanlin; Zhang, Nannan

    2017-10-01

    As a high-hardness and anti-frictional material, titanium carbonitride (TiCN) thick coatings or thin films are increasingly being used in many industrial fields. In the present study, TiCN coatings were obtained by atmospheric plasma spray synthesis or reactive plasma spray. In order to promote the reaction between the Ti particles and reactive gases, a home-made gas tunnel was mounted on a conventional plasma gun to perform the spray process. The oxidation behavior of the TiCN coatings under different temperatures in static air was carefully investigated. As a result, when the temperature was over 700 °C, the coatings suffered from serious oxidation, and finally they were entirely oxidized to the TiO2 phase at 1100 °C. The principal oxidation mechanism was clarified, indicating that the oxygen can permeate into the defects and react with TiCN at high temperatures. In addition, concerning the use of a TiCN coating in high-temperature conditions, the microhardness of the oxidized coatings at different treatment temperatures was also evaluated.

  7. Parametric behaviors of CLUBB in simulations of low clouds in the Community Atmosphere Model (CAM)

    DOE PAGES

    Guo, Zhun; Wang, Minghuai; Qian, Yun; ...

    2015-07-03

    In this study, we investigate the sensitivity of simulated low clouds to 14 selected tunable parameters of Cloud Layers Unified By Binormals (CLUBB), a higher order closure (HOC) scheme, and 4 parameters of the Zhang-McFarlane (ZM) deep convection scheme in the Community Atmosphere Model version 5 (CAM5). A quasi-Monte Carlo (QMC) sampling approach is adopted to effectively explore the high-dimensional parameter space and a generalized linear model is applied to study the responses of simulated cloud fields to tunable parameters. Our results show that the variance in simulated low-cloud properties (cloud fraction and liquid water path) can be explained bymore » the selected tunable parameters in two different ways: macrophysics itself and its interaction with microphysics. First, the parameters related to dynamic and thermodynamic turbulent structure and double Gaussians closure are found to be the most influential parameters for simulating low clouds. The spatial distributions of the parameter contributions show clear cloud-regime dependence. Second, because of the coupling between cloud macrophysics and cloud microphysics, the coefficient of the dissipation term in the total water variance equation is influential. This parameter affects the variance of in-cloud cloud water, which further influences microphysical process rates, such as autoconversion, and eventually low-cloud fraction. Furthermore, this study improves understanding of HOC behavior associated with parameter uncertainties and provides valuable insights for the interaction of macrophysics and microphysics.« less

  8. Measuring and modeling the low-frequency behavior of atmospheric distortion

    NASA Astrophysics Data System (ADS)

    McGaughey, Donald R.; Aitken, George J.

    2000-07-01

    The low-frequency behavior of atmospherically distorted wavefronts is not accurately known at this time. It is expected that the phase delays will be a zero mean random process. A new zero-low-frequency model of spatial PSD of the phase distortions is presented in this paper. This model has a low frequency, called the roll-over frequency, for which the PSD starts to approach zero as the frequency decreases and approaches zero. This roll-over frequency is proportional to the outer-scale of turbulence. To verify the zero-low- frequency model, wavefront slope data was analyzed from the GSM experiment with a nonlinear modelling technique called Robust Orthogonal Search (ROS). One property of ROS is that it can detect frequency components at frequencies lower than the resolution of the discrete Fourier transform. This investigation consistently indicates a lowest frequency in the data for which any lower frequency components have lower power. This results supports the low-frequency model which rolls over and approaches zero for low spatial frequencies.

  9. Atomic oxygen behavior at downstream of AC excited atmospheric pressure He plasma jet

    NASA Astrophysics Data System (ADS)

    Takeda, Keigo; Ishikawa, Kenji; Tanaka, Hiromasa; Sekine, Makoto; Hori, Masaru

    2016-09-01

    Applications of atmospheric pressure plasma jets (APPJ) have been investigated in the plasma medical fields such as cancer therapy, blood coagulation, etc. Reactive species generated by the plasma jet interacts with the biological surface. Therefore, the issue attracts much attentions to investigate the plasma effects on targets. In our group, a spot-size AC excited He APPJ have been used for the plasma medicine. From diagnostics of the APPJ using optical emission spectroscopy, the gas temperature and the electron density was estimated to be 299 K and 3.4 ×1015 cm-3. The AC excited He APPJ which affords high density plasma at room temperature is considered to be a powerful tool for the medical applications. In this study, by using vacuum ultraviolet absorption spectroscopy, the density of atomic oxygen on a floating copper as a target irradiated by the He APPJ was measured as a function of the distance between the plasma source and the copper wire. The measured density became a maximum value around 8 ×1013 cm-3 at 12 mm distance, and then decreased over the distance. It is considered that the behavior was due to the changes in the plasma density on the copper wire and influence of ambient air.

  10. Parametric behaviors of CLUBB in simulations of low clouds in the Community Atmosphere Model (CAM)

    SciTech Connect

    Guo, Zhun; Wang, Minghuai; Qian, Yun; Larson, Vincent E.; Ghan, Steven; Ovchinnikov, Mikhail; A. Bogenschutz, Peter; Gettelman, Andrew; Zhou, Tianjun

    2015-07-03

    In this study, we investigate the sensitivity of simulated low clouds to 14 selected tunable parameters of Cloud Layers Unified By Binormals (CLUBB), a higher order closure (HOC) scheme, and 4 parameters of the Zhang-McFarlane (ZM) deep convection scheme in the Community Atmosphere Model version 5 (CAM5). A quasi-Monte Carlo (QMC) sampling approach is adopted to effectively explore the high-dimensional parameter space and a generalized linear model is applied to study the responses of simulated cloud fields to tunable parameters. Our results show that the variance in simulated low-cloud properties (cloud fraction and liquid water path) can be explained by the selected tunable parameters in two different ways: macrophysics itself and its interaction with microphysics. First, the parameters related to dynamic and thermodynamic turbulent structure and double Gaussians closure are found to be the most influential parameters for simulating low clouds. The spatial distributions of the parameter contributions show clear cloud-regime dependence. Second, because of the coupling between cloud macrophysics and cloud microphysics, the coefficient of the dissipation term in the total water variance equation is influential. This parameter affects the variance of in-cloud cloud water, which further influences microphysical process rates, such as autoconversion, and eventually low-cloud fraction. Furthermore, this study improves understanding of HOC behavior associated with parameter uncertainties and provides valuable insights for the interaction of macrophysics and microphysics.

  11. Periodic behaviors in the observed vertical column abundances of atmospheric hydroxyl

    NASA Technical Reports Server (NTRS)

    Burnett, Elizabeth Beaver; Burnett, Clyde R.; Minschwaner, Kenneth R.

    1989-01-01

    The data base for the vertical column abundance of atmospheric hydroxyl (OH) for Fritz Peak Observatory, Colorado (40 N, 105 W), now extends from 1976 through 1988 and is composed of 8849 independent data sets, averaging about 15 percent uncertainty and 20-minute time resolution each. The dominant solar zenith angle (chi) dependence of the OH abundance is characterized by an empirical curve, N(88), which has been updated from N(82) to include all valid data from 1980 through 1988. The chi-dependence of the OH abundance has been, to a first order, removed from the data base by a normalization procedure in which each data point is divided by the N(88,AM) value for the corresponding solar zenith angle. The resulting normalized OH values may then be examined for other systematic effects, particularly for periodic variations. Observations have also been made at Boca Raton, Florida (26 N, 80 W) and at Truk, Federated States of Micronesia (7 N, 152 E). These data bases are much less extensive and, as such, are less amenable to analysis for periodic behaviors. Some comparisons with the Colorado data may be made, however.

  12. Modeling of the spatiotemporal behavior of an argon glow discharge at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Becker, Markus M.; Loffhagen, Detlef

    2009-10-01

    The spatiotemporal behavior of gas discharges is described by means of a fluid model which comprises the coupled set of balance equations for the densities of electrons, ions and neutral particles, the electron energy balance equation as well as Poisson's equation for the electric potential. This system of equations is numerically solved using a stabilized finite element method. The discharge voltage required for the solution of Poisson's equation is determined from the solution of the external electric circuit equations taking into account the time-dependent capacity and resistance of the plasma. In the present contribution first results related to an argon plasma at atmospheric pressure in a discharge configuration designed to generate small homogeneous high-pressure glow dischargesfootnotetextW. B"otticher et al., Appl. Phys. B 54 (1992) 295 are presented. Main features of the temporal evolution of the discharge, which can be divided into Townsend, ignition, quasi-steady-state and recombination phase, are discussed. It is found that the cathode-fall thickness and current density in the quasi-steady state are of the order of the values given by the similarity laws for normal glow discharges.

  13. Parametric behaviors of CLUBB in simulations of low clouds in the Community Atmosphere Model (CAM)

    NASA Astrophysics Data System (ADS)

    Guo, Zhun; Wang, Minghuai; Qian, Yun; Larson, Vincent E.; Ghan, Steven; Ovchinnikov, Mikhail; Bogenschutz, Peter A.; Gettelman, Andrew; Zhou, Tianjun

    2015-09-01

    In this study, we investigate the sensitivity of simulated low clouds to 14 selected tunable parameters of Cloud Layers Unified By Binormals (CLUBB), a higher-order closure (HOC) scheme, and four parameters of the Zhang-McFarlane (ZM) deep convection scheme in the Community Atmosphere Model version 5 (CAM5). A Quasi-Monte Carlo (QMC) sampling approach is adopted to effectively explore the high-dimensional parameter space and a generalized linear model is applied to study the responses of simulated cloud fields to tunable parameters. Our results show that the variance in simulated low-cloud properties (cloud fraction and liquid water path) can be explained by the selected tunable parameters in two different ways: macrophysics itself and its interaction with microphysics. First, the parameters related to dynamic and thermodynamic turbulent structure and double Gaussian closure are found to be the most influential parameters for simulating low clouds. The spatial distributions of the parameter contributions show clear cloud-regime dependence. Second, because of the coupling between cloud macrophysics and cloud microphysics, the coefficient of the dissipation term in the total water variance equation is influential. This parameter affects the variance of in-cloud cloud water, which further influences microphysical process rates, such as autoconversion, and eventually low-cloud fraction. This study improves understanding of HOC behavior associated with parameter uncertainties and provides valuable insights for the interaction of macrophysics and microphysics.

  14. Nitrosyl sulfuric acid and stratospheric aerosols

    NASA Astrophysics Data System (ADS)

    Burley, Joel D.; Johnston, H. S.

    1992-07-01

    It is proposed on the basis of information found in the atmospheric and chemical literature that nitrosyl sulfuric acid (NSA), NOHSO4 may play an important role in stratospheric chemistry. If the reaction probability of forming NSA per collision of NO with a sulfuric acid aerosol is 0.001, 1 percent of the sulfuric acid would be converted to NSA within 1 d at 20 km altitude. If NSA in the sulfate aerosols is 1 percent of the sulfuric acid and if the second order rate constant for (HCl + NOHSO4 = H2SO4 + ClNO) in sulfuric acid solution is greater than 10 exp -18 cu cm/molecule s under conditions at 20 km altitude, the rate of HCl + NSA is faster than the rate of HO + HCl. In this case, this heterogeneous catalysis is expected to affect the balance of No sub y, Cl sub y, and the ozone in the lower stratosphere.

  15. Spatially-differentiated atmospheric source-receptor relationships for nitrogen oxides, sulfur oxides and ammonia emissions at the global scale for life cycle impact assessment

    NASA Astrophysics Data System (ADS)

    Roy, Pierre-Olivier; Huijbregts, Mark; Deschênes, Louise; Margni, Manuele

    2012-12-01

    This paper aims to advance regional worldwide source-receptor relationships, providing fate factors for acidifying and eutrophying air emissions (NOx, HNO3, SO2, SO4 and NH3) to be used within life cycle impact assessment. A simulation for the reference year 2005 of the three-dimensional global scale tropospheric GEOS-Chem model was used as the basis of a novel methodological approach to derive source-receptor matrices (SRMs) whose elements are fate factors at a global 2° × 2.5° grid. This new approach makes it possible to assess the impact of transboundary emissions while maintaining regional scale emission differentiation. These 2° × 2.5° grid resolution fate factors were later aggregated at continental and country resolutions using emission weighting. Continental fate factor results showed that 50-70% of nitrogen oxides (NOx, HNO3) and sulfur oxides (SO2, SO4) and approximately 80% of ammonia (NH3) emissions will deposit on the same continent. Results showed that the developed fate factor derivation approach was within a ±10% agreement with GEOS-Chem simulations in which fate factors were determined by withdrawing the regional emission inventory over Canada and in ±50% agreement with current state-of-the-art LCIA fate factors (calculated with the European Monitoring and Evaluation Programme (EMEP) model). The SRMs outlined in this paper facilitate further modeling developments without having to run the underlying tropospheric model, thus opening the door to the assessment of the regional life cycle inventories of a global economy.

  16. Are climate warming and enhanced atmospheric deposition of sulfur and nitrogen threatening tufa landscapes in Jiuzhaigou National Nature Reserve, Sichuan, China?

    PubMed

    Qiao, Xue; Du, Jie; Lugli, Stefano; Ren, Jinhai; Xiao, Weiyang; Chen, Pan; Tang, Ya

    2016-08-15

    Massive deposition of calcium carbonate in ambient temperature waters (tufa) can form magnificent tufa landscapes, many of which are designated as protected areas. However, tufa landscapes in many areas are threatened by both local anthropogenic activities and climate change. This study, for the first time, posed the question whether the tufa landscape degradation (characterized by tufa degradation and increased biomass of green algae) in Jiuzhaigou National Nature Reserve of China is partially caused by regional air pollution and climate warming. The results indicate that wet deposition (including rain and snow) polluted by anthropogenic SO2, NOx, and NH3 emissions dissolves exposed tufa and may considerably reduce tufa deposition rate and even cause tufa dissolution within shallow waters. These effects of wet deposition on tufa enhanced as pH of wet deposition decreased from 8.01 to 5.06. Annual Volume Weighted Mean concentration of reactive nitrogen (including NH4(+) and NO3(-)) in wet deposition (26.1μmolL(-1)) was 1.8 times of the corresponding value of runoff (14.8μmolL(-1)) and exceeded China's national standard of total nitrogen in runoff for nature reserves (14.3μmolL(-1)), indicating a direct nitrogen fertilization effect of wet deposition on green algae. As water temperature is the major limiting factor of algal growth in Jiuzhaigou and temperature in the top layer (0-5cm) of runoff (depth<1m, no canopy coverage of trees and shrubs) was significantly higher at the sites with increased biomass of green algae (p<0.05), climate warming in this region would favor algal growth. In sum, this study suggests that climate warming and enhanced sulfur and nitrogen deposition have contributed to the current degradation of tufa landscape in Jiuzhaigou, but in order to quantify the contributions, further studies are needed, as many other anthropogenic and natural processes also influence tufa landscape evolution.

  17. Properties of Sulfur Concrete.

    DTIC Science & Technology

    1979-07-06

    This report summarizes the state of the art of sulfur concrete . Sulfur concrete is created by mixing molten sulfur with aggregate and allowing the...and many organic compounds. It works well as a rapid runway repair material. Sulfur concrete also has unfavorable properties. It has poor durability

  18. Silica- and sulfate-bearing rock coatings in smelter areas: Part II. Forensic tools for atmospheric metal(loid)- and sulfur-isotope compositions

    NASA Astrophysics Data System (ADS)

    Mantha, Nathalie M.; Schindler, Michael; Kyser, T. Kurtis

    2012-08-01

    Black silica- and sulfate-bearing rock coatings in the Greater Sudbury area, Canada provide a record of atmospheric processes and emitted particulate matter associated with historical smelting operations in this area. Coating samples collected over the Greater Sudbury region are characterized with scanning electron microscopy, electron microprobe analysis, laser ablation inductively coupled mass-spectrometry, S-stable isotope measurements and micro X-ray fluorescence. On the micrometer scale, Cu, Pb, As, Se and S occur in close association within metal-sulfate rich layers composed of Fe- and Cu-sulfates. The concentrations of these and other elements do not represent their chemical proportions in the smelter plumes due to dissolution-precipitation processes, element substitutions and the stability of various phases involved in the coating formation. On the regional scale, the atomic ratios of Pb:Ni, As:Ni and Se:Ni decrease in the coatings with increasing distance from the smelting centers. This observation is consistent with higher wet deposition rates of small diameter Pb, As and Se-bearing primary sulfate aerosols (<2.5 μm), compared to larger diameter (>2.5 μm) Ni-bearing particulate matter. The mixing of primary (higher δ34S values) and secondary (lower δ34S values) sulfates explains the δ34S values of sulfates within the coatings close to smelting centers and the decrease in these values is attributed to the decrease in the ratio of primary to secondary sulfates with distance from the smelting centers. The information preserved in mineral surface-coatings together with an understanding of stoichiometry, geochemical processes and former environmental conditions provide a valuable record of atmospheric compositions, mixing, scavenging, deposition rates and oxidation processes, and the nature and source of anthropogenic releases to the atmosphere.

  19. Phanerozoic cycles of sedimentary carbon and sulfur.

    PubMed

    Garrels, R M; Lerman, A

    1981-08-01

    A reservoir model of a Recent steady-state sedimentary system in which the reduced sulfur and oxidized sulfur reservoirs were coupled with the oxidized carbon and reduced carbon reservoirs was constructed. The time curve of the sulfur isotope ratios of the sedimentary sulfate reservoir was used to drive the model back to the beginning of Cambrian time (600 million years ago), producing the reservoir sizes and isotope values and material fluxes of the carbon-sulfur system. The predicted values of carbon isotope ratios of the carbonate reservoir agree well with observed values, showing that the model is basically sound. Some general conclusions from this success are (i) material flux rates in the carbon-oxygen-sulfur system of the geologic past (averaged over tens of millions of years) lie within about a factor of 2 of Recent rates. (ii) The oxidation-reduction balances of Phanerozoic time were dominated by reciprocal relationships between carbon and sulfur compounds. (iii) The rate of production of atmospheric oxygen by storage in sediments of organic carbon of photosynthetic origin increased from the Cambrian Period to the Permian Period and declined somewhat from the Permian Period to the Present. (iv) The storage of oxygen in oxidized sulfur compounds kept pace (within the limits of the data) with oxygen production. (v) Transfer of oxygen from CO(2) to SO(4) from the Cambrian to the Permian Period was several times the Recent free oxygen content of the atmosphere.

  20. Catalyst for elemental sulfur recovery process

    DOEpatents

    Flytzani-Stephanopoulos, M.; Liu, W.

    1995-01-24

    A catalytic reduction process is described for the direct recovery of elemental sulfur from various SO[sub 2]-containing industrial gas streams. The catalytic process provides high activity and selectivity, as well as stability in the reaction atmosphere, for the reduction of SO[sub 2] to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over a metal oxide composite catalyst having one of the following empirical formulas: [(FO[sub 2])[sub 1[minus]n](RO)[sub n

  1. Photochemical Formation of Sulfur-Containing Aerosols

    NASA Astrophysics Data System (ADS)

    Kroll, Jay A.; Vaida, Veronica

    2017-06-01

    In order to understand planetary climate systems, modeling the properties of atmospheric aerosols is vital. Aerosol formation plays an important role in planetary climates and is tied to feedback loops that can either warm or cool a planet. Sulfur compounds are known to play an important role in new particle aerosol formation and have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere; however, several discrepancies arise when comparing observations of the Venusian atmosphere with model predictions. This suggests that there are still problems in our fundamental understanding of sulfur chemistry. This is concerning given recent renewed interest in sulfate injections in the stratosphere for solar radiation management geo-engineering schemes. We investigate the role of sunlight as a potential driver of the formation of sulfur-containing aerosols. I will present recent work investigating the generation of large quantities of aerosol from the irradiation of mixtures of SO_2 with water and organic species, using a solar simulator that mimics the light that is available in the Earth's troposphere and the Venusian middle atmosphere. I will present on recent work done in our lab suggesting the formation of sulfurous acid, H_2SO_3, and describe experimental work that supports this proposed mechanism. Additionally I will present on new work showing the highly reactive nature of electronically excited SO_2 with saturated alkane species. The implications of this photochemically induced sulfur aerosol formation in the atmosphere of Earth and other planetary atmospheres will be discussed.

  2. Experimental Study into the Partitioning Behavior of Fluorine, Chlorine, Hydroxyl, and Sulfur (S2-) Between Apatite and a Synthetic Kreep Basalt Melt

    NASA Technical Reports Server (NTRS)

    Turner, Amber; Vander Kaaden, Kathleen; McCubbin, Francis; Danielson, Lisa R.

    2017-01-01

    The mineral apatite (Ca5 (PO4)3(F, Cl, OH)) is known for its ability to constrain the petrogenesis of the rock in which it is hosted and for its ubiquity throughout the Solar System, as it is found in lunar, martian, and terrestrial rocks alike (McCubbin et. al, 2015). The abundance of volatile elements, and for this particular study, the elevated abundance of sulfur (S2-) in high-Al basalt samples bearing apatite, could provide more insight for inquiries posed about the behavior of volatiles in lunar and martian magmatic systems (Boyce et. al, 2010). Oxygen fugacity will be an important parameter for these experiments, as the Moon, Mars, and Earth have different redox states (Herd, 2008). The objective of this experimental endeavor is to determine apatite-melt partition coefficients for the volatile elements (F-, Cl-, OH-, S2-) that make up the X-site (i.e., the typically monovalent anion site) in the mineral apatite in a lunar melt composition under lunar oxygen fugacity conditions approx.1-2 log units below the iron-wüstite buffer). All experiments will be conducted at NASA, Johnson Space Center in the High Pressure Experimental Petrology Laboratory. In order to conduct apatite-melt partition experiments with oxygen fugacity as an additional parameter, we will create a synthetic mix of the lunar KREEP basalt 15386, a sample retrieved during Apollo 15 that is believed to represent an indigenous volcanic melt derived from the lunar interior (Rhodes, J.M et. al, 2006). Other geochemically significant elements including C, Co, Ni, Mo, and rare earth elements will be included in the mix at trace abundances in order to assess their partitioning behavior without effecting the overall behavior of the system. The synthetic mix will then be loaded into a piston cylinder, an apparatus used to simulate high-pressure/high-temperature conditions of planetary interiors, and exposed to 0.5 GPa of pressure, the pressure observed in the upper mantle of the Moon, and heated to

  3. The composition, seasonal variation, and potential sources of the atmospheric wet sulfur (S) and nitrogen (N) deposition in the southwest of China.

    PubMed

    Liu, Lei; Zhang, Xiuying; Lu, Xuehe

    2016-04-01

    The composition, seasonal variation, and potential sources of sulfate (S) and nitrogen (N) deposition in precipitation in the southwest of China from 2003 to 2013 were investigated. The results showed that the concentration of SO4 (2-), NO3 (-), and NH4 (+) in rainwater were 10.57-1360, 7.16-523.71, and 7.54-1020 μeq l(-1), with an annual volume-weighted mean (VWM) concentration of 103.99, 46.73, and 97.30 μeq l(-1), respectively. The annual wet deposition of SO4 (2-), NO3 (-), and NH4 (+) was 21.66, 8.16, and 17.49 kg S (N) ha(-1), respectively. The temporal variations of the ions showed that the abrupt decreasing breakpoints were in 2008 for SO4 (2-) and in 2009 for NO3 (-) and NH4 (+), and increasing trends were observed after 2010 for the three ions. These trends reflected the effect of economy recession and the policy of controlling SO2 and NOx emissions. The acid rain type of precipitation was shifted from sulfur to a mixed one. The ions of SO4 (2-), NO3 (-), and NH4 (+) presented high values in winter and spring and low values in autumn and summer. A highly positive linear correlation between SO4 (2-) and NO3 (-) (R(2) = 0.71), SO4 (2-) and NH4 (+) (R(2) = 0.74), and NO3 (-) and NH4 (+) (R(2) = 0.84) existed while a strong negative correlation was found between the three main ionic concentrations and precipitation. The SO4 (2-) was mainly from fossil fuel combustion (60.53%), aged sea salt (19.03%), agriculture (11.38%), crust (6.66%), and biomass burning (2.40%); the NO3 (-) was mainly from fossil fuel combustion (75.41%), biomass burning (9.67%), aged sea salt (7.97%), and agriculture (6.96%); and the NH4 (+) was mainly from agriculture (86.38%), fossil fuel combustion (10.52%), and aged sea salt (3.09%).

  4. A primer on sulfur for the planetary geologist

    NASA Technical Reports Server (NTRS)

    Theilig, E.

    1982-01-01

    Sulfur has been proposed as the dominant composition for the volcanic material on Io. Sulfur is a complex element which forms many intramolecular and intermolecular allotropes exhibiting a variety of physical properties. Cyclo-S8 sulfur is the most abundant and stable molecular form. The important molecular species within liquid sulfur change in concentration with temperature. Concentrations of the allotropes control the physical properties of the melt. Discontinuities in density, viscosity, and thermal properties reflect the polymerization process within liquid sulfur. Variations in the melting point are related to autodissociation of the liquid. Many solids forms of sulfur have been identified but only orthorhombic alpha and monoclinic beta sulfur, both composed of cyclo-S8 sulfur, are stable under terrestrial conditions. Physical properties of solid sulfur are dependent on the allotrope and, in some cases, the thermal history. Three natural terrestrial sulfur flows are described: (1) Siretoko-Iosan, Japan; (2) Volcan Azufre, Galapagos Islands; and (3) Mauna Loa, Hawaii. All of the flows are associated with fumarolic areas and are considered to have formed by the melting and mobilization of sulfur deposits. Surface textures of the flows indicate a behavior of molten sulfur similar to that of silicate lava. Channels, rivulets, and lobate edges were described for the flows. The solidification of man-made sulfur flows formed as part of the Frasch mining process by which sulfur is removed from the subsurface in a liquid state is described.

  5. Smaller sulfur molecules promise better lithium-sulfur batteries.

    PubMed

    Xin, Sen; Gu, Lin; Zhao, Na-Hong; Yin, Ya-Xia; Zhou, Long-Jie; Guo, Yu-Guo; Wan, Li-Jun

    2012-11-14

    The lithium-sulfur battery holds a high theoretical energy density, 4-5 times that of today's lithium-ion batteries, yet its applications have been hindered by poor electronic conductivity of the sulfur cathode and, most importantly, the rapid fading of its capacity due to the formation of soluble polysulfide intermediates (Li(2)S(n), n = 4-8). Despite numerous efforts concerning this issue, combatting sulfur loss remains one of the greatest challenges. Here we show that this problem can be effectively diminished by controlling the sulfur as smaller allotropes. Metastable small sulfur molecules of S(2-4) were synthesized in the confined space of a conductive microporous carbon matrix. The confined S(2-4) as a new cathode material can totally avoid the unfavorable transition between the commonly used large S(8) and S(4)(2-). Li-S batteries based on this concept exhibit unprecedented electrochemical behavior with high specific capacity, good cycling stability, and superior rate capability, which promise a practicable battery with high energy density for applications in portable electronics, electric vehicles, and large-scale energy storage systems.

  6. Influence of voltage magnitude on the dynamic behavior of a stable helium atmospheric pressure plasma jet

    NASA Astrophysics Data System (ADS)

    Ning, Wenjun; Wang, Lijun; Wu, Chen; Jia, Shenli

    2014-08-01

    Effects of voltage magnitude on the development of a stable helium atmospheric pressure plasma jet are investigated by current measurements and high temporal-resolution streak images. Generated by a coaxial dielectric barrier discharge structure, the entire discharge can be classified into three regions: discharges in the tube gap, downstream jet, and up-streamer. The discharge morphologies of each region are analyzed. In the positive discharge phase, there are two discharges in the tube gap between the electrodes; the first one is ignited as corona and then developed into streamer corona, and the second one is similar with positive glow. The downstream jet is ignited independently from the discharge in the tube gap. Referred as "plasma bullet," the dynamic behavior of the jet can be well described as a positive streamer. Under specific applied voltage, the jet is found to be composed by double bullets in which case the jet length decreases since that less charge is carried by the first bullet. The up-streamer can be captured as long as the discharge in the tube gap is activated. Propagating with velocity of ˜4 km/s, the up-streamer can be regarded as the extension of the first discharge in the tube gap. In the negative discharge phase, the discharge is confined in the tube gap with nearly symmetrical morphology with the positive one. Besides, with the rising of voltage, the negative discharge is initially intensified and then turns weaker after surpassing certain voltage, which may provide suitable condition for the occurrence of double-bullet phenomenon.

  7. Sulfur metabolism in phototrophic sulfur bacteria.

    PubMed

    Frigaard, Niels-Ulrik; Dahl, Christiane

    2009-01-01

    Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative of the Chromatiaceae), and many are well characterized also on a molecular genetic level. Complete genome sequence data are currently available for 10 strains of GSB and for one strain of PSB. We present here a genome-based survey of the distribution and phylogenies of genes involved in oxidation of sulfur compounds in these strains. It is evident from biochemical and genetic analyses that the dissimilatory sulfur metabolism of these organisms is very complex and incompletely understood. This metabolism is modular in the sense that individual steps in the metabolism may be performed by different enzymes in different organisms. Despite the distant evolutionary relationship between GSB and PSB, their photosynthetic nature and their dependency on oxidation of sulfur compounds resulted in similar ecological roles in the sulfur cycle as important anaerobic oxidizers of sulfur compounds.

  8. Performance and cost models for the direct sulfur recovery process. Task 1 Topical report, Volume 3

    SciTech Connect

    Frey, H.C.; Williams, R.B.

    1995-09-01

    The purpose of this project is to develop performance and cost models of the Direct Sulfur Recovery Process (DSRP). The DSRP is an emerging technology for sulfur recovery from advanced power generation technologies such as Integrated Gasification Combined Cycle (IGCC) systems. In IGCC systems, sulfur present in the coal is captured by gas cleanup technologies to avoid creating emissions of sulfur dioxide to the atmosphere. The sulfur that is separated from the coal gas stream must be collected. Leading options for dealing with the sulfur include byproduct recovery as either sulfur or sulfuric acid. Sulfur is a preferred byproduct, because it is easier to handle and therefore does not depend as strongly upon the location of potential customers as is the case for sulfuric acid. This report describes the need for new sulfur recovery technologies.

  9. Thiophenic Sulfur Compounds Released During Coal Pyrolysis

    PubMed Central

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-01-01

    Abstract Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography–mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126

  10. Thiophenic Sulfur Compounds Released During Coal Pyrolysis.

    PubMed

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-06-01

    Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography-mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis.

  11. Behavior of the Brightness Temperature of the Ocean-Atmosphere System Under Conditions of Midlatitude and Tropical Cyclone Activity

    NASA Astrophysics Data System (ADS)

    Grankov, A. G.; Milshin, A. A.; Novichikhin, E. P.

    2014-03-01

    We analyze the behavior of the ocean-atmosphere system characteristics based on direct (contact) and satellite microwave radiometric measurements. Some common and distinctive features of their dynamics in the mid-latitudes of the North Atlantic (in its Norwegian, Newfoundland, and Gulf Stream energy-active zones), which significanty affect the weather conditions in Europe, and in the tropical latitudes of the Atlantic (the Gulf of Mexico and the Bahamas area), which are the sources of tropical cyclogenesis, are considered.

  12. High Temperature Oxidation Behavior of P91, P92 and E911 Alloy Steels in Dry andWet Atmospheres

    NASA Astrophysics Data System (ADS)

    Mathiazhagan, Palanivel; Khanna, Anand Sawroop

    2011-04-01

    The oxidation behavior has been studied under both dry and wet oxidation atmosphere at 873 K to 1073 K. In dry atmosphere the oxidation resistance of these alloys has been described by the formation of a protective oxide FeCr2O4 at 873 K to 973 K. At 1073 K, the kinetics are parabolic with fast growing oxide leading to spalling of oxide for P92 alloy. Oxide scale formed in air was protective with a chromium rich scale at 873-973 K, while double layered oxides were formed at 1073 K with iron oxide an outer layer and inner Cr-rich spinel FeCr2O4. In wet atmosphere oxide scale was reasonably different. The oxide layer showed porous in wet atmospheres where as dense oxide layer formed during dry oxidation. The oxidation rate of P92 alloy is about 3, 2 and 1 orders of magnitude higher than the P9, P91 and E911 alloys in wet atmospheres.

  13. Solubility of Sulfur Dioxide in Sulfuric Acid

    NASA Technical Reports Server (NTRS)

    Chang, K. K.; Compton, L. E.; Lawson, D. D.

    1982-01-01

    The solubility of sulfur dioxide in 50% (wt./wt.) sulfuric acid was evaluated by regular solution theory, and the results verified by experimental measurements in the temperature range of 25 C to 70 C at pressures of 60 to 200 PSIA. The percent (wt./wt.) of sulfur dioxide in 50% (wt./wt.) sulfuric acid is given by the equation %SO2 = 2.2350 + 0.0903P - 0.00026P 10 to the 2nd power with P in PSIA.

  14. Sulfur dioxide - Episodic injection shows evidence for active Venus volcanism

    NASA Technical Reports Server (NTRS)

    Esposito, L. W.

    1984-01-01

    Pioneer Venus ultraviolet spectra from the first 5 years of operation show a decline (by more than a factor of 10) in sulfur dioxide abundance at the cloud tops and in the amount of submicron haze above the clouds. At the time of the Pioneer Venus encounter, the values for both parameters greatly exceeded earlier upper limits. However, Venus had a similar appearance in the late 1950's, implying the episodic injection of sulfur dioxide possibly caused by episodic volcanism. The amount of haze in the Venus middle atmosphere is about ten times that found in earth's stratosphere after the most recent major volcanic eruptions, and the thermal energy required for this injection on Venus is greater by about an order of magnitude than the largest of these recent earth eruptions and about as large as the Krakatoa eruption of 1883. The episodic behavior of sulfur dioxide implies that steady-state models of the chemistry and dynamics of cloud-top regions may be of limited use.

  15. Sulfur dioxide - Episodic injection shows evidence for active Venus volcanism

    NASA Astrophysics Data System (ADS)

    Esposito, L. W.

    1984-03-01

    Pioneer Venus ultraviolet spectra from the first 5 years of operation show a decline (by more than a factor of 10) in sulfur dioxide abundance at the cloud tops and in the amount of submicron haze above the clouds. At the time of the Pioneer Venus encounter, the values for both parameters greatly exceeded earlier upper limits. However, Venus had a similar appearance in the late 1950's, implying the episodic injection of sulfur dioxide possibly caused by episodic volcanism. The amount of haze in the Venus middle atmosphere is about ten times that found in earth's stratosphere after the most recent major volcanic eruptions, and the thermal energy required for this injection on Venus is greater by about an order of magnitude than the largest of these recent earth eruptions and about as large as the Krakatoa eruption of 1883. The episodic behavior of sulfur dioxide implies that steady-state models of the chemistry and dynamics of cloud-top regions may be of limited use.

  16. Non-conservative behavior of bromide in surface waters and brines of Central Andes: A release into the atmosphere?

    NASA Astrophysics Data System (ADS)

    Risacher, François; Fritz, Bertrand; Alonso, Hugo

    2006-05-01

    The transfer of reactive bromine into the atmosphere was recently observed by Hönninger et al. [Hönninger, G., Bobrowski, N., Palenque, E.R., Torrez, R., Platt, U., 2004. Reactive bromine and sulfur emission at salar de Uyuni, Bolivia. Geophys. Res. Lett.31, doi:10.1029/2003GL018818] in a large salt pan of the Bolivian Altiplano: the salar de Uyuni. However, bromide is considered to be an excellent conservative tracer, which leads to the questioning of its actual conservation in surficial geochemical processes. The relation between bromide and lithium, thought to be a conservative component in waters and brines of the Central Andes, points to a depletion of Br relative to Li in Uyuni brines of about 50-300 kg/day, a flux close to that measured by Hönninger et al. (2004): ⩾200 kg/day. Such values are very low in regard to the size of the salar (5-30 g/km 2/day). Salt efflorescences have a much higher surface area than a flat salt crust, which should enhance the release of bromine. Leach solutions of salt efflorescences in closed basins of northern Chile are compared to their parent waters. Conservative components should have the same concentration ratios in both solutions. Actually, a strong depletion in Br is observed in the leach solutions, which could suggest a significant release of Br from the salt into the atmosphere. During the rainy season, efflorescences are leached and their dissolved components brought in saline lakes and salars. Evaporative profiles show a slight but noticeable fractionation between Li and Br which could be due to the contribution of Br-depleted leach solutions of salt efflorescences. Therefore, bromide does not behave conservatively in surface waters and brines of the Central Andes. If the loss of Br is really due to its transfer into the atmosphere, then the flux would be much higher than that estimated for the salar de Uyuni alone. Numerous salt pans, saline lakes, and widespread efflorescences covering large land surfaces would

  17. Plant sulfur nutrition: From Sachs to Big Data.

    PubMed

    Kopriva, Stanislav

    2015-01-01

    Together with water and carbon dioxide plants require 14 essential mineral nutrients to finish their life cycle. The research in plant nutrition can be traced back to Julius Sachs, who was the first to experimentally prove the essentiality of mineral nutrients for plants. Among those elements Sachs showed to be essential is sulfur. Plant sulfur nutrition has been not as extensively studied as the nutrition of nitrogen and phosphate, probably because sulfur was not limiting for agriculture. However, with the reduction of atmospheric sulfur dioxide emissions sulfur deficiency has become common. The research in sulfur nutrition has changed over the years from using yeast and algae as experimental material to adopting Arabidopsis as the plant model as well as from simple biochemical measurements of individual parameters to system biology. Here the evolution of sulfur research from the times of Sachs to the current Big Data is outlined.

  18. Plant sulfur nutrition: From Sachs to Big Data

    PubMed Central

    Kopriva, Stanislav

    2015-01-01

    Together with water and carbon dioxide plants require 14 essential mineral nutrients to finish their life cycle. The research in plant nutrition can be traced back to Julius Sachs, who was the first to experimentally prove the essentiality of mineral nutrients for plants. Among those elements Sachs showed to be essential is sulfur. Plant sulfur nutrition has been not as extensively studied as the nutrition of nitrogen and phosphate, probably because sulfur was not limiting for agriculture. However, with the reduction of atmospheric sulfur dioxide emissions sulfur deficiency has become common. The research in sulfur nutrition has changed over the years from using yeast and algae as experimental material to adopting Arabidopsis as the plant model as well as from simple biochemical measurements of individual parameters to system biology. Here the evolution of sulfur research from the times of Sachs to the current Big Data is outlined. PMID:26305261

  19. Constitutive Model for the Time-Dependent Mechanical Behavior of 430 Stainless Steel and FeCrAlY Foams in Sulfur-Bearing Environments

    SciTech Connect

    Hemrick, James Gordon; Lara-Curzio, Edgar

    2013-01-01

    The mechanical behavior of 430 stainless steel and pre-oxidized FeCrAlY open-cell foam materials of various densities was evaluated in compression at temperatures between 450 C and 600 C in an environment containing hydrogen sulfide and water vapor. Both materials showed negligible corrosion due to the gaseous atmosphere for up to 168 hours. The monotonic stress-strain response of these materials was found to be dependent on both the strain rate and their density, and the 430 stainless steel foam materials exhibited less stress relaxation than FeCrAlY for similar experimental conditions. Using the results from multiple hardening-relaxation and monotonic tests, an empirical constitutive equation was derived to predict the stress-strain behavior of FeCrAlY foams as a function of temperature and strain rate. These results are discussed in the context of using these materials in a black liquor gasifier to accommodate the chemical expansion of the refractory liner resulting from its reaction with the soda in the black liquor.

  20. Constitutive Model for the Time-Dependent Mechanical Behavior of 430 Stainless Steel and FeCrAlY Foams in Sulfur-Bearing Environments

    NASA Astrophysics Data System (ADS)

    Hemrick, James G.; Lara-Curzio, Edgar

    2013-03-01

    The mechanical behavior of 430 stainless steel and pre-oxidized FeCrAlY open-cell foam materials of various densities was evaluated in compression at temperatures between 450°C and 600°C in an environment containing hydrogen sulfide and water vapor. Both materials showed negligible corrosion due to the gaseous atmosphere for up to 168 h. The monotonic stress-strain response of these materials was found to be dependent on both the strain rate and their density, and the 430 stainless steel foam materials exhibited less stress relaxation than the FeCrAlY for similar experimental conditions. Using the results from multiple hardening-relaxation and monotonic tests, an empirical constitutive equation was derived to predict the stress-strain behavior of FeCrAlY foams as a function of temperature, and strain rate. These results are discussed in the context of using these materials in a black liquor gasifier to accommodate the chemical expansion of the refractory liner resulting from its reaction with the soda in the black liquor.

  1. The Aggregate Behavior of Branch Points - A Proposal for an Atmospheric Turbulence Layer Sensor: Postprint

    DTIC Science & Technology

    2010-07-01

    enhanced controUer (Predictive Fourier Controll ). MeAO inlProves compensation by assuming a "best-fit" two layered structure to the atmospheric...turbu1ence2 even when the atmosphere is broadly distributed. This common assumption is borne out experimentally.3 Predictive Fourier Controll modifies the...hN. The structure function is then given by (6) The Parumelera oJlntere.t in Adaptive Optica - ro. a~. 80 and Ie A turbulence layer sensor must

  2. Clouds in Planetary Atmospheres

    NASA Astrophysics Data System (ADS)

    West, R.; Murdin, P.

    2000-11-01

    What are clouds? The answer to that question is both obvious and subtle. In the terrestrial atmosphere clouds are familiar as vast collections of small water drops or ice crystals suspended in the air. In the atmospheres of Venus, Mars, Jupiter, Saturn, Saturn's moon Titan, Uranus, Neptune, and possibly Pluto, they are composed of several other substances including sulfuric acid, ammonia, hydroge...

  3. The significance of glucosinolates for sulfur storage in Brassicaceae seedlings

    PubMed Central

    Aghajanzadeh, Tahereh; Hawkesford, Malcolm J.; De Kok, Luit J.

    2014-01-01

    Brassica juncea seedlings contained a twofold higher glucosinolate content than B. rapa and these secondary sulfur compounds accounted for up to 30% of the organic sulfur fraction. The glucosinolate content was not affected by H2S and SO2 exposure, demonstrating that these sulfur compounds did not form a sink for excessive atmospheric supplied sulfur. Upon sulfate deprivation, the foliarly absorbed H2S and SO2 replaced sulfate as the sulfur source for growth of B. juncea and B. rapa seedlings. The glucosinolate content was decreased in sulfate-deprived plants, though its proportion of organic sulfur fraction was higher than that of sulfate-sufficient plants, both in absence and presence of H2S and SO2. The significance of myrosinase in the in situ turnover in these secondary sulfur compounds needs to be questioned, since there was no direct co-regulation between the content of glucosinolates and the transcript level and activity of myrosinase. Evidently, glucosinolates cannot be considered as sulfur storage compounds upon exposure to excessive atmospheric sulfur and are unlikely to be involved in the re-distribution of sulfur in B. juncea and B. rapa seedlings upon sulfate deprivation. PMID:25566279

  4. The transient behavior of scaling in the atmosphere: stratiform/convective transition and applications to sub-grid scale statistics

    NASA Astrophysics Data System (ADS)

    Nogueira, M.; Barros, A. P.

    2014-12-01

    Multifractal behavior holds to a remarkable approximation over wide ranges of spatial scales in orographic rainfall and cloud fields. The scaling exponents characterizing this behavior are shown to be fundamentally transient with nonlinear dependencies on the particular atmospheric state and terrain forcing. In particular, a robust transition is found in the scaling parameters between non-convective (stable) and convective (unstable) regimes, with clear physical correspondence to the transition from stratiform to organized convective orographic precipitation. These results can explain two often reported scaling regimes for atmospheric wind, temperature and water observations. On the one hand, spectral slopes around 2-2.3 arise under non-convective or very weak convective conditions when the spatial patterns are dominated by large-scale gradients and landform. On the other hand, under convective conditions the scaling exponents generally fluctuate around 5/3, in agreement with the Kolmogorov turbulent regime accounting for the intermittency correction. High-resolution numerical weather prediction (NWP) models are able to reproduce the ubiquitous scaling behavior of observed atmospheric fields down to their effective resolution length-scale, below which the variability is misrepresented by the model. The effective resolution is shown to be a transient property dependent on the particular simulated conditions and NWP formulation, implying that a blunt decrease in grid spacing without adjusting numerical techniques may not lead to the improvements desired.Finally, the application of transient spatial scaling behavior for stochastic downscaling and sub-grid scale parameterization of cloud and rainfall fields is investigated. The proposed fractal methods are able to rapidly generate large ensembles of high-resolution statistically robust fields from the coarse resolution information alone, which can provide significant improvements for stochastic hydrological prediction

  5. Observations of industrial sulfur flows and implications for Io

    NASA Technical Reports Server (NTRS)

    Lee, S. W.; Crown, D. A.; Lancaster, N.; Greeley, R.

    1987-01-01

    The possibility of sulfur flows on the Jovian satellite Io is discussed. Although the primary problem is lack of sufficient information to resolve the issue, interpretations of existing data are hampered by poor knowledge of the thermal properties and rheologic behavior of sulfur flows, especially under conditions present on Io. Relatively few natural sulfur flows occur on Earth and only one has been seen in active flow. However, recent observations of industrial sulfur flows, which are much larger than those produced experimentally, may provide important information concerning natural sulfur flows on both Earth and Io.

  6. 40 CFR 60.173 - Standard for sulfur dioxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 7 2014-07-01 2014-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain...

  7. 40 CFR 60.173 - Standard for sulfur dioxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain...

  8. 40 CFR 60.173 - Standard for sulfur dioxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 7 2012-07-01 2012-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain...

  9. 40 CFR 60.173 - Standard for sulfur dioxide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain...

  10. Sulfur compound concentrations at swine and poultry facilities

    USDA-ARS?s Scientific Manuscript database

    Reduced sulfur compounds are emitted from waste handling at animal agriculture operations. These sulfur compounds are responsible for odor production as well as participating in atmospheric chemistry. We have adapted a chromatographic method for providing 10 minute online monitoring capability of re...

  11. 40 CFR 60.173 - Standard for sulfur dioxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 7 2013-07-01 2013-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain...

  12. Investigation on the sulfur state and phase transformation of spent and regenerated S zorb sorbents using XPS and XRD

    NASA Astrophysics Data System (ADS)

    Qiu, Limei; Zou, Kang; Xu, Guangtong

    2013-02-01

    A series of industrial S zorb sorbents extracted from production line were characterized by XPS and XRD. The formation of ZnAl2O4 and Zn2SiO4 is the major reason for the deactivation of spent sorbent. The stability of the Zn-containing spinel species leads to the decrease of the desulfurization efficiency of regenerated sorbent. The chemical states of sulfur atom were examined by XPS. The depth distribution of sulfur species and the reductive behavior of sulfate in H2 atmosphere were explored using Ar+ etching XPS and in situ XPS. The formation of sulfate species in the regeneration process decreases the content of ZnO in the surface significantly and should be avoided. XPS and XRD are excellent tools to follow the sulfur chemical states and phase evolution of S zorb sorbent, respectively, which provide important information for the investigation of deactivation pathways and regenerated mechanisms for S zorb sorbent.

  13. Unique, Non-Earthlike, Meteoritic Ion Behavior in Upper Atmosphere of Mars

    NASA Technical Reports Server (NTRS)

    Grebowsky, J. M.; Benna, M.; Plane, J. M. C.; Collinson, G. A.; Mahaffy, P. R.; Jakosky, B. M.

    2017-01-01

    Abstract Interplanetary dust particles have long been expected to produce permanent ionospheric metal ion layers at Mars, as on Earth, but the two environments are so different that uncertainty existed as to whether terrestrial-established understanding would apply to Mars. The Mars Atmosphere and Volatile EvolutioN (MAVEN) mission made the first in situ detection of the continuous presence of Na+, Mg+, and Fe+ at Mars and indeed revealed non-Earthlike features/processes. There is no separation of the light Mg+ and the heavy Fe+ with increasing altitude as expected for gravity control. The metal ions are well-mixed with the neutral atmosphere at altitudes where no mixing process is expected. Isolated metal ion layers mimicking Earths sporadic E layers occur despite the lack of a strong magnetic field as required at Earth. Further, the metal ion distributions are coherent enough to always show atmospheric gravity wave signatures. All features and processes are unique to Mars.

  14. Unique, non-Earthlike, meteoritic ion behavior in upper atmosphere of Mars

    NASA Astrophysics Data System (ADS)

    Grebowsky, J. M.; Benna, M.; Plane, J. M. C.; Collinson, G. A.; Mahaffy, P. R.; Jakosky, B. M.

    2017-04-01

    Interplanetary dust particles have long been expected to produce permanent ionospheric metal ion layers at Mars, as on Earth, but the two environments are so different that uncertainty existed as to whether terrestrial-established understanding would apply to Mars. The Mars Atmosphere and Volatile EvolutioN (MAVEN) mission made the first in situ detection of the continuous presence of Na+, Mg+, and Fe+ at Mars and indeed revealed non-Earthlike features/processes. There is no separation of the light Mg+ and the heavy Fe+ with increasing altitude as expected for gravity control. The metal ions are well-mixed with the neutral atmosphere at altitudes where no mixing process is expected. Isolated metal ion layers mimicking Earth's sporadic E layers occur despite the lack of a strong magnetic field as required at Earth. Further, the metal ion distributions are coherent enough to always show atmospheric gravity wave signatures. All features and processes are unique to Mars.

  15. Effects of Platinum Additions and Sulfur Impurities on the Microstructure and Scale Adhesion Behavior of Single-Phase CVD Aluminide Bond Coatings

    SciTech Connect

    Cooley, K.M.; Haynes, J.A.; Lee, W.Y.; Pint, B.A.; Wright, I.G.; Zhang, Y.

    1999-02-28

    The adhesion of alumina scales to aluminide bond coats is a life-limiting factor for some advanced thermal barrier coating systems. This study investigated the effects of aluminide bond coat sulfur and platinum contents on alumina scale adhesion and coating microstructural evolution during isothermal and cyclic oxidation testing at 1150 C. Low-sulfur NiAl and NiPtAl bond coats were fabricated by chemical vapor deposition (CVD). Lowering the sulfur contents of CVD NiAl bond coatings significantly improved scale adhesion, but localized scale spallation eventually initiated along coating grain boundaries. Further improvements in scale adhesion were obtained with Pt additions. The observed influences of Pt additions included: (1) mitigation of the detrimental effects of high sulfur levels, (2) drastic reductions in void growth along the scale-metal interface, (3) alteration of the oxide-metal interface morphology, and (4) elimination of Ta-rich oxides in the Al{sub 2}O{sub 3} scales during thermal cycling. The results of this study also suggested that the microstructure (especially the grain size) of CVD aluminide bond coatings plays a significant role in scale adhesion.

  16. Fire self-extinguishing cotton fabric: development of piperazine derivatives containing phosphorous-sulfur-nitrogen and their flame retardant and thermal behaviors

    USDA-ARS?s Scientific Manuscript database

    Recent studies have shown interest in flame retardants containing phosphorus, nitrogen and sulfur a combination small molecule with a promising new approach in preparing an important class of flame retardant materials. Tetraethyl piperazine-1,4-diyldiphosphonate (TEPP) and O,O,O',O'-tetramethyl pip...

  17. Generation of Sulfur-rich, Sulfur-undersaturated Basaltic Melts in Oxidized Arc Sources.

    NASA Astrophysics Data System (ADS)

    Jugo, P. J.; Luth, R. W.; Richards, J. P.

    2003-12-01

    Although sulfur is a minor element in the Earth, it has a disproportionate impact because it commonly occurs as sulfide. Sulfides largely control the behavior of chalcophile (e.g., Cu, Ni) and highly siderophile elements (Ru, Rh, Pd, Re, Os, Ir, Pt, and Au) that are of interest because either they are economically important or because they provide valuable information about geochemical processes. Island arc basalts are more oxidized than basalts from other tectonic settings and therefore, in these settings, sulfur maybe present not as sulfide but as sulfate. In addition to the impact on the behavior of chalcophile and siderophile elements, sulfur speciation as sulfate may have a role on the occurrence of sulfur-rich explosive volcanism, which has been linked to significant short-term variations in global climate. However, little is known about the range in oxygen fugacity for the transition from solubility as sulfide to solubility as sulfate. We used experimental data on the solubility of sulfur in basaltic melts saturated with either sulfide or sulfate at different oxygen fugacities to model this transition. Our model shows that the ten-fold increase in the solubility of sulfur (from 0.14 wt.% to 1.5 wt.%) observed experimentally occurs at oxygen fugacities between ˜FMQ+1 and ˜FMQ+2, conditions under which many arc magmas are thought to be generated. The increase in the solubility of sulfur with increasing oxygen fugacity implies that in oxidized arc sources very low degrees of partial melting are sufficient to generate basaltic melts that are simultaneously sulfur-rich and sulfur-undersaturated. In the absence of sulfides, oxides and metallic alloys may influence the behavior of some (but not all) the highly siderophile elements whereas the chalcophile and some siderophile elements become incompatible. As a consequence, melting of oxidized sources in which sulfides are not stable would favor incorporation of metals such as Cu, Ni, Au and Pd in the melts and

  18. Meniscus behavior of metals and oxides in molten carbonate under oxidant and reducing atmospheres. 1: Contact angle and electrolyte displacement

    SciTech Connect

    Mugikura, Y.; Selman, J.R.

    1996-08-01

    The wetting of metals and oxides by molten carbonate is an important factor affecting the performance of a molten carbonate fuel cell (MCFC). The distribution of the electrolyte among electrodes and matrix in the MCFC is dominated by the pore characteristics and wetting properties of these components. However, data on wetting, especially under load (current passage), are limited. In this study, the behavior of the meniscus at a metal is used to obtain information on wetting and electrochemical reactions. Meniscus height and current were measured under various atmospheres. The contact angle was calculated from the meniscus height. The electrolyte distribution in the MCFC was estimated using contact angles thus obtained in oxidant and reducing atmospheres. The results suggest that upon application of load the electrolyte moves from the anode to the cathode and that capillary effects can worsen the performance of a cell, especially if it is in an unbalanced state of electrolyte filling.

  19. Tracing Archean sulfur across stitched lithospheric blocks

    NASA Astrophysics Data System (ADS)

    LaFlamme, Crystal; Fiorentini, Marco; Lindsay, Mark; Wing, Boswell; Selvaraja, Vikraman; Occhipinti, Sandra; Johnson, Simon; Bui, Hao Thi

    2017-04-01

    Craton margins are loci for volatile exchange among lithospheric geochemical reservoirs during crust formation processes. Here, we seek to revolutionise the current understanding of the planetary flux and lithospheric transfer of volatiles during supercontinent formation by tracing sulfur from the atmosphere-hydrosphere through to the lithosphere during crust formation. To do so, we trace the transfer of sulfur by following mass independently fractionated sulfur at ancient tectonic boundaries has the potential to. Mass independent fractionation of sulfur (MIF-S) is a signature (quantified as Δ33S and Δ36S) that is unique to the Archean sedimentary rock record and imparted to sulfur reservoirs that interacted with the oxygen-poor atmosphere before the Great Oxidation Event (GOE) at ca. 2.4 Ga. Here we present multiple sulfur isotopes from across a Proterozoic post-GOE orogenic belt, formed when Archean cratons were stitched together during supercontinent amalgamation. For the first time, multiple sulfur isotope data are presented spatially to elucidate volatile pathways across lithospheric blocks. Across the orogenic belt, the Proterozoic granitoid and hydrothermal rock records proximal to Archean cratons preserve values of Δ33S up to +0.8\\permil and a Δ33S-Δ36S array of -1.2, whereas magmatic and hydrothermal systems located more distally from the margin do not display any evidence of MIF-S. This is the first study to identify MIF-S in a Proterozoic orogen indicates that tectonic processes controlling lithospheric evolution and crust formation at tectonic boundaries are able to transfer sulfur from Archean supracrustal rock reservoirs to newly formed Proterozoic granitoid crust. The observation of MIF-S in the Proterozoic granitoid rock record has the potential to revolutionise our understanding of secular changes in the evolution of crust formation mechanisms through time.

  20. Sulfuric acid on Europa and the radiolytic sulfur cycle.

    PubMed

    Carlson, R W; Johnson, R E; Anderson, M S

    1999-10-01

    A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

  1. Sulfuric acid on Europa and the radiolytic sulfur cycle

    NASA Technical Reports Server (NTRS)

    Carlson, R. W.; Johnson, R. E.; Anderson, M. S.

    1999-01-01

    A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

  2. Biochemistry of sulfur

    SciTech Connect

    Huxtable, R.J.; LaFranconi, W.M.

    1986-01-01

    This book presents information on the following topics: the chemistry of sulfur; the oxidation states of sulfur; the reduction of sulfate and the oxidation of sulfide; the sulfur cycle; oxidation of inorganic sulfide; the metabolism and functions of methionine; taurine and the oxidative metabolism of cysteine; thiols, disulfides, and thioesters; thioethers; thiamine; biotin; sulfates; inherited disorders of sulfur metabolism; cystinuria; sulfur and the metabolism of xenobiotics; general aspects of xenobiotic metabolism; glutathione and sulfation of xenobiotics; and metabolic activation as a result of sulfate conjugation.

  3. Sulfur tolerant anode materials

    SciTech Connect

    Not Available

    1987-02-01

    The goal of this program is the development of a molten carbonate fuel cell (MCFC) anode which is more tolerant of sulfur contaminants in the fuel than the current state-of-the-art nickel-based anode structures. This program addresses two different but related aspects of the sulfur contamination problem. The primary aspect is concerned with the development of a sulfur tolerant electrocatalyst for the fuel oxidation reaction. A secondary issue is the development of a sulfur tolerant water-gas-shift reaction catalyst and an investigation of potential steam reforming catalysts which also have some sulfur tolerant capabilities. These two aspects are being addressed as two separate tasks.

  4. Sulfur tolerant anode materials

    SciTech Connect

    Not Available

    1988-02-01

    The goal of this program is the development of a molten carbonate fuel cell (MCFC) anode which is more tolerant of sulfur contaminants in the fuel than the current state-of-the-art nickel-based anode structures. This program addresses two different but related aspects of the sulfur contamination problem. The primary aspect is concerned with the development of a sulfur tolerant electrocatalyst for the fuel oxidation reaction. A secondary issue is the development of a sulfur tolerant water-gas-shift reaction catalyst and an investigation of potential steam reforming catalysts which also have some sulfur tolerant capabilities. These two aspects are being addressed as two separate tasks.

  5. Atmospheric moisture's influence on fire behavior: surface moisture and plume dynamics.

    Treesearch

    Brian E. Potter; Joseph J. Charney; Lesley A. Fusina

    2006-01-01

    Nine measures of atmospheric surface moisture are tested for statistical relationships with fire size and number of fires using data from the Great Lakes region of the United States. The measures include relative humidity, water vapor mixing ratio, mixing ratio deficit, vapor pressure, vapor pressure deficit, dew point temperature, dew point depression, wet bulb...

  6. Numerical study of effects of atmosphere temperature profile on wildfire behavior

    Treesearch

    Chunmei Xia; M. Yousuff Hussaini; Philip Cunningham; Rodman R. Linn; Scott L. Goodrick

    2003-01-01

    The vertical temperature profile and hence the stability in the atmosphere near the ground vanes significantly between day and night. Typically, the potential temperature at the surface is higher than that above the ground during the day and lower than that above the ground during the night. Such differences in the vertical temperature profile might act to accelerate...

  7. ATMOSPHERIC MERCURY BEHAVIOR AT DIFFERENT ALTITUDES AT NY-ALESUND DURING SPRING 2003

    EPA Science Inventory

    Intensive field measurements of atmospheric mercury and related species were carried out in Ny Alesund, Spitsbergen during the spring of 2003 at two altitudes. Measurements were made at the Italian research station Dirigibile Italia (12m a.s.l.) and on the top of Zeppelin Mountai...

  8. ATMOSPHERIC MERCURY BEHAVIOR AT DIFFERENT ALTITUDES AT NY-ALESUND DURING SPRING 2003

    EPA Science Inventory

    Intensive field measurements of atmospheric mercury and related species were carried out in Ny Alesund, Spitsbergen during the spring of 2003 at two altitudes. Measurements were made at the Italian research station Dirigibile Italia (12m a.s.l.) and on the top of Zeppelin Mountai...

  9. Sulfuric Acid on Europa

    NASA Image and Video Library

    1999-09-30

    Frozen sulfuric acid on Jupiter's moon Europa is depicted in this image produced from data gathered by NASA's Galileo spacecraft. The brightest areas, where the yellow is most intense, represent regions of high frozen sulfuric acid concentration. Sulfuric acid is found in battery acid and in Earth's acid rain. This image is based on data gathered by Galileo's near infrared mapping spectrometer. Europa's leading hemisphere is toward the bottom right, and there are enhanced concentrations of sulfuric acid in the trailing side of Europa (the upper left side of the image). This is the face of Europa that is struck by sulfur ions coming from Jupiter's innermost moon, Io. The long, narrow features that crisscross Europa also show sulfuric acid that may be from sulfurous material extruded in cracks. http://photojournal.jpl.nasa.gov/catalog/PIA02500

  10. Influence of Nitrogen Gas Flow Rate on the Electrical Behavior of an Atmospheric Pressure Dielectric Barrier Jet Discharge

    SciTech Connect

    Choo, C. Y.; Chin, O. H.

    2011-03-30

    The dielectric barrier discharge configuration used consists of a hemispherical electrode insulated by 1 mm thick borosilicate glass and a grounded plate with a hole through which the jet is formed externally in the surrounding air. The effect of gas flow rate on the behavior of an atmospheric pressure dielectric barrier jet discharge was studied for different air-gap distance and drive voltage, V{sub DD}, to the MOSFET. It is found that at higher rate of nitrogen gas flow, the current spikes reduce in number when the driving voltage and air-gap distance are kept constant.

  11. Characterization of Atmospheric Aerosol Behavior and Climatic Effects by Analysis of SAGE 2 and Other Space, Air, and Ground Measurements

    NASA Technical Reports Server (NTRS)

    Livingston, John M.

    1999-01-01

    This report documents the research performed under NASA Ames Cooperative Agreement NCC 2-991, which covered the period 1 April 1997 through 31 March 1999. Previously, an interim technical report (Technical Report No. 1, 20 March 1998) summarized the work completed during the period 1 April 1997 through 31 March 1998. The objective of the proposed research was to advance our understanding of atmospheric aerosol behavior, aerosol-induced climatic effects, and the remote measurement and retrieval capabilities of spaceborne sensors such as SAGE II by combining and comparing data from these instruments and from airborne and ground-based instruments.

  12. The Abundance of Sulfur in Venus Magmas

    NASA Astrophysics Data System (ADS)

    Bullock, M. A.; Grinspoon, D. H.

    1999-09-01

    Outgassing of sulfur gases due to volcanism within the past 100 My on Venus is probably responsible for the planet's globally encircling H2SO4 cloud layers. Dramatic changes in volcanic output on Venus would have altered the atmospheric inventory of sulfur gases, and hence the structure of its clouds (Bullock and Grinspoon, Icarus, submitted 1999). Although Magellan radar images provide some constraints on the magnitude of volcanism in the geologically recent past, little is known of the sulfur content of Venus lavas. In order to assess the effects that Venus' volcanic history may have had on cloud and therefore climate change, it is desirable to place some constraints on the abundance of sulfur in Venus magmas. The sulfur content of terrestrial volcanic lavas varies widely, depending upon the local sedimentary environment and the source and history of upwelling magmas. We estimate the average abundance of sulfur in Venus lavas from an analysis of the production and loss of atmospheric SO2. The volumetric rate of resurfacing on Venus in the recent past is approximately 0.1 to 2 km3/yr (Bullock et al., JGR 20, 1993, Basilevsky and Head, GRL 23, 1996). Outgassed SO2 reacts quickly with crustal carbonate -- residence times in the atmosphere with respect to the reaction SO2 + CaCO3 <=> CaSO4 + CO are about 2-30 My (Fegley and Prinn, Nature 337, 1989, Bullock and Grinspoon, Icarus, submitted 1999). Assuming steady state conditions and an abundance of 25-180 ppm of atmospheric SO2 (Oyama et al., JGR 85, 1980, Bertaux et al., JGR 101, 1996), we will discuss constraints on the abundance of this important greenhouse and cloud-precursor gas in Venus lavas.

  13. REGIONAL TRENDS IN RURAL SULFUR CONCENTRATIONS

    EPA Science Inventory

    This paper presents an analysis of trends in atmospheric concentrations of sulfur dioxide (SO,) and particulate sulfate (SO42-) at rural monitoring sites in the Clean Air Act Status and Trends Monitoring Network (CASTNet) from 1990 to 1999. A two-stage approach is used to estimat...

  14. REGIONAL TRENDS IN RURAL SULFUR CONCENTRATIONS

    EPA Science Inventory

    This paper presents an analysis of trends in atmospheric concentrations of sulfur dioxide (SO,) and particulate sulfate (SO42-) at rural monitoring sites in the Clean Air Act Status and Trends Monitoring Network (CASTNet) from 1990 to 1999. A two-stage approach is used to estimat...

  15. Biotic and abiotic carbon to sulfur bond cleavage

    SciTech Connect

    Frost, J.W.

    1991-01-01

    Cleavage of aliphatic organosulfonate carbon to sulfur (C-S) bonds, a critical link in the global biogeochemical sulfur cycle, has been identified in Escherichia coli K-12. Enormous quantities of inorganic sulfate are continuously converted (Scheme I) into methanesulfonic acid 1 and acylated 3-(6-sulfo-{alpha}-D-quinovopyranosyl)-L-glycerol 2. Biocatalytic desulfurization (Scheme I) of 1 and 2, which share the structural feature of an aliphatic carbon bonded to a sulfonic acid sulfur, completes the cycle, Discovery of this desulfurization in E. coli provides an invaluable paradigm for study of a biotic process which, via the biogeochemical cycle, significantly influences the atmospheric concentration of sulfur-containing molecules.

  16. Temporal behavior of the SO 1.707 μm ro-vibronic emission band in Io's atmosphere

    NASA Astrophysics Data System (ADS)

    Laver, Conor; de Pater, Imke; Roe, Henry; Strobel, Darrell F.

    2007-08-01

    We report observations of the ro-vibronic aΔ→XΣ transition of SO at 1.707 μm on Io. These data were taken while Io was eclipsed by Jupiter, on four nights between July 2000 and March 2003. We analyze these results in conjunction with a previously published night to investigate the temporal behavior of these emissions. The observations were all conducted using the near-infrared spectrometer NIRSPEC on the W.M. Keck II telescope. The integrated emitted intensity for this band varies from 0.8×10 to 2.4×10 photons/s, with a possible link to variations in Loki's infrared brightness. The band-shapes imply rotational temperatures of 550-1000 K for the emitting gas, lending further evidence to a volcanic origin for sulfur monoxide. An attempt to detect the BΣ→XΣ transition of SO at 0.97 μm was unsuccessful; simultaneous detection with the 1.707 μm band would permit determination of the SO column abundance.

  17. Hot Corrosion Resistance and Mechanical Behavior of Atmospheric Plasma Sprayed Conventional and Nanostructured Zirconia Coatings

    NASA Astrophysics Data System (ADS)

    Saremi, Mohsen; Keyvani, Ahmad; Heydarzadeh Sohi, Mahmoud

    Conventional and nanostructured zirconia coatings were deposited on In-738 Ni super alloy by atmospheric plasma spray technique. The hot corrosion resistance of the coatings was measured at 1050°C using an atmospheric electrical furnace and a fused mixture of vanadium pent oxide and sodium sulfate respectively. According to the experimental results nanostructured coatings showed a better hot corrosion resistance than conventional ones. The improved hot corrosion resistance could be explained by the change of structure to a dense and more packed structure in the nanocoating. The evaluation of mechanical properties by nano indentation method showed the hardness (H) and elastic modulus (E) of the YSZ coating increased substantially after hot corrosion.

  18. PMP-1: A coordinated study of the behavior of the middle atmosphere in winter

    NASA Technical Reports Server (NTRS)

    Labitzke, K.

    1982-01-01

    The following observations of the middle atmosphere were available regularly: radiosonde data distributed through arrangements made by the World Meteorological Organization (WMO); radiosonde data; and the infrared radiances of the SSU (stratospheric sounding unit onboard the operational NOAA satellites). Other data of more experimental nature which are or will become available are, data from the Nimbus-7 satellite, especially from the Stratosphere and Mesospheric Sounder (SAMS) and the Limb Infrared Monitor of the Stratosphere (LIMS), but only for the winter of 1978 to 1979. These data are collected and integrated into the large-scale meteorological field analysis. Parameters necessary for the understanding of the large-scale dynamics of the middle atmosphere are derived.

  19. Erosion behavior of composite Al-Cr cathodes in cathodic arc plasmas in inert and reactive atmospheres

    SciTech Connect

    Franz, Robert Mendez Martin, Francisca; Hawranek, Gerhard; Polcik, Peter

    2016-03-15

    Al{sub x}Cr{sub 1−x} composite cathodes with Al contents of x = 0.75, 0.5, and 0.25 were exposed to cathodic arc plasmas in Ar, N{sub 2}, and O{sub 2} atmospheres and their erosion behavior was studied. Cross-sectional analysis of the elemental distribution of the near-surface zone in the cathodes by scanning electron microscopy revealed the formation of a modified layer for all cathodes and atmospheres. Due to intermixing of Al and Cr in the heat-affected zone, intermetallic Al-Cr phases formed as evidenced by x-ray diffraction analysis. Cathode poisoning effects in the reactive N{sub 2} and O{sub 2} atmospheres were nonuniform as a result of the applied magnetic field configuration. With the exception of oxide islands on Al-rich cathodes, reactive layers were absent in the circular erosion zone, while nitrides and oxides formed in the less eroded center region of the cathodes.

  20. Hygroscopic behavior of atmospherically relevant water-soluble carboxylic salts and their influence on the water uptake of ammonium sulfate

    NASA Astrophysics Data System (ADS)

    Wu, Z. J.; Nowak, A.; Poulain, L.; Herrmann, H.; Wiedensohler, A.

    2011-12-01

    The hygroscopic behavior of atmospherically relevant water-soluble carboxylic salts and their effects on ammonium sulfate were investigated using a hygroscopicity tandem differential mobility analyzer (H-TDMA). No hygroscopic growth is observed for disodium oxalate, while ammonium oxalate shows slight growth (growth factor = 1.05 at 90%). The growth factors at 90% RH for sodium acetate, disodium malonate, disodium succinate, disodium tartrate, diammonium tartrate, sodium pyruvate, disodium maleate, and humic acid sodium salt are 1.79, 1.78, 1.69, 1.54, 1.29, 1.70, 1.78, and 1.19, respectively. The hygroscopic growth of mixtures of organic salts with ammonium sulfate, which are prepared as surrogates of atmospheric aerosols, was determined. A clear shift in deliquescence relative humidity to lower RH with increasing organic mass fraction was observed for these mixtures. Above 80% RH, the contribution to water uptake by the organic salts was close to that of ammonium sulfate for the majority of investigated compounds. The observed hygroscopic growth of the mixed particles at RH above the deliquescence relative humidity of ammonium sulfate agreed well with that predicted using the Zdanovskii-Stokes-Robinson (ZSR) mixing rule. Mixtures of ammonium sulfate with organic salts are more hygroscopic than mixtures with organic acids, indicating that neutralization by gas-phase ammonia and/or association with cations of dicarbonxylic acids may enhance the hygroscopicity of the atmospheric particles.

  1. Comparative evaluation of thermal decomposition behavior and thermal stability of powdered ammonium nitrate under different atmosphere conditions.

    PubMed

    Yang, Man; Chen, Xianfeng; Wang, Yujie; Yuan, Bihe; Niu, Yi; Zhang, Ying; Liao, Ruoyu; Zhang, Zumin

    2017-09-05

    In order to analyze the thermal decomposition characteristics of ammonium nitrate (AN), its thermal behavior and stability under different conditions are studied, including different atmospheres, heating rates and gas flow rates. The evolved decomposition gases of AN in air and nitrogen are analyzed with a quadrupole mass spectrometer. Thermal stability of AN at different heating rates and gas flow rates are studied by differential scanning calorimetry, thermogravimetric analysis, paired comparison method and safety parameter evaluation. Experimental results show that the major evolved decomposition gases in air are H2O, NH3, N2O, NO, NO2 and HNO3, while in nitrogen, H2O, NH3, NO and HNO3 are major components. Compared with nitrogen atmosphere, lower initial and end temperatures, higher heat flux and broader reaction temperature range are obtained in air. Meanwhile, higher air gas flow rate tends to achieve lower reaction temperature and to reduce thermal stability of AN. Self-accelerating decomposition temperature of AN in air is much lower than that in nitrogen. It is considered that thermostability of AN is influenced by atmosphere, heating rate and gas flow rate, thus changes of boundary conditions will influence its thermostability, which is helpful to its safe production, storage, transportation and utilization. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Corrosion Behavior of Fe41Co7Cr15Mo14C15B6Y2 Bulk Metallic Glass in Sulfuric Acid Solutions

    NASA Astrophysics Data System (ADS)

    Fan, H. B.; Zheng, W.; Wang, G. Y.; Liaw, P. K.; Shen, J.

    2011-06-01

    An Fe41Co7Cr15Mo14C15B6Y2 bulk metallic glass with a diameter of 5 mm was prepared with the copper-mold-casting method. The corrosion resistance of this amorphous steel in sulfuric-acid solutions was determined by electrochemical measurements. The passive film formed on the surface of the alloy after immersion in the 0.5-mol/l H2SO4 solution for 1 week was analyzed by X-ray photoelectron spectroscopy (XPS). Electrochemical measurements show that the corrosion resistance of the amorphous steel in the 1 mol/l-H2SO4 solution is superior to a stainless steel (SUS 321), and is almost the same as Ti6Al4V, which shows that the amorphous steel has an excellent corrosion resistance in sulfuric-acid solutions. As the concentration of the sulfuric-acid solutions increases from 0.5 mol/l to 4 mol/l, the corrosion resistance of the amorphous steel decreases. The XPS result reveals that a bilayer structure of protective film formed on the surface of the amorphous steel in a H2SO4 solution. The compositions of the inner part of the film are MoO2, Cr2O3, CoO, and FeO, and those of the outer film are MoO3, Cr(OH)3, Co(OH)2, and Fe(OH)3.

  3. Behavior of Listeria monocytogenes in Sliced Ready-to-Eat Meat Products Packaged under Vacuum or Modified Atmosphere Conditions.

    PubMed

    Menéndez, Rosa Ana; Rendueles, Eugenia; Sanz, José Javier; Capita, Rosa; García-Fernández, Camino

    2015-10-01

    The objective of this research was to determine the behavior of Listeria monocytogenes in three types of sliced ready-to-eat meat products packaged under vacuum or modified atmosphere conditions and stored at three temperatures. Slices of about 25 g of chorizo (a fermented dry pork sausage), jamón (cured ham), and cecina (a salted, dried beef product) were inoculated with L. monocytogenes NCTC 11994. Slices were packaged in a vacuum or in a modified atmosphere (20% CO2, 80% N2). After packaging, samples were stored for 6 months at three temperatures: 3, 11, or 20°C. Microbiological analyses were performed after 0, 1, 7, 15, 30, 45, 90, and 180 days of storage. The type of meat product, the type of packaging, the temperature, and the day of storage all influenced microbial levels (P < 0.001). L. monocytogenes counts decreased throughout the course of storage in samples of chorizo (quick decrease) and jamón (gradual decrease). In cecina samples, counts of L. monocytogenes increased from day 0 to day 1 of storage and then remained constant until day 90 of the study. These results may be of use for enhancing the safety of these ready-to-eat meat product types. Additional evaluation of the behavior of L. monocytogenes in cecina is needed.

  4. Simulating Fine-Scale Atmospheric Processes: A New Core Capability and its Application to Predicting Wildfire Behavior

    SciTech Connect

    Bradley, M M; Leach, M J; Molenkamp, C R; Hall, C H; Wilder, L; Neher, L A

    2003-02-07

    This LDRD project consisted of the development, testing, and prototype application of a new capability to couple atmospheric models of different spatial and temporal scales with a state-of-the-science vegetation-fuel combustion model and a GIs-based analysis system. The research addressed the complex, multi-scale interactions of atmospheric processes, combustion, and vegetative fuel conditions, using a suite of models to simulate their impact on wildfire behavior in areas of complex terrain. During the course of the project, we made substantial progress toward the implementation of a world-class modeling system that could be used as a tool for wildfire risk assessment, wildfire consequence analysis, wildfire suppression planning, fuels management, firefighter training, and public fire-safety education. With one additional year of funding we would have been able conduct combined modeling and field experiments to evaluate the models capability to predict the behavior of prescribed burns before they are ignited. Because of its investment in this LDRD project, LLNL is very close to having a new core capability--likely the world's most generally applicable, most scientifically sound, and most respected wildfire simulation system.

  5. Sulfuric acid in the Venus clouds.

    NASA Technical Reports Server (NTRS)

    Sill, G. T.

    1972-01-01

    The extremely dry nature of the Venus upper atmosphere appears to demand the presence of an efficient desiccating agent as the chief constituent of the clouds of Venus. On the basis of polarization measures it is to be expected that this substance is present as spherical droplets, 1 to 2 microns in diameter, with a refractive index n of 1.46 plus or minus 0.02 at 3500A in the observed region of the atmosphere, with T about equal to 235 K. This substance must have ultraviolet, visible, and infrared reflection properties not inconsistent with the observed spectrum of Venus. Sulfuric acid, of about 86% by weight composition, roughly fulfills the first of these properties. The visible and ultraviolet transmission features of a thin layer of elemental bromine and hydrobromic acid dissolved in sulfuric acid somewhat resemble the Venus spectrum, up to 14 microns. The chemical process postulated for forming sulfuric acid involves the oxidation of sulfur and its compounds to sulfuric acid through the agency of elemental bromine produced by the photolytic decomposition of hydrogen bromide.

  6. Sulfuric acid in the Venus clouds.

    NASA Technical Reports Server (NTRS)

    Sill, G. T.

    1972-01-01

    The extremely dry nature of the Venus upper atmosphere appears to demand the presence of an efficient desiccating agent as the chief constituent of the clouds of Venus. On the basis of polarization measures it is to be expected that this substance is present as spherical droplets, 1 to 2 microns in diameter, with a refractive index n of 1.46 plus or minus 0.02 at 3500A in the observed region of the atmosphere, with T about equal to 235 K. This substance must have ultraviolet, visible, and infrared reflection properties not inconsistent with the observed spectrum of Venus. Sulfuric acid, of about 86% by weight composition, roughly fulfills the first of these properties. The visible and ultraviolet transmission features of a thin layer of elemental bromine and hydrobromic acid dissolved in sulfuric acid somewhat resemble the Venus spectrum, up to 14 microns. The chemical process postulated for forming sulfuric acid involves the oxidation of sulfur and its compounds to sulfuric acid through the agency of elemental bromine produced by the photolytic decomposition of hydrogen bromide.

  7. Behavior of Particulate Mercury in the Bulk Atmospheric Aerosols Simultaneously Collected at 2 Sites in Okinawa, Japan

    NASA Astrophysics Data System (ADS)

    Miyagi, Y.; Arakaki, T.; Azechi, S.; Somada, Y.; Oshiro, Y.; Tsuhako, A.; Murayama, H.; Tanahara, A.

    2013-12-01

    Mercury is toxic to animals. Mercury is emitted to the atmosphere mainly from two sources; natural and anthropogenic sources. Natural sources include volcanic eruption, forest fire and so on. Anthropogenic sources include fossil fuel combustion, metal and cement production and so on. There are three forms of mercury in the atmosphere: gaseous elemental mercury, reactive gaseous mercury and particulate mercury. Gaseous elemental mercury is the most abundant form in the atmosphere, and has long atmospheric lifetime, ca. a few years. This study focuses on particulate mercury, which has a relatively short lifetime, ca. a few days, in the atmosphere because it reflects characteristics of nearby emission sources. Objectives of this study were to elucidate the behavior of particulate mercury in aerosols and to understand relationships between mercury and other metals and water-soluble anions. Aerosol samples were collected at two sites; Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS, Jan.2008-Nov.2012), northern tip of Okinawa island, and University of the Ryukyus (UR, Jan.2008-Nov.2012), central and more populated area of Okinawa island. They were collected by using identical high-volume air samplers on quartz filters. Concentrations of particulate mercury in aerosols were determined by using a MA-3000 (Nippon Instruments Corporation). The results showed that particulate Hg concentrations were mostly higher for the aerosols collected at UR site than those at CHAAMS site, suggesting locally emitted Hg. Samples collected at UR showed clear seasonal variation, the lowest in summer and the highest winter. On the other hand, the CHAAMS samples showed lower concentration in winter and higher concentration in summer, but the difference was relatively small. Both UR and CHAAMS samples had similar concentration levels in summer season. Back trajectory analysis showed that particulate Hg at CHAAMS site during summer was not from Asian continent. Since samples

  8. Sulfur "Concrete" for Lunar Applications - Sublimation Concerns

    NASA Technical Reports Server (NTRS)

    Grugel, Richard N.; Toutanji, Houssam

    2006-01-01

    Melting sulfur and mixing it with an aggregate to form "concrete" is commercially well established and constitutes a material that is particularly well-suited for use in corrosive environments. Discovery of the mineral troilite (FeS) on the moon poses the question of extracting the sulfur for use as a lunar construction material. This would be an attractive alternative to conventional concrete as it does not require water. However, the viability of sulfur concrete in a lunar environment, which is characterized by lack of an atmosphere and extreme temperatures, is not well understood. Here it is assumed that the lunar ore can be mined, refined, and the raw sulfur melded with appropriate lunar regolith to form, for example, bricks. This study evaluates pure sulfur and two sets of small sulfur concrete samples that have been prepared using JSC-1 lunar stimulant and SiO2 powder as aggregate additions. Each set was subjected to extended periods in a vacuum environment to evaluate sublimation issues. Results from these experiments are presented and discussed within the context of the lunar environment.

  9. Sulfur "Concrete" for Lunar Applications - Sublimation Concerns

    NASA Technical Reports Server (NTRS)

    Grugel, Richard N.; Toutanji, Houssam

    2006-01-01

    Melting sulfur and mixing it with an aggregate to form "concrete" is commercially well established and constitutes a material that is particularly well-suited for use in corrosive environments. Discovery of the mineral troilite (FeS) on the moon poses the question of extracting the sulfur for use as a lunar construction material. This would be an attractive alternative to conventional concrete as it does not require water. However, the viability of sulfur concrete in a lunar environment, which is characterized by lack of an atmosphere and extreme temperatures, is not well understood. Here it is assumed that the lunar ore can be mined, refined, and the raw sulfur melded with appropriate lunar regolith to form, for example, bricks. This study evaluates pure sulfur and two sets of small sulfur concrete samples that have been prepared using JSC-1 lunar stimulant and SiO2 powder as aggregate additions. Each set was subjected to extended periods in a vacuum environment to evaluate sublimation issues. Results from these experiments are presented and discussed within the context of the lunar environment.

  10. Behaviors of trace elements in Neoarchean and Paleoproterozoic paleosols: Implications for atmospheric oxygen evolution and continental oxidative weathering

    NASA Astrophysics Data System (ADS)

    Murakami, Takashi; Matsuura, Kei; Kanzaki, Yoshiki

    2016-11-01

    The behaviors of redox-sensitive and/or bio-essential trace elements in Neoarchean and Paleoproterozoic paleosols (ancient weathering profiles) were investigated to better understand atmospheric oxygen evolution. The loss or retention of individual trace elements in the paleosols can show how continental oxidative weathering, and thus atmospheric oxygen evolution, took place against age mainly due to their various redox potentials. The V, Cr, Ni, Cu, Zn and Mo concentrations of two Paleoproterozoic paleosols were measured by inductively coupled plasma optical emission spectrometry and mass spectrometry, and those, as well as Co, W and U concentrations, of nine Neoarchean and Paleoproterozoic paleosols were obtained from the literature. The trace element behaviors were constrained by their degrees of loss or retention in the paleosols. We applied two methods to the estimation: (i) retention fraction of element M (a mass ratio of element M of paleosol to parent rock using immobile elements such as Ti) and (ii) element-element (in particular, Si-element) correlations at different profile depths of a paleosol. There are two distinct groups in trace element behavior in the Neoarchean and Paleoproterozoic paleosols: Co, Ni, Zn and W were lost from weathering profiles until the early Paleoproterozoic but retained in the middle and late Paleoproterozoic, while V, Cr, Cu, Mo and U were retained in the profiles until the early Paleoproterozoic or slightly later but lost from the profiles in the middle and late Paleoproterozoic. More precisely, the timings of such loss and retention were different between trace elements during the Paleoproterozoic. The characteristics of these changes from retention to loss or from loss to retention indicate that the changes occurred and lasted throughout the Paleoproterozoic. The trace element behaviors, accordingly, suggest that continental weathering became oxidative progressively with age during almost the whole Paleoproterozoic, and thus

  11. Comparative analysis of the mechanisms of sulfur anion oxidation and reduction by dsr operon to maintain environmental sulfur balance.

    PubMed

    Ghosh, Semanti; Bagchi, Angshuman

    2015-12-01

    Sulfur metabolism is one of the oldest known redox geochemical cycles in our atmosphere. These redox processes utilize different sulfur anions and the reactions are performed by the gene products of dsr operon from phylogenetically diverse sets of microorganisms. The operon is involved in the maintenance of environmental sulfur balance. Interestingly, the dsr operon is found to be present in both sulfur anion oxidizing and reducing microorganisms and in both types of organisms DsrAB protein complex plays a vital role. Though there are various reports regarding the genetics of dsr operon there are practically no reports dealing with the structural aspects of sulfur metabolism by dsr operon. In our present study, we tried to compare the mechanisms of sulfur anion oxidation and reduction by Allochromatium vinosum and Desulfovibrio vulgaris respectively through DsrAB protein complex. We analyzed the modes of bindings of sulfur anions to the DsrAB protein complex and observed that for sulfur anion oxidizers, sulfide and thiosulfate are the best substrates whereas for reducers sulfate and sulfite have the best binding abilities. We analyzed the binding interaction pattern of the DsrA and DsrB proteins while forming the DsrAB protein complexes in Desulfovibrio vulgaris and Allochromatium vinosum. To our knowledge this is the first report that analyzes the differences in binding patterns of sulfur substrates with DsrAB protein from these two microorganisms. This study would therefore be essential to predict the biochemical mechanism of sulfur anion oxidation and reduction by these two microorganisms i.e., Desulfovibrio vulgaris (sulfur anion reducer) and Allochromatium vinosum (sulfur anion oxidizer). Our observations also highlight the mechanism of sulfur geochemical cycle which has important implications in future study of sulfur metabolism as it has a huge application in waste remediation and production of industrial bio-products viz. vitamins, bio-polyesters and bio-hydrogen.

  12. The global sulfur cycle

    NASA Technical Reports Server (NTRS)

    Sagan, D. (Editor)

    1985-01-01

    The results of the planetary biology microbial ecology's 1984 Summer Research Program, which examined various aspects of the global sulfur cycle are summarized. Ways in which sulfur flows through the many living and chemical species that inhabit the surface of the Earth were investigated. Major topics studied include: (1) sulfur cycling and metabolism of phototropic and filamentous sulfur bacteria; (2) sulfur reduction in sediments of marine and evaporite environments; (3) recent cyanobacterial mats; (4) microanalysis of community metabolism in proximity to the photic zone in potential stromatolites; and (5) formation and activity of microbial biofilms on metal sulfides and other mineral surfaces. Relationships between the global sulfur cycle and the understanding of the early evolution of the Earth and biosphere and current processes that affect global habitability are stressed.

  13. Investigation of the effects of nonhomogeneous (or nonstationary) behavior on the spectra of atmospheric turbulence

    NASA Technical Reports Server (NTRS)

    Mark, W. D.; Fischer, R. W.

    1976-01-01

    A new series expansion of the instantaneous power spectrum is used that has for its first term the usual quasi-stationary spectrum approximation. The minimum duration of a burst of turbulence and the minimum rise time of an abrupt onset of turbulence that will not give rise to changes in the spectrum due to the nonstationary behavior are determined. A general criterion for envelope behavior that will not give rise to changes in the spectrum is also determined. Spectra computed from recorded turbulence time histories are shown to be consistent with the theoretical predictions.

  14. Sulfur removal from coal

    SciTech Connect

    Lompa-Krzymien, L.

    1985-01-01

    Coal is treated to remove both pyritic and organic sulfur by contacting with an aqueous solution comprising cupric ions at temperatures of about 140/sup 0/ C.-200/sup 0/ C. under autogenic pressure, until substantial amounts of the sulfur are solubilized, separating the coal solids, and washing the solids with water to remove soluble forms of sulfur, iron and copper therefrom. The copper can be recovered and recycled as a cupric salt.

  15. Corona-like atmospheric escape from KBOs. II. The behavior of aerosols

    NASA Astrophysics Data System (ADS)

    Levi, Amit; Podolak, Morris

    2009-10-01

    In Levi and Podolak (Levi, A., Podolak, M. [in press] Icarus) we applied the theory of coronal expansion to gas escape from a small, cold, object such as those found in the Kuiper belt. Here we extend the theory to include aerosols that are lifted off the surface by the escaping gas. Aerosols carried by the gas but still gravitationally bound, tend to be lifted to a height above the surface that is dependent on the aerosol radius, so that in steady state the variation of aerosol radius with height is well-defined. We develop an extension of Parker's coronal flow theory to include the effect of aerosols carried along by the gas and use this to estimate the optical depth of such an atmosphere. For KBOs with CO evaporation from the surface and with radii in the range 245-334 km, line-of-site optical depths through the atmosphere can exceed one at heights of a few hundred kilometers above the surface. Such aerosol layers should be observable, and might be used to infer the flow proprieties of the escaping gas.

  16. Low-frequency nonlinearity and regime behavior in the Northern Hemisphere extratropical atmosphere

    NASA Astrophysics Data System (ADS)

    Hannachi, Abdel.; Straus, David M.; Franzke, Christian L. E.; Corti, Susanna; Woollings, Tim

    2017-03-01

    The extratropical atmosphere is characterized by robust circulations which have time scales longer than that associated with developing baroclinic systems but shorter than a season. Such low-frequency variability is governed to a large extent by nonlinear dynamics and, hence, is chaotic. A useful aspect of this low-frequency circulation is that it can often be described by just a few quasi-stationary regime states, broadly defined as recurrent or persistent large-scale structures, that exert a significant impact on the probability of experiencing extreme surface weather conditions. We review a variety of techniques for identifying circulation regimes from reanalysis and numerical model output. While various techniques often yield similar regime circulation patterns, they offer different perspectives on the regimes. The regimes themselves are manifest in planetary scale patterns. They affect the structure of synoptic scale patterns. Extratropical flow regimes have been identified in simplified atmospheric models and comprehensive coupled climate models and in reanalysis data sets. It is an ongoing challenge to accurately model these regime states, and high horizontal resolutions are often needed to accurately reproduce them. The regime paradigm helps to understand the response to external forcing on a variety of time scales, has been helpful in categorizing a large number of weather types and their effect on local conditions, and is useful in downscaling. Despite their usefulness, there is a debate on the "nonequivocal" and systematic existence of these nonlinear circulation regimes. We review our current understanding of the nonlinear and regime paradigms and suggest future research.

  17. Multiple sulfur isotopes and the evolution of Earth's surface sulfur cycle

    NASA Astrophysics Data System (ADS)

    Johnston, David T.

    2011-05-01

    The distribution of sulfur isotopes in geological materials reveals information about Earth history and biogeochemical processes. Research during the last several decades has used sulfur isotope geochemistry as a tool to better understand microbial processes ( Harrison and Thode, 1958; Kaplan, 1975; Monster et al., 1979; Peck, 1959, 1962; Rees, 1973) and sediment diagenesis ( Berner, 1969, 1982; Canfield et al., 1993b). Earth historians also realized this potential, as there exists a rich record of environmental change within the sedimentary records ( Canfield and Teske, 1996; Claypool et al., 1980; Goodwin et al., 1976; Habicht et al., 2002; Kah et al., 2004; Monster et al., 1979; Shen et al., 2001; Strauss, 1993; Thode and Goodwin, 1983). These applications have championed the use of the two most abundant sulfur isotopes [ 32S and 34S], and provide a rich introduction to what the sulfur isotope record has to offer [see ( Canfield, 2004; Canfield and Raiswell, 1999)]. Within the last decade, this information has been supplemented by new data derived from the less abundant isotopes [ 33S and 36S]. The measurement of all four stable sulfur isotopes - multiple sulfur isotope geochemistry - has expanded our understanding of biological evolution and activity, atmospheric chemistry and transport, crustal recycling, and many more fields related to Earth surface processes [see ( Farquhar and Wing, 2003)]. Here, I present a review of recent works in multiple sulfur isotope geochemistry with a focus on results that inform our understanding of biogeochemical processes and Earth surface evolution.

  18. Microwave Characterization of Propiolic Sulfuric Anhydride and Two Conformers of Acrylic Sulfuric Anhydride

    NASA Astrophysics Data System (ADS)

    Smith, CJ; Huff, Anna; Mackenzie, Becca; Leopold, Ken

    2017-06-01

    Sulfur trioxide reacts with propiolic acid and acrylic acid to form propiolic sulfuric anhydride (HC\\equivC-COOSO_{2}OH) and acrylic sulfuric anhydride (H_{2}C=CH-COOSO_{2}OH), respectively. Both species have been observed by chirped-pulse and conventional cavity microwave spectroscopy. In the case of acrylic acid, two conformers derived from the cis and trans form of the acid have been observed. The reaction mechanism and energetics are investigated by density functional theory and CCSD calculations. These results add to a growing body of evidence that establishes carboxylic sulfuric anhydrides, RCOOSO_{2}OH, as a class of molecules formed readily from SO_{3} + RCOOH in the gas phase and which, therefore, may be of significance in the nucleation and growth of atmospheric aerosol particles.

  19. Decoupling the Impacts of Heterotrophy and Autotrophy on Sulfuric Acid Speleogenesis

    NASA Astrophysics Data System (ADS)

    Jones, A. A.; Bennett, P.

    2013-12-01

    Within caves such as Movile Caves (Romania), the Frasassi Caves (Italy), and Lower Kane Cave (LKC, Wyoming, USA) the combination of abiotic autoxidation and microbiological oxidation of H2S produces SO42- and H+ that promotes limestone dissolution through sulfuric-acid speleogenesis (SAS). Microbial sulfide oxidation by sulfur-oxidizing bacteria (SOB) has been shown recently to be the dominant process leading to speleogenesis in these caves. However, due to the inherently large diversity of microbial communities within these environments, there are a variety of metabolic pathways that can impact limestone dissolution and carbon cycling to varying degrees. In order to investigate these variations we outfitted a continuous flow bioreactor with a Picarro Wavelength-Scanned Cavity Ring Down Spectrometer (WS-CRDS) that continuously monitored and logged 12CO2 and 13CO2 at ppmv sensitivity and isotope ratios at <0.3‰ precision in simulated cave atmospheres. Bioreactors containing Madison Limestone were inoculated with either a monoculture of the mixotrophic sulfur-oxidizing Thiothrix unzii or a mixed environmental (LKC) sulfur-metabolizing community. Ca2+ and pH were also continuously logged in order to quantify the impact of microbial metabolism on limestone dissolution rate. We found an order of magnitude of variability in limestone dissolution rates that were closely tied to microbial metabolism. In monocultures, limestone dissolution was inhibited by excessive reduced sulfur as T. unzii prefers to store sulfur internally as So under these conditions, generating no acidity. The headspace was depleted in 13C when sulfur was being stored as So and enriched in 13C when sulfur was being converted to SO42-. This suggests a preference for a heterotrophy during periods of high sulfur input and autotrophy when sulfur input is low. This was corroborated by an increase in SO42- during low sulfide input and microscope images showed loss of internal sulfur within the filaments

  20. Corrosion behavior of Ni-Base alloys in a hot lithium molten salt under an oxidizing atmosphere

    NASA Astrophysics Data System (ADS)

    Cho, Soo-Haeng; Cho, Il-Je; You, Gil-Sung; Yoon, Ji-Sup; Park, Seong-Won

    2007-08-01

    The electrolytic reduction of a spent oxide fuel involves the liberation of the oxygen in molten LiCl electrolyte, which is a chemically aggressive environment that is excessively corrosive for typical structural materials. Accordingly, it is essential to choose the optimum material for the processing equipment that handles the molten salt. In this study, the corrosion behaviors of Haynes 263, Haynes 75, Inconel 718 and Inconel X-750 in a molten LiCl-Li2O salt under an oxidizing atmosphere were investigated at 650°C for 72 to 216 hrs. The Haynes 263 alloy showed the best corrosion resistance among the examined alloys. The corrosion products of Haynes 263 were Li(Ni,Co)O2 and LiTiO2; those of Haynes 75 were Cr2O3, NiFe2O4, LiNiO2 and Li2FiFe2O4; while Cr2O3, NiFe2O4 and CrNbO4 were identified as the corrosion products of Inconel 718. Inconel X-750 produced Cr2O3, NiFe2O4 and (Cr, Nb, Ti)O2 as its corrosion products. Haynes 263 showed a localized corrosion behavior while Haynes 75, Inconel 718 and Inconel X-750 showed a uniform corrosion behavior.