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Sample records for estimate atmospheric sulfur

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  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. 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.

  11. 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.

  12. 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

  13. New methodology for estimating biofuel consumption for cooking: Atmospheric emissions of black carbon and sulfur dioxide from India

    NASA Astrophysics Data System (ADS)

    Habib, Gazala; Venkataraman, Chandra; Shrivastava, Manish; Banerjee, Rangan; Stehr, J. W.; Dickerson, Russell R.

    2004-09-01

    The dominance of biofuel combustion emissions in the Indian region, and the inherently large uncertainty in biofuel use estimates based on cooking energy surveys, prompted the current work, which develops a new methodology for estimating biofuel consumption for cooking. This is based on food consumption statistics, and the specific energy for food cooking. Estimated biofuel consumption in India was 379 (247-584) Tg yr-1. New information on the user population of different biofuels was compiled at a state level, to derive the biofuel mix, which varied regionally and was 74:16:10%, respectively, of fuelwood, dung cake and crop waste, at a national level. Importantly, the uncertainty in biofuel use from quantitative error assessment using the new methodology is around 50%, giving a narrower bound than in previous works. From this new activity data and currently used black carbon emission factors, the black carbon (BC) emissions from biofuel combustion were estimated as 220 (65-760) Gg yr-1. The largest BC emissions were from fuelwood (75%), with lower contributions from dung cake (16%) and crop waste (9%). The uncertainty of 245% in the BC emissions estimate is now governed by the large spread in BC emission factors from biofuel combustion (122%), implying the need for reducing this uncertainty through measurements. Emission factors of SO2 from combustion of biofuels widely used in India were measured, and ranged 0.03-0.08 g kg-1 from combustion of two wood species, 0.05-0.20 g kg-1 from 10 crop waste types, and 0.88 g kg-1 from dung cake, significantly lower than currently used emission factors for wood and crop waste. Estimated SO2 emissions from biofuels of 75 (36-160) Gg yr-1 were about a factor of 3 lower than that in recent studies, with a large contribution from dung cake (73%), followed by fuelwood (21%) and crop waste (6%).

  14. 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.

  15. 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.

  16. 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.

  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. 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).

  19. 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.

  20. 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.

  1. 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.

  2. 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).

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. An estimate of the juvenile sulfur content of basalt

    USGS Publications Warehouse

    Moore, J.G.; Fabbi, Brent P.

    1971-01-01

    Sulfur analyses by X-ray fluorescence give an average content of 107 ppm for 9 samples of fresh subaerially-erupted oceanic basalt and 680 ppm for 38 samples of submarine erupted basalt. This difference is the result of retention of sulfur in basalt quenched on the sea floor and loss of sulfur in basalt by degassing at the surface. The outer glassy part of submarine erupted basalt contains 800??150 ppm sulfur, and this amount is regarded as an estimate of the juvenile sulfur content of the basalt melt from the mantle. The slower cooled interiors of basalt pillows are depleted relative to the rims owing to degassing and escape through surface fractures. Available samples of deep-sea basalts do not indicate a difference in original sulfur content between low-K tholeiite, Hawaiian tholeiite, and alkali basalt. The H2O/S ratio of analyzed volcanic gases is generally lower than the H2O/S ratio of gases presumed lost from surface lavas as determined by chemical differences between pillow rims and surface lavas. This enrichment of volcanic gases in sulfur relative to water may result from a greater degassing of sulfur relative to water from shallow intrusive bodies beneath the volcano. ?? 1971 Springer-Verlag.

  16. 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.

  17. 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.

  18. 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.

  19. 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)

  20. 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)

  1. 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

  2. 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.

  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. 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.

  5. 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.

  6. 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.

  7. 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).

  8. 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.

  9. 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.

  10. 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...

  11. 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.

  12. 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.

  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. 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.

  15. 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.

  16. 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

  17. 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

  18. 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.

  19. ZASPE: Zonal Atmospheric Stellar Parameters Estimator

    NASA Astrophysics Data System (ADS)

    Brahm, Rafael; Jordan, Andres; Hartman, Joel; Bakos, Gaspar

    2016-07-01

    ZASPE (Zonal Atmospheric Stellar Parameters Estimator) computes the atmospheric stellar parameters (Teff, log(g), [Fe/H] and vsin(i)) from echelle spectra via least squares minimization with a pre-computed library of synthetic spectra. The minimization is performed only in the most sensitive spectral zones to changes in the atmospheric parameters. The uncertainities and covariances computed by ZASPE assume that the principal source of error is the systematic missmatch between the observed spectrum and the sythetic one that produces the best fit. ZASPE requires a grid of synthetic spectra and can use any pre-computed library minor modifications.

  20. 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

  1. 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.

  2. Source estimation methods for atmospheric dispersion

    NASA Astrophysics Data System (ADS)

    Shankar Rao, K.

    Both forward and backward transport modeling methods are being developed for characterization of sources in atmospheric releases of toxic agents. Forward modeling methods, which describe the atmospheric transport from sources to receptors, use forward-running transport and dispersion models or computational fluid dynamics models which are run many times, and the resulting dispersion field is compared to observations from multiple sensors. Forward modeling methods include Bayesian updating and inference schemes using stochastic Monte Carlo or Markov Chain Monte Carlo sampling techniques. Backward or inverse modeling methods use only one model run in the reverse direction from the receptors to estimate the upwind sources. Inverse modeling methods include adjoint and tangent linear models, Kalman filters, and variational data assimilation, among others. This survey paper discusses these source estimation methods and lists the key references. The need for assessing uncertainties in the characterization of sources using atmospheric transport and dispersion models is emphasized.

  3. 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

  4. 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

  5. Estimation theory and atmospheric data assimilation

    NASA Astrophysics Data System (ADS)

    Todling, Ricardo

    This article is an introduction to estimation theory for problems in atmospheric data assimilation. A background on estimation theory is given using the Bayesian view point. The approaches of minimum variance, maximum α posteriori probability, and maximum likelihood estimation are reviewed. The linear Kalman filter and fixed-lag Kaiman smoother are derived as they serve as motivator for the development of advanced data assimilation procedures. The connection of the Kaiman filter and smoother with the probabilistic Bayesian approach is made. Exercises are provided in a separate chapter to help solidify understanding.

  6. 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.

  7. 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.

  8. 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.

  9. 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'.

  10. 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.

  11. [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).

  12. Estimating Atmospheric Turbulence From Flight Records

    NASA Technical Reports Server (NTRS)

    Wingrove, R. C.; Bach, R. E., Jr.; Schultz, T. A.

    1991-01-01

    Method for estimation of atmospheric turbulence encountered by airplanes utilizes wealth of data captured by multichannel digital flight-data recorders and air-traffic-control radar. Developed as part of continuing effort to understand how airplanes respond to such potentially hazardous phenomena as: clear-air turbulence generated by destabilized wind-shear layers above mountains and thunderstorms, and microbursts (intense downdrafts striking ground), associated with thunderstorms. Reconstructed wind fields used to predict and avoid future hazards.

  13. Estimating Atmospheric Turbulence From Flight Records

    NASA Technical Reports Server (NTRS)

    Wingrove, R. C.; Bach, R. E., Jr.; Schultz, T. A.

    1991-01-01

    Method for estimation of atmospheric turbulence encountered by airplanes utilizes wealth of data captured by multichannel digital flight-data recorders and air-traffic-control radar. Developed as part of continuing effort to understand how airplanes respond to such potentially hazardous phenomena as: clear-air turbulence generated by destabilized wind-shear layers above mountains and thunderstorms, and microbursts (intense downdrafts striking ground), associated with thunderstorms. Reconstructed wind fields used to predict and avoid future hazards.

  14. 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.

  15. 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

  16. 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.

  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. Estimating atmospheric mercury concentrations with lichens.

    PubMed

    Vannini, Andrea; Nicolardi, Valentina; Bargagli, Roberto; Loppi, Stefano

    2014-01-01

    The uptake kinetics of elemental gaseous Hg (Hg(0)) in three species of epiphytic lichens (Pseudevernia furfuracea, Evernia prunastri, and Xanthoria parietina) were investigated under four different Hg concentrations (10, 15, 30, and 45 μg/m(3)) and three different temperatures (10, 20, and 30 °C) with the aim of evaluating the lichen efficiency for Hg(0) accumulation and their potential use in the estimate of atmospheric concentrations of this metal in the field. The results showed that under our experimental conditions the lichens accumulated Hg according to exposure time and that the metal is not released back to the atmosphere after Hg(0) was removed from the air (clearance). Pseudevernia furfuracea showed the highest Hg accumulation capacity and Evernia prunastri showed the lowest, but in these species the metal uptake kinetics was affected by temperature. Xanthoria parietina showed an intermediate metal accumulation capacity and a Hg accumulation rate independent of temperature (in the range 10-30 °C). The use of first-order kinetics equations for Hg uptake in X. parietina and available field data on Hg bioaccumulation in this species allowed reliable estimates of atmospheric Hg concentrations in the environment.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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).

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Sulfur dioxide estimations in the planetary boundary layer using dispersion models and satellite retrievals

    NASA Astrophysics Data System (ADS)

    Zarauz, Jorge V.

    The health and environmental conditions in the Central Andes city La Oroya, Peru, have been seriously damaged by the heavy metal mining activities in the region. The situation has been exacerbated by the complex topography, which prevents proper mixing and dissolution of particles and gases released into the atmosphere. Understanding how pollutants are dispersed in populated regions, especially in complex terrain, would help to create mitigation strategies. The present study uses CALPUFF and HYSPLIT dispersion/deposition models to estimate sulfur dioxide (SO2) dispersion from the main stack of the La Oroya metallurgical plant. Due to the lack of meteorological data in the area, the Weather Research and Forecasting model (WRF) is used with observational nudging for temperature, relative humidity, and wind fields of three surface meteorological stations specifically installed for the study. The pollutant dispersion models are sensitive to a precise estimation of the turbulent vertical transport of mass, energy and moisture in the low atmosphere; therefore, two planetary boundary layer (PBL) schemes are tested, the Mellor-Yamada-Janjic and Yonsei University models. The dispersion models are run and results compared with field measurements at La Oroya, and Huancayo. The observation-nudging and YSU scheme considerably improved the prognostic variables. CALPUFF and HYSPLIT models showed similar patterns; however, HYSPLIT overestimated SO2 concentrations for low PBLs. Moreover, recent enhancements on spectral, spatial and temporal resolution of atmospheric scanning sensors of chemical constituents from the space, have led to detecting trace gases of anthropogenic origin in the lower troposphere. This contribution also explores the SO2 level 2 dataset from Ozone Mapping Instrument (OMI), in conjunction with atmospheric optical depth and Angstrom coefficient data products, extracted from MODerate Resolution Imaging Spectroradiometer (MODIS) to estimate SO2 loads in the PBL

  2. 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.

  3. 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

  4. 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.

  5. Estimation of microwave absorption in the Jupiter atmosphere

    NASA Technical Reports Server (NTRS)

    Coombs, W. C.

    1971-01-01

    A procedure for estimating the microwave absorption loss of the Jupiter atmosphere is presented. Estimation of microwave absorption by planetary atmospheres involves two different investigative disciplines (1) the determination of an acceptable model of the atmosphere itself and (2) the determination of the microwave attenuation rate applicable to each different volume sample of the atmosphere, and the integration of this loss over the varying radio propagation path for any given entry trajectory to obtain the total loss.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. Estimating atmospheric parameters and reducing noise for multispectral imaging

    DOEpatents

    Conger, James Lynn

    2014-02-25

    A method and system for estimating atmospheric radiance and transmittance. An atmospheric estimation system is divided into a first phase and a second phase. The first phase inputs an observed multispectral image and an initial estimate of the atmospheric radiance and transmittance for each spectral band and calculates the atmospheric radiance and transmittance for each spectral band, which can be used to generate a "corrected" multispectral image that is an estimate of the surface multispectral image. The second phase inputs the observed multispectral image and the surface multispectral image that was generated by the first phase and removes noise from the surface multispectral image by smoothing out change in average deviations of temperatures.

  11. 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

  12. 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.

  13. 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.

  14. 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

  15. Venus volcanism: Rate estimates from laboratory studies of sulfur gas-solid reactions

    NASA Technical Reports Server (NTRS)

    Ehlers, K.; Fegley, B., Jr.; Prinn, R. G.

    1989-01-01

    Thermochemical reactions between sulfur-bearing gases in the atmosphere of Venus and calcium-, iron-, magnesium-, and sulfur-bearing minerals on the surface of Venus are an integral part of a hypothesized cycle of thermochemical and photochemical reactions responsible for the maintenance of the global sulfuric acid cloud cover on Venus. SO2 is continually removed from the Venus atmosphere by reaction with calcium bearing minerals on the planet's surface. The rate of volcanism required to balance SO2 depletion by reactions with calcium bearing minerals on the Venus surface can therefore be deduced from a knowledge of the relevant gas-solid reaction rates combined with reasonable assumptions about the sulfur content of the erupted material (gas + magma). A laboratory program was carried out to measure the rates of reaction between SO2 and possible crustal minerals on Venus. The reaction of CaCO3(calcite) + SO2 yields CaSO4 (anhydrite) + CO was studied. Brief results are given.

  16. 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

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. Atmospheric visibility estimation and image contrast calibration

    NASA Astrophysics Data System (ADS)

    Hermansson, Patrik; Edstam, Klas

    2016-10-01

    A method, referred to as contrast calibration, has been developed for transforming digital color photos of outdoor scenes from the atmospheric conditions, illumination and visibility, prevailing at the time of capturing the image to a corresponding image for other atmospheric conditions. A photo captured on a hazy day can, for instance, be converted to resemble a photo of the same scene for good visibility conditions. Converting digital color images to specified lightning and transmission conditions is useful for image based assessment of signature suppression solutions. The method uses "calibration objects" which are photographed at about the same time as the scene of interest. The calibration objects, which (indirectly) provide information on visibility and lightning conditions, consist of two flat boards, painted in different grayscale colors, and a commercial, neutral gray, reference card. Atmospheric extinction coefficient and sky intensity can be determined, in three wavelength bands, from image pixel values on the calibration objects and using this information the image can be converted to other atmospheric conditions. The image is transformed in contrast and color. For illustration, contrast calibration is applied to sample images of a scene acquired at different times. It is shown that contrast calibration of the images to the same reference values of extinction coefficient and sky intensity results in images that are more alike than the original images. It is also exemplified how images can be transformed to various other atmospheric weather conditions. Limitations of the method are discussed and possibilities for further development are suggested.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Atmospheric Turbulence Estimates from a Pulsed Lidar

    NASA Technical Reports Server (NTRS)

    Pruis, Matthew J.; Delisi, Donald P.; Ahmad, Nash'at N.; Proctor, Fred H.

    2013-01-01

    Estimates of the eddy dissipation rate (EDR) were obtained from measurements made by a coherent pulsed lidar and compared with estimates from mesoscale model simulations and measurements from an in situ sonic anemometer at the Denver International Airport and with EDR estimates from the last observation time of the trailing vortex pair. The estimates of EDR from the lidar were obtained using two different methodologies. The two methodologies show consistent estimates of the vertical profiles. Comparison of EDR derived from the Weather Research and Forecast (WRF) mesoscale model with the in situ lidar estimates show good agreement during the daytime convective boundary layer, but the WRF simulations tend to overestimate EDR during the nighttime. The EDR estimates from a sonic anemometer located at 7.3 meters above ground level are approximately one order of magnitude greater than both the WRF and lidar estimates - which are from greater heights - during the daytime convective boundary layer and substantially greater during the nighttime stable boundary layer. The consistency of the EDR estimates from different methods suggests a reasonable ability to predict the temporal evolution of a spatially averaged vertical profile of EDR in an airport terminal area using a mesoscale model during the daytime convective boundary layer. In the stable nighttime boundary layer, there may be added value to EDR estimates provided by in situ lidar measurements.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. A review of atmospheric nitrogen loading estimates to Chesapeake Bay

    SciTech Connect

    Valigura, R.A.; Baker, J.E.; McConnell, L.L.

    1994-12-31

    The importance of atmospheric nitrogen deposition to the Chesapeake Bay and its watershed has been reflected in the number of articles recently published on the peer reviewed literature. Based upon a recent literature synthesis, an evaluation of the magnitude and relative importance of atmospheric nitrogen deposition to the Chesapeake Bay and its watershed will be presented. Key steps required to reduce the uncertainty in atmospheric deposition loading estimates will be outlined. Estimates of nitrogen loadings to Chesapeake Bay will be compared to estimates published for other waterbodies.

  1. 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.

  2. 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...

  3. 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...

  4. Kalman-variant estimators for state of charge in lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Propp, Karsten; Auger, Daniel J.; Fotouhi, Abbas; Longo, Stefano; Knap, Vaclav

    2017-03-01

    Lithium-sulfur batteries are now commercially available, offering high specific energy density, low production costs and high safety. However, there is no commercially-available battery management system for them, and there are no published methods for determining state of charge in situ. This paper describes a study to address this gap. The properties and behaviours of lithium-sulfur are briefly introduced, and the applicability of 'standard' lithium-ion state-of-charge estimation methods is explored. Open-circuit voltage methods and 'Coulomb counting' are found to have a poor fit for lithium-sulfur, and model-based methods, particularly recursive Bayesian filters, are identified as showing strong promise. Three recursive Bayesian filters are implemented: an extended Kalman filter (EKF), an unscented Kalman filter (UKF) and a particle filter (PF). These estimators are tested through practical experimentation, considering both a pulse-discharge test and a test based on the New European Driving Cycle (NEDC). Experimentation is carried out at a constant temperature, mirroring the environment expected in the authors' target automotive application. It is shown that the estimators, which are based on a relatively simple equivalent-circuit-network model, can deliver useful results. If the three estimators implemented, the unscented Kalman filter gives the most robust and accurate performance, with an acceptable computational effort.

  5. Comparison between Sulfur Dioxide estimates using COSPEC and MODIS images

    NASA Astrophysics Data System (ADS)

    Jimenez-Escalona, Jose Carlos; Monsivais-Huertero, Alejandro; Ddelgado-Granados, Hugo

    2015-04-01

    The purpose of this work is to show the synergy of both remote sensing methods in order to utilize information derived from these two techniques for continuous volcano monitoring. Particularly, this paper aims at (1) showing the advantages and disadvantages of both techniques individually and (2) Comparing both sources of measurements and (3) coupling the dynamics showed by COSPEC measurements and static satellite image (MODIS) information. For this end, we use as a case of study the emissions of Popocatépetl volcano between November 2006 and February 2007. During this period, Popocatépetl volcano showed a phase of increased activity, and COSPEC measurement campaigns were made. A few days the dates and times of acquisition of MODIS images coincide with the COSPEC measurements. In the case to make a comparison of both techniques some considerations must be made in such a way that seeks to reproduce the conditions that used a method and the other. In the case of COSPEC is to be understood that measurements are carried out in transects of the plume. On the other hand, we must consider the vehicle that transports the COSPEC, which in this case was terrain, Δt takes a while to cross the plume from side to side and you need to consider that the plume is moving at all times measuring the effect of the prevailing wind at the height where it is located. On the other hand, a satellite image provides instant volcanic plume. It also has information of the whole event in a given time. The resolution of each pixel is one square kilometer while for COSPEC the resolution is a few hundred meters. Results showed that the SO2 estimates data could be comparable in magnitude but should take into account gaps and drawbacks for both methods such as the time spent in making the measurement COSPEC and the route used to transect the plume. While for MODIS, it should be taken into account the image resolution that limits the ability to measure relatively small areas of SO2 concentration

  6. 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.

  7. 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.

  8. 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).

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Using high time resolution aerosol and number size distribution measurements to estimate atmospheric extinction.

    PubMed

    Malm, William C; McMeeking, Gavin R; Kreidenweis, Sonia M; Levin, Ezra; Carrico, Christian M; Day, Derek E; Collett, Jeffrey L; Lee, Taehyoung; Sullivan, Amy P; Raja, Suresh

    2009-09-01

    Rocky Mountain National Park is experiencing reduced visibility and changes in ecosystem function due to increasing levels of oxidized and reduced nitrogen. The Rocky Mountain Atmospheric Nitrogen and Sulfur (RoMANS) study was initiated to better understand the origins of sulfur and nitrogen species as well as the complex chemistry occurring during transport from source to receptor. As part of the study, a monitoring program was initiated for two 1-month time periods--one during the spring and the other during late summer/fall. The monitoring program included intensive high time resolution concentration measurements of aerosol number size distribution, inorganic anions, and cations, and 24-hr time resolution of PM2.5 and PM10 mass, sulfate, nitrate, carbon, and soil-related elements concentrations. These data are combined to estimate high time resolution concentrations of PM2.5 and PM10 aerosol mass and fine mass species estimates of ammoniated sulfate, nitrate, and organic and elemental carbon. Hour-by-hour extinction budgets are calculated by using these species concentration estimates and measurements of size distribution and assuming internal and external particle mixtures. Summer extinction was on average about 3 times higher than spring extinction. During spring months, sulfates, nitrates, carbon mass, and PM10 - PM2.5 mass contributed approximately equal amounts of extinction, whereas during the summer months, carbonaceous material extinction was 2-3 times higher than other species.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Atmospheric water on Mars, energy estimates for extraction

    NASA Technical Reports Server (NTRS)

    Meyer, Tom

    1991-01-01

    The Mars atmosphere is considered as a resource for water to support a human expedition. Information obtained from the Viking mission is used to estimate the near-surface water vapor level. The variability over the diurnal cycle is examined and periods of greatest water abundance are identified. Various methods for extracting atmospheric water are discussed including energy costs and the means for optimizing water extraction techniques.

  5. Atmospheric water on Mars, energy estimates for extraction

    NASA Technical Reports Server (NTRS)

    Meyer, Tom

    1991-01-01

    The Mars atmosphere is considered as a resource for water to support a human expedition. Information obtained from the Viking mission is used to estimate the near-surface water vapor level. The variability over the diurnal cycle is examined and periods of greatest water abundance are identified. Various methods for extracting atmospheric water are discussed including energy costs and the means for optimizing water extraction techniques.

  6. 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

  7. 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

  8. Estimate of sulfur, arsenic, mercury, fluorine emissions due to spontaneous combustion of coal gangue: An important part of Chinese emission inventories.

    PubMed

    Wang, Shaobin; Luo, Kunli; Wang, Xing; Sun, Yuzhuang

    2016-02-01

    A rough estimate of the annual amount of sulfur, arsenic, mercury and fluoride emission from spontaneous combustion of coal gangue in China was determined. The weighted mean concentrations of S, As, Hg, and F in coal gangue are 1.01%, 7.98, 0.18, and 365.54 mg/kg, respectively. Amounts of S, As, Hg, and F emissions from coal gangue spontaneous combustion show approximately 1.13 Mt, and 246, 45, and 63,298 tons in 2013, respectively. The atmospheric release amount of sulfur from coal gangue is more than one tenth of this from coal combustion, and the amounts of As, Hg, and F are close to or even exceed those from coal combustion. China's coal gangue production growth from 1992 to 2013 show an obvious growth since 2002. It may indicate that Chinese coal gangue has become a potential source of air pollution, which should be included in emission inventories.

  9. Estimation and evaluation of exposures from a large sulfur fire in South Africa

    SciTech Connect

    Batterman, S.A.; Cairncross, E.; Huang, Y.L.

    1999-11-01

    A massive fire at a sulfur stockpile in the Western Cape Province of South Africa in December 1995 is estimated to have released over 14,000 t of sulfur dioxide (SO{sub 2}) over a 20-h period. High and persistent winds greatly reduced the effectiveness of fire-fighting activities and increased the severity of impacts. nearby urban and agricultural areas were seriously affected. Thousands of people were evacuated from the nearby town of Macassar located 2.5--4 km downwind, and at least several deaths occurred. Agricultural impacts ranged over a broad area extending to 30 km from the fire site and included severe damage to plants and some animal deaths. This paper describes the chronology of the fire, the emergency responses, and the immediate impacts. SO{sub 2} concentrations are estimated using dispersion modeling, and predictions are evaluated using available monitoring information. Sensitivity analyses are used to test unknown or uncertain model parameters. The SO{sub 2} concentrations estimated in Macassar reached extremely dangerous levels, at times over the IDLH level (100 ppm). predictions agree with the available but very limited monitoring data, as well as with the symptomology of Macassar residents and plant damage patterns. Procedures to deal with the limited information and variability in this fire and similar incidents are suggested. The fire is a tragic demonstration of shortcomings in hazardous material management and emergency response.

  10. Estimate of mercury emissions to the atmosphere from petroleum.

    PubMed

    Wilhelm, S M

    2001-12-15

    An estimate of the contribution of mercury to the atmospheric environment from petroleum processed in the United States is constructed from recent data. The estimate is based on a mass balance approach for mercury in crude oil, in refined products, and in waste streams (air, water, solid waste) from refineries. Although there are insufficient data at present to have a high degree of confidence in the mean amount and range of mercury concentrations in crude oil or in refined products, the framework of the estimate should assist direction for the acquisition of additional data. On the basis of selected data that put the estimated mean concentration of total mercury in crude oil close to 10 ppb, it is calculated that the total amount of mercury in U.S. petroleum processed yearly is slightly over 8000 kg/yr. Of this amount, approximately 6000 kg/yr is estimated to be emitted to the atmosphere from combustion of liquid hydrocarbon fuels, which represents about 10% of the U.S. yearly emission rate of atmospheric mercury from coal combustion. The material balance predicts that the amount of mercury in air emissions from all U.S. refineries is on the order of 1500 kg/yr based on the assumption that fugitive mercury emissions from refineries are negligible. Atmospheric emissions of mercury from fuel oil burned in the United States are estimated in the U.S. EPA Mercury Report to Congress to be approximately 10000 kg/yr, and this estimate may be in error on the high side by a factor of 3-10. If the mean amounts of mercury in U.S. distillate and residual fuel oils are in the range of 5-15 ppb, as suggested by more recent data, then U.S. fuel oil combustion should contribute no more that about 1000-3000 kg/yr (emission ratio = 1) of mercury to the atmospheric burden.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Spectral estimation of global levels of atmospheric pollutants.

    PubMed

    Fernández-Macho, Javier

    2011-10-01

    Underlying levels of atmospheric pollutants, assumed to be governed by smoothing mechanisms due to atmospheric dispersion, can be estimated from global emissions source databases on greenhouse gases and ozone-depleting compounds. However, spatial data may be contaminated with noise or even missing or zero-valued at many locations. Therefore, a problem that arises is how to extract the underlying smooth levels. This paper sets out a structural spatial model that assumes data evolve across a global grid constrained by second-order smoothing restrictions. The frequency-domain approach is particularly suitable for global datasets, reduces the computational burden associated with two-dimensional models and avoids cumbersome zero-inflated skewed distributions. Confidence intervals of the underlying levels are also obtained. An application to the estimation of global levels of atmospheric pollutants from anthropogenic emissions illustrates the technique which may also be useful in the analysis of other environmental datasets of similar characteristics.

  16. Friction- and mountain-torque estimates from global atmospheric data

    NASA Technical Reports Server (NTRS)

    Wahr, J. M.; Oort, A. H.

    1984-01-01

    Seasonal, zonal surface torques between the atmosphere and the earth are estimated and compared, using data from a number of independent sources. The mountain torque is computed both from surface pressure data and from isobaric height data. The friction torque is estimated from the oceanic stress data of Hellerman and Rosenstein. Results for the total torque are inferred from atmospheric angular momentum data. Finally, the globally integrated total torque is compared with astronomical observations of the earth's rotation rate. These comparisons help us to assess the quality of the different results. Zonal torques are also computed using results from a GFDL general circulation model of the atmosphere. A comparison with the corresponding results inferred from real data is presented and interpreted in terms of model accuracy.

  17. Range estimation of passive infrared targets through the atmosphere

    NASA Astrophysics Data System (ADS)

    Cho, Hoonkyung; Chun, Joohwan; Seo, Doochun; Choi, Seokweon

    2013-04-01

    Target range estimation is traditionally based on radar and active sonar systems in modern combat systems. However, jamming signals tremendously degrade the performance of such active sensor devices. We introduce a simple target range estimation method and the fundamental limits of the proposed method based on the atmosphere propagation model. Since passive infrared (IR) sensors measure IR signals radiating from objects in different wavelengths, this method has robustness against electromagnetic jamming. The measured target radiance of each wavelength at the IR sensor depends on the emissive properties of target material and various attenuation factors (i.e., the distance between sensor and target and atmosphere environment parameters). MODTRAN is a tool that models atmospheric propagation of electromagnetic radiation. Based on the results from MODTRAN and atmosphere propagation-based modeling, the target range can be estimated. To analyze the proposed method's performance statistically, we use maximum likelihood estimation (MLE) and evaluate the Cramer-Rao lower bound (CRLB) via the probability density function of measured radiance. We also compare CRLB and the variance of MLE using Monte-Carlo simulation.

  18. Planetary Probe Entry Atmosphere Estimation Using Synthetic Air Data System

    NASA Technical Reports Server (NTRS)

    Karlgaard, Chris; Schoenenberger, Mark

    2017-01-01

    This paper develops an atmospheric state estimator based on inertial acceleration and angular rate measurements combined with an assumed vehicle aerodynamic model. The approach utilizes the full navigation state of the vehicle (position, velocity, and attitude) to recast the vehicle aerodynamic model to be a function solely of the atmospheric state (density, pressure, and winds). Force and moment measurements are based on vehicle sensed accelerations and angular rates. These measurements are combined with an aerodynamic model and a Kalman-Schmidt filter to estimate the atmospheric conditions. The new method is applied to data from the Mars Science Laboratory mission, which landed the Curiosity rover on the surface of Mars in August 2012. The results of the new estimation algorithm are compared with results from a Flush Air Data Sensing algorithm based on onboard pressure measurements on the vehicle forebody. The comparison indicates that the new proposed estimation method provides estimates consistent with the air data measurements, without the use of pressure measurements. Implications for future missions such as the Mars 2020 entry capsule are described.

  19. Net atmospheric mercury deposition to Svalbard: Estimates from lacustrine sediments

    NASA Astrophysics Data System (ADS)

    Drevnick, Paul E.; Yang, Handong; Lamborg, Carl H.; Rose, Neil L.

    2012-11-01

    In this study we used lake sediments, which faithfully record Hg inputs, to derive estimates of net atmospheric Hg deposition to Svalbard, Norwegian Arctic. With the exception of one site affected by local pollution, the study lakes show twofold to fivefold increases in sedimentary Hg accumulation since 1850, likely due to long-range atmospheric transport and deposition of anthropogenic Hg. Sedimentary Hg accumulation in these lakes is a linear function of the ratio of catchment area to lake area, and we used this relationship to model net atmospheric Hg flux: preindustrial and modern estimates are 2.5 ± 3.3 μg m-2 y-1 and 7.0 ± 3.0 μg m-2 y-1, respectively. The modern estimate, by comparison with data for Hg wet deposition, indicates that atmospheric mercury depletion events (AMDEs) or other dry deposition processes contribute approximately half (range 0-70%) of the net flux. Hg from AMDEs may be moving in significant quantities into aquatic ecosystems, where it is a concern because of contamination of aquatic food webs.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. Estimation of Residual Peritoneal Volume Using Technetium-99m Sulfur Colloid Scintigraphy.

    PubMed

    Katopodis, Konstantinos P; Fotopoulos, Andrew D; Balafa, Olga C; Tsiouris, Spyridon Th; Triandou, Eleni G; Al-Bokharhli, Jichad B; Kitsos, Athanasios C; Dounousi, Evagelia C; Siamopoulos, Konstantinos C

    2015-01-01

    Residual peritoneal volume (RPV) may contribute in the development of ultrafiltration failure in patients with normal transcapillary ultrafiltration. The aim of this study was to estimate the RPV using intraperitoneal technetium-99m Sulfur Colloid (Tc). Twenty patients on peritoneal dialysis were studied. RPV was estimated by: 1) intraperitoneal instillation of Tc (RPV-Tc) and 2) classic Twardowski calculations using endogenous solutes, such as urea (RPV-u), creatinine (RPV-cr), and albumin (RPV-alb). Each method's reproducibility was assessed in a subgroup of patients in two consecutive measurements 48 h apart. Both methods displayed reproducibility (r = 0.93, p = 0.001 for RPVTc and r = 0.90, p = 0.001 for RPV-alb) between days 1 and 2, respectively. We found a statistically significant difference between RPV-Tc and RPV-cr measurements (347.3 ± 116.7 vs. 450.0 ± 67.8 ml; p =0.001) and RPV-u (515.5 ± 49.4 ml; p < 0.001), but not with RPV-alb (400.1 ± 88.2 ml; p = 0.308). A good correlation was observed only between RPV-Tc and RPV-alb (p < 0.001). The Tc method can estimate the RPV as efficiently as the high molecular weight endogenous solute measurement method. It can also provide an imaging estimate of the intraperitoneal distribution of RPV.

  5. [Automatic Measurement of the Stellar Atmospheric Parameters Based Mass Estimation].

    PubMed

    Tu, Liang-ping; Wei, Hui-ming; Luo, A-li; Zhao, Yong-heng

    2015-11-01

    We have collected massive stellar spectral data in recent years, which leads to the research on the automatic measurement of stellar atmospheric physical parameters (effective temperature Teff, surface gravity log g and metallic abundance [Fe/ H]) become an important issue. To study the automatic measurement of these three parameters has important significance for some scientific problems, such as the evolution of the universe and so on. But the research of this problem is not very widely, some of the current methods are not able to estimate the values of the stellar atmospheric physical parameters completely and accurately. So in this paper, an automatic method to predict stellar atmospheric parameters based on mass estimation was presented, which can achieve the prediction of stellar effective temperature Teff, surface gravity log g and metallic abundance [Fe/H]. This method has small amount of computation and fast training speed. The main idea of this method is that firstly it need us to build some mass distributions, secondly the original spectral data was mapped into the mass space and then to predict the stellar parameter with the support vector regression (SVR) in the mass space. we choose the stellar spectral data from the United States SDSS-DR8 for the training and testing. We also compared the predicted results of this method with the SSPP and achieve higher accuracy. The predicted results are more stable and the experimental results show that the method is feasible and can predict the stellar atmospheric physical parameters effectively.

  6. Estimation of atmospheric parameters from time-lapse imagery

    NASA Astrophysics Data System (ADS)

    McCrae, Jack E.; Basu, Santasri; Fiorino, Steven T.

    2016-05-01

    A time-lapse imaging experiment was conducted to estimate various atmospheric parameters for the imaging path. Atmospheric turbulence caused frame-to-frame shifts of the entire image as well as parts of the image. The statistics of these shifts encode information about the turbulence strength (as characterized by Cn2, the refractive index structure function constant) along the optical path. The shift variance observed is simply proportional to the variance of the tilt of the optical field averaged over the area being tracked. By presuming this turbulence follows the Kolmogorov spectrum, weighting functions can be derived which relate the turbulence strength along the path to the shifts measured. These weighting functions peak at the camera and fall to zero at the object. The larger the area observed, the more quickly the weighting function decays. One parameter we would like to estimate is r0 (the Fried parameter, or atmospheric coherence diameter.) The weighting functions derived for pixel sized or larger parts of the image all fall faster than the weighting function appropriate for estimating the spherical wave r0. If we presume Cn2 is constant along the path, then an estimate for r0 can be obtained for each area tracked, but since the weighting function for r0 differs substantially from that for every realizable tracked area, it can be expected this approach would yield a poor estimator. Instead, the weighting functions for a number of different patch sizes can be combined through the Moore-Penrose pseudo-inverse to create a new weighting function which yields the least-squares optimal linear combination of measurements for estimation of r0. This approach is carried out, and it is observed that this approach is somewhat noisy because the pseudo-inverse assigns weights much greater than one to many of the observations.

  7. 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.

  8. 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

  9. Chernobyl source term, atmospheric dispersion, and dose estimation

    SciTech Connect

    Gudiksen, P.H.; Harvey, T.F.; Lange, R.

    1988-02-01

    The Chernobyl source term available for long-range transport was estimated by integration of radiological measurements with atmospheric dispersion modeling, and by reactor core radionuclide inventory estimation in conjunction with WASH-1400 release fractions associated with specific chemical groups. These analyses indicated that essentially all of the noble gases, 80% of the radioiodines, 40% of the radiocesium, 10% of the tellurium, and about 1% or less of the more refractory elements were released. Atmospheric dispersion modeling of the radioactive cloud over the Northern Hemisphere revealed that the cloud became segmented during the first day, with the lower section heading toward Scandinavia and the uppper part heading in a southeasterly direction with subsequent transport across Asia to Japan, the North Pacific, and the west coast of North America. The inhalation doses due to direct cloud exposure were estimated to exceed 10 mGy near the Chernobyl area, to range between 0.1 and 0.001 mGy within most of Europe, and to be generally less than 0.00001 mGy within the US. The Chernobyl source term was several orders of magnitude greater than those associated with the Windscale and TMI reactor accidents, while the /sup 137/Cs from the Chernobyl event is about 6% of that released by the US and USSR atmospheric nuclear weapon tests. 9 refs., 3 figs., 6 tabs.

  10. Chernobyl source term, atmospheric dispersion, and dose estimation

    SciTech Connect

    Gudiksen, P.H.; Harvey, T.F.; Lange, R. )

    1989-11-01

    The Chernobyl source term available for long-range transport was estimated by integration of radiological measurements with atmospheric dispersion modeling and by reactor core radionuclide inventory estimation in conjunction with WASH-1400 release fractions associated with specific chemical groups. These analyses indicated that essentially all of the noble gases, 60% of the radioiodines, 40% of the radiocesium, 10% of the tellurium, and about 1% or less of the more refractory elements were released. Atmospheric dispersion modeling of the radioactive cloud over the Northern Hemisphere revealed that the cloud became segmented during the first day, with the lower section heading toward Scandinavia and the upper part heading in a southeasterly direction with subsequent transport across Asia to Japan, the North Pacific, and the west coast of North America. The inhalation doses due to direct cloud exposure were estimated to exceed 10 mGy near the Chernobyl area, to range between 0.1 and 0.001 mGy within most of Europe, and to be generally less than 0.00001 mGy within the United States. The Chernobyl source term was several orders of magnitude greater than those associated with the Windscale and TMI reactor accidents. However, the 137Cs from the Chernobyl event is about 6% of that released by the U.S. and U.S.S.R. atmospheric nuclear weapon tests, while the 131I and 90Sr released by the Chernobyl accident was only about 0.1% of that released by the weapon tests.

  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. Atmospheric Inverse Estimates of Methane Emissions from Central California

    SciTech Connect

    Zhao, Chuanfeng; Andrews, Arlyn E.; Bianco, Laura; Eluszkiewicz, Janusz; Hirsch, Adam; MacDonald, Clinton; Nehrkorn, Thomas; Fischer, Marc L.

    2008-11-21

    Methane mixing ratios measured at a tall-tower are compared to model predictions to estimate surface emissions of CH{sub 4} in Central California for October-December 2007 using an inverse technique. Predicted CH{sub 4} mixing ratios are calculated based on spatially resolved a priori CH{sub 4} emissions and simulated atmospheric trajectories. The atmospheric trajectories, along with surface footprints, are computed using the Weather Research and Forecast (WRF) coupled to the Stochastic Time-Inverted Lagrangian Transport (STILT) model. An uncertainty analysis is performed to provide quantitative uncertainties in estimated CH{sub 4} emissions. Three inverse model estimates of CH{sub 4} emissions are reported. First, linear regressions of modeled and measured CH{sub 4} mixing ratios obtain slopes of 0.73 {+-} 0.11 and 1.09 {+-} 0.14 using California specific and Edgar 3.2 emission maps respectively, suggesting that actual CH{sub 4} emissions were about 37 {+-} 21% higher than California specific inventory estimates. Second, a Bayesian 'source' analysis suggests that livestock emissions are 63 {+-} 22% higher than the a priori estimates. Third, a Bayesian 'region' analysis is carried out for CH{sub 4} emissions from 13 sub-regions, which shows that inventory CH{sub 4} emissions from the Central Valley are underestimated and uncertainties in CH{sub 4} emissions are reduced for sub-regions near the tower site, yielding best estimates of flux from those regions consistent with 'source' analysis results. The uncertainty reductions for regions near the tower indicate that a regional network of measurements will be necessary to provide accurate estimates of surface CH{sub 4} emissions for multiple regions.

  15. 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.

  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. 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)

  18. Characterization, parameter estimation, and aircraft response statistics of atmospheric turbulence

    NASA Technical Reports Server (NTRS)

    Mark, W. D.

    1981-01-01

    A nonGaussian three component model of atmospheric turbulence is postulated that accounts for readily observable features of turbulence velocity records, their autocorrelation functions, and their spectra. Methods for computing probability density functions and mean exceedance rates of a generic aircraft response variable are developed using nonGaussian turbulence characterizations readily extracted from velocity recordings. A maximum likelihood method is developed for optimal estimation of the integral scale and intensity of records possessing von Karman transverse of longitudinal spectra. Formulas for the variances of such parameter estimates are developed. The maximum likelihood and least-square approaches are combined to yield a method for estimating the autocorrelation function parameters of a two component model for turbulence.

  19. Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems: Highlighting the role of isomers in the sulfite and sulfoxylate systems

    NASA Astrophysics Data System (ADS)

    Eldridge, D. L.; Guo, W.; Farquhar, J.

    2016-12-01

    We present theoretical calculations for all three isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S) at the B3LYP/6-31+G(d,p) level of theory for aqueous sulfur compounds modeled in 30-40H2O clusters spanning the range of sulfur oxidation state (Sn, n = -2 to +6) for estimating equilibrium fractionation factors in aqueous systems. Computed 34β values based on major isotope (34S/32S) reduced partition function ratios (RPFRs) scale to a first order with sulfur oxidation state and coordination, where 34β generally increase with higher oxidation state and increasing coordination of the sulfur atom. Exponents defining mass dependent relationships based on β values (x/34κ = ln(xβ)/ln(34β), x = 33 or 36) conform to tight ranges over a wide range of temperature for all aqueous compounds (33/34κ ≈ 0.5148-0.5159, 36/34κ ≈ 1.89-1.90 from T ⩾ 0 °C). The exponents converge near a singular value for all compounds at the high temperature limit (33/34κT→∞ = 0.51587 ± 0.00003 and 36/34κT→∞ = 1.8905 ± 0.0002; 1 s.d. of all computed compounds), and typically follow trends based on oxidation state and coordination similar to those seen in 34β values at lower temperatures. Theoretical equilibrium fractionation factors computed from these β-values are compared to experimental constraints for HSO3-T(aq)/SO2(g, aq), SO2(aq)/SO2(g), H2S(aq)/H2S(g), H2S(aq)/HS-(aq), SO42-(aq)/H2ST(aq), S2O32-(aq) (intramolecular), and S2O32-(aq)/H2ST(aq), and generally agree within a reasonable estimation of uncertainties. We make predictions of fractionation factors where other constraints are unavailable. Isotope partitioning of the isomers of protonated compounds in the sulfite and sulfoxylate systems depend strongly on whether protons are bound to either sulfur or oxygen atoms. The magnitude of the HSO3-T/SO32- major isotope (34S/32S) fractionation factor is predicted to increase with temperature from 0 to 70 °C due to the combined effects of the large magnitude (HS)O3

  20. 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.

  1. Solar Radiation Estimated Through Mesoscale Atmospheric Modeling over Northeast Brazil

    NASA Astrophysics Data System (ADS)

    de Menezes Neto, Otacilio Leandro; Costa, Alexandre Araújo; Ramalho, Fernando Pinto; de Maria, Paulo Henrique Santiago

    2009-03-01

    The use of renewable energy sources, like solar, wind and biomass is rapidly increasing in recent years, with solar radiation as a particularly abundant energy source over Northeast Brazil. A proper quantitative knowledge of the incoming solar radiation is of great importance for energy planning in Brazil, serving as basis for developing future projects of photovoltaic power plants and solar energy exploitation. This work presents a methodology for mapping the incoming solar radiation at ground level for Northeast Brazil, using a mesoscale atmospheric model (Regional Atmospheric Modeling System—RAMS), calibrated and validated using data from the network of automatic surface stations from the State Foundation for Meteorology and Water Resources from Ceará (Fundação Cearense de Meteorologia e Recursos Hídricos- FUNCEME). The results showed that the model exhibits systematic errors, overestimating surface radiation, but that, after the proper statistical corrections, using a relationship between the model-predicted cloud fraction, the ground-level observed solar radiation and the incoming solar radiation estimated at the top of the atmosphere, a correlation of 0.92 with a confidence interval of 13.5 W/m2 is found for monthly data. Using this methodology, we found an estimate for annual average incoming solar radiation over Ceará of 215 W/m2 (maximum in October: 260 W/m2).

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

    NASA Astrophysics Data System (ADS)

    Eldridge, D. L.; Farquhar, J.; Guo, W.

    2015-12-01

    Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate

  10. 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

  11. Atmospheric trend and emission estimates for HFC-43-10mee (1999 to 2010)

    NASA Astrophysics Data System (ADS)

    Arnold, T.; Ivy, D. J.; Muhle, J.; Harth, C. M.; Salameh, P.; Weiss, R. F.

    2010-12-01

    We present the first atmospheric measurements of HFC-43-10mee (1,1,1,2,2,3,4,5,5,5-decafluoropentane), an anthropogenic gas introduced in the mid-1990s as a substitute for CFC-113 (1,1,2-trichlorotrifluoroethane). The global warming potential of this HFC (hydrofluorocarbon) has been reported as 1640 (100-year time horizon), hence, its inclusion within a class of chemicals in the Kyoto Protocol and now its consideration for addition in the Montreal Protocol. Commercial HFC-43-10mee is a mixture of two diastereomers; both detectable using the Medusa GC-MS cryogenic trapping system (Miller et al., 2008), and included in our calculations for total HFC-43-10mee concentration. Chen et al. [2010] recently reported that the diastereomers have identical lifetimes in the troposphere of ≈18 years. Our northern hemisphere (NH) tropospheric record spans from 1999 to present day, utilizing 12 archive samples together with recent in situ measurements from the Advanced Global Atmospheric Gases Experiment (AGAGE) program at Trinidad Head and La Jolla, California. Precisions of < 0.01 ppt (parts-per-trillion, dry air mole fraction) allow for observation of an accelerated rise from 0.04 ppt in 2000 (growth rate of 0.01 ppt/yr) to 0.10 ppt in 2005 (0.02 ppt/yr) and 0.21 ppt in 2010 (0.03 ppt/yr). From the experimentally defined mole fractions in the background NH, we estimate the growth trend in the southern hemisphere using a simple box model which includes the stratosphere. Further, we estimate ‘top-down’ emissions to the global atmosphere for 2009 at ≈ 1200 tonnes. ‘Bottom-up’ estimates from the Emission Database for Global Atmospheric Research (EDGAR) v.4.0 only include emissions from Austria and France in 2005, which total 206 tonnes. For comparison, the global emissions in 2005 from our model equate to ≈ 800 tonnes. Further measurement and modeling efforts are warranted together with projections of future consumption. References: Miller, B. R., R. F. Weiss, P. K

  12. A Direct Estimate of Climate Sensitivity from Atmospheric Structure

    NASA Astrophysics Data System (ADS)

    Lacis, A. A.

    2014-12-01

    The nominal equilibrium climate sensitivity of about 3°C for doubled CO2 is obtained from direct climate model calculations and from simulations of the historical surface temperature record. A similar value of equilibrium climate sensitivity has been inferred from the geological ice core record. A further independent estimate of climate sensitivity can be derived directly from the atmospheric temperature, cloud, and absorbing gas structure. Attribution of individual contributions to the terrestrial greenhouse effect by individual atmospheric constituents shows that water vapor and clouds account for about 75% of the total greenhouse effect, while CO2 and the other minor non-condensing green house gases account for the remaining 25%. It is generally understood that water vapor and cloud contributions to the greenhouse effect arise as feedback effects, and that the non-condensing greenhouse gas contribution can be identified as the radiative forcing component. From this alone, a climate feedback sensitivity of f = 4, or about 5°C for doubled CO2 can be inferred. Accounting further for the negative temperature lapse rate feedback that is not directly included in the attribution analysis, and allowing for a residual non-condensing component of the water vapor feedback, brings the equilibrium climate sensitivity that is inferred from atmospheric structural analysis to the 3°C range for doubled CO2, in good agreement with the equilibrium climate sensitivity that is obtained from comparisons to historical and geological global temperature changes.

  13. Estimating the dose from atmospheric releases of HT

    SciTech Connect

    Murphy, C.E. Jr.

    1990-11-13

    Measurements of uptake of tritium by humans and laboratory animals following exposure to tritiated hydrogen gas, HT, suggest that the radiotoxicity of HT is four orders of magnitude less than that of tritiated water, HTO. However, this analysis does not take into account the conversion of HT into HTO following release into the environment. Experimental releases of HT have demonstrated that HT release to the environment is converted to HTO by soil microorganisms. In this report two methods are used to estimate the effect of HT to HTO conversion on the inhalation dose of individuals exposed to tritium downwind of a release of HT. From this analysis it is predicted that the ratio of dose from inhalation of tritium following an atmospheric release of HT, as compared to inhalation of HTO, is closer to 0.01 than the 0.0001 attributed to simple HT inhalation. Under meteorologic conditions which keep the HT release near the surface and promote optimum soil microbial activity, the analysis suggests that the ratio of dose from an atmospheric HT release could be as high as 25% of that from an atmospheric HTO release.

  14. 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.

  15. Uncertainties associated with parameter estimation in atmospheric infrasound arrays

    NASA Astrophysics Data System (ADS)

    Szuberla, Curt A. L.; Olson, John V.

    2004-01-01

    This study describes a method for determining the statistical confidence in estimates of direction-of-arrival and trace velocity stemming from signals present in atmospheric infrasound data. It is assumed that the signal source is far enough removed from the infrasound sensor array that a plane-wave approximation holds, and that multipath and multiple source effects are not present. Propagation path and medium inhomogeneities are assumed not to be known at the time of signal detection, but the ensemble of time delays of signal arrivals between array sensor pairs is estimable and corrupted by uncorrelated Gaussian noise. The method results in a set of practical uncertainties that lend themselves to a geometric interpretation. Although quite general, this method is intended for use by analysts interpreting data from atmospheric acoustic arrays, or those interested in designing and deploying them. The method is applied to infrasound arrays typical of those deployed as a part of the International Monitoring System of the Comprehensive Nuclear-Test-Ban Treaty Organization.

  16. Nitrogen trifluoride global emissions estimated from updated atmospheric measurements

    PubMed Central

    Arnold, Tim; Harth, Christina M.; Mühle, Jens; Manning, Alistair J.; Salameh, Peter K.; Kim, Jooil; Ivy, Diane J.; Steele, L. Paul; Petrenko, Vasilii V.; Severinghaus, Jeffrey P.; Baggenstos, Daniel; Weiss, Ray F.

    2013-01-01

    Nitrogen trifluoride (NF3) has potential to make a growing contribution to the Earth’s radiative budget; however, our understanding of its atmospheric burden and emission rates has been limited. Based on a revision of our previous calibration and using an expanded set of atmospheric measurements together with an atmospheric model and inverse method, we estimate that the global emissions of NF3 in 2011 were 1.18 ± 0.21 Gg⋅y−1, or ∼20 Tg CO2-eq⋅y−1 (carbon dioxide equivalent emissions based on a 100-y global warming potential of 16,600 for NF3). The 2011 global mean tropospheric dry air mole fraction was 0.86 ± 0.04 parts per trillion, resulting from an average emissions growth rate of 0.09 Gg⋅y−2 over the prior decade. In terms of CO2 equivalents, current NF3 emissions represent between 17% and 36% of the emissions of other long-lived fluorinated compounds from electronics manufacture. We also estimate that the emissions benefit of using NF3 over hexafluoroethane (C2F6) in electronics manufacture is significant—emissions of between 53 and 220 Tg CO2-eq⋅y−1 were avoided during 2011. Despite these savings, total NF3 emissions, currently ∼10% of production, are still significantly larger than expected assuming global implementation of ideal industrial practices. As such, there is a continuing need for improvements in NF3 emissions reduction strategies to keep pace with its increasing use and to slow its rising contribution to anthropogenic climate forcing. PMID:23341630

  17. Estimating Longwave Atmospheric Emissivity in the Canadian Rocky Mountains

    NASA Astrophysics Data System (ADS)

    Ebrahimi, S.; Marshall, S. J.

    2014-12-01

    Incoming longwave radiation is an important source of energy contributing to snow and glacier melt. However, estimating the incoming longwave radiation from the atmosphere is challenging due to the highly varying conditions of the atmosphere, especially cloudiness. We analyze the performance of some existing models included a physically-based clear-sky model by Brutsaert (1987) and two different empirical models for all-sky conditions (Lhomme and others, 2007; Herrero and Polo, 2012) at Haig Glacier in the Canadian Rocky Mountains. Models are based on relations between readily observed near-surface meteorological data, including temperature, vapor pressure, relative humidity, and estimates of shortwave radiation transmissivity (i.e., clear-sky or cloud-cover indices). This class of models generally requires solar radiation data in order to obtain a proxy for cloud conditions. This is not always available for distributed models of glacier melt, and can have high spatial variations in regions of complex topography, which likely do not reflect the more homogeneous atmospheric longwave emissions. We therefore test longwave radiation parameterizations as a function of near-surface humidity and temperature variables, based on automatic weather station data (half-hourly and mean daily values) from 2004 to 2012. Results from comparative analysis of different incoming longwave radiation parameterizations showed that the locally-calibrated model based on relative humidity and vapour pressure performs better than other published models. Performance is degraded but still better than standard cloud-index based models when we transfer the model to another site, roughly 900 km away, Kwadacha Glacier in the northern Canadian Rockies.

  18. 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.

  19. Stratospheric sulfuric acid fraction and mass estimate for the 1982 volcanic eruption of El Chichon

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.

    1983-01-01

    The stratospheric sulfuric acid fraction and mass for the 1982 volcanic eruptions of El Chichon are investigated using data from balloon soundings at Laramie (41 deg N) and in southern Texas (27-29 deg N). The total stratospheric mass of these eruptions is estimated to be approximately 8 Tg about 6.5 months after the eruption with possibly as much as 20 Tg in the stratosphere about 45 days after the eruption. Observations of the aerosol in Texas revealed two primary layers, both highly volatile at 150 C. Aerosol in the upper layer at about 25 km was composed of an approximately 80 percent H2SO4 solution while the lower layer at approximately 18 km was composed of a 60-65 percent H2SO4 solution aerosol. It is calculated that an H2SO4 vapor concentration of at least 3 x 10 to the 7th molecules/cu cm is needed to sustain the large droplets in the upper layer. An early bi-modal nature in the size distribution indicates droplet nucleation from the gas phase during the first 3 months, while the similarity of the large particle profiles 2 months apart shows continued particle growth 6.5 months after the explosion.

  20. Stratospheric sulfuric acid fraction and mass estimate for the 1982 volcanic eruption of El Chichon

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.

    1983-01-01

    The stratospheric sulfuric acid fraction and mass for the 1982 volcanic eruptions of El Chichon are investigated using data from balloon soundings at Laramie (41 deg N) and in southern Texas (27-29 deg N). The total stratospheric mass of these eruptions is estimated to be approximately 8 Tg about 6.5 months after the eruption with possibly as much as 20 Tg in the stratosphere about 45 days after the eruption. Observations of the aerosol in Texas revealed two primary layers, both highly volatile at 150 C. Aerosol in the upper layer at about 25 km was composed of an approximately 80 percent H2SO4 solution while the lower layer at approximately 18 km was composed of a 60-65 percent H2SO4 solution aerosol. It is calculated that an H2SO4 vapor concentration of at least 3 x 10 to the 7th molecules/cu cm is needed to sustain the large droplets in the upper layer. An early bi-modal nature in the size distribution indicates droplet nucleation from the gas phase during the first 3 months, while the similarity of the large particle profiles 2 months apart shows continued particle growth 6.5 months after the explosion.

  1. 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

  2. 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.

  3. Paradigms and commonalities in atmospheric source term estimation methods

    NASA Astrophysics Data System (ADS)

    Bieringer, Paul E.; Young, George S.; Rodriguez, Luna M.; Annunzio, Andrew J.; Vandenberghe, Francois; Haupt, Sue Ellen

    2017-05-01

    Modeling the downwind hazard area resulting from the unknown release of an atmospheric contaminant requires estimation of the source characteristics of a localized source from concentration or dosage observations and use of this information to model the subsequent transport and dispersion of the contaminant. This source term estimation problem is mathematically challenging because airborne material concentration observations and wind data are typically sparse and the turbulent wind field chaotic. Methods for addressing this problem fall into three general categories: forward modeling, inverse modeling, and nonlinear optimization. Because numerous methods have been developed on various foundations, they often have a disparate nomenclature. This situation poses challenges to those facing a new source term estimation problem, particularly when selecting the best method for the problem at hand. There is, however, much commonality between many of these methods, especially within each category. Here we seek to address the difficulties encountered when selecting an STE method by providing a synthesis of the various methods that highlights commonalities, potential opportunities for component exchange, and lessons learned that can be applied across methods.

  4. 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

  5. Estimating sources, sinks and fluxes of reactive atmospheric compounds within a forest canopy

    NASA Astrophysics Data System (ADS)

    Ghannam, K.; Duman, T.; Walker, J. T.; Bash, J. O.; Huang, C. W.; Khlystov, A.; Katul, G. G.

    2015-12-01

    While few dispute the significance of within-canopy sources or sinks of reactive gaseous and particulate compounds, their estimation continues to be the subject of active research and debate. Reactive species undergo turbulent dispersion within an inhomogeneous flow field, and may be subjected to chemical, biological and/or physical deposition, emissions or transformations on leaves, woody elements, and the forest floor. This system involves chemical reactions and biological processes with multiple time scales and represents the terrestrial ecosystem's exposure to nutrient and acid deposition and atmospheric oxidants. The quantification of these processes is a first step in better understanding the ecological impact of air pollution and feedback to atmospheric composition. Hence, it follows that direct measurements of sources or sinks is difficult to conduct in the presence of all these processes. However, mean scalar concentration profiles measured within the canopy can be used to infer the profile distribution of effective sinks and sources if the flow field is known. This is commonly referred to as the 'inverse problem'. In-canopy and above-canopy multi-level concentration measurements of reactive nitrogen compounds (ammonia, nitric acid, nitrous acid), as well as other compounds that are highly reactive to ammonia and its secondary products (hydrochloric acid and sulfur dioxide), are presented within a deciduous second-growth 180 year old oak-hickory forest situated within the Southeastern U.S. Two different approaches are used to solve for the source-sink distribution from the measured mean scalar concentration profiles: (1) an Eulerian high-order closure model that solves the scalar flux budget equation and (2) a new Lagrangian stochastic model that estimates the dispersion matrix. As each of these methods is subject to different assumptions, the combination of the two can be used to constrain the solution to the inverse problem and permit inference on the

  6. 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...

  7. 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

  8. 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.

  9. 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.

  10. 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).

  11. 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.

  12. 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%.

  13. 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.

  14. Estimating Uncertainty in Atmospheric Models - Application and new Approaches of Lyapunov Vector Estimations

    NASA Astrophysics Data System (ADS)

    Keller, J. D.; Hense, A.; Rhodin, A.

    2010-12-01

    The atmosphere, like other geophysical non-linear systems, is chaotic by nature. Therefore, estimating the predictability of the atmosphere is among the main focuses of the scientific community. The degree of chaos or predictability of a system can be expressed by the Lyapunov exponents which represents the temporal growth rate of the distance between two system states initially lying close to another. The corresponding spatial representations of uncertainty are the Lyapunov vectors. The estimation or approximation of Lyapunov vectors is therefore of great interest to the researcher dealing with a chaotic system. However, for the atmosphere estimation methods often tend to approximate the leading Lyapunov vectors or the vectors corresponding to the largest Lyapunov exponents. Depending on the system and situation, smaller Lyapunov exponents may indeed be of more interest. We therefore present research results from two fields of work: (1) uncertainty estimation applied to weather forecasting using techniques adapted to the given practical limitations and (2) idealized Lyapunov analysis using a simple global circulation model (GCM). Perturbation structures intended for ensemble initialization and generated using the Bred Vector (BV) technique for example, tend to converge with the Leading Lyapunov vector disregarding other possibly important information on system/model uncertainty. Our Ensemble Transform Bred Vector (ETBV) approach (Keller et al., 2010) based on the exploitation of the similarities in the BV structures to generate perturbations with different error growth characteristics. We present results from ETBV-driven ensemble forecasts with a global numerical weather prediction model and the performance gain over forecasts driven by simple BVs. We further investigate the effect of downscaling of the resulting large scale uncertainty patterns as forcing for meso-scale weather prediction, thereby testing several different downscaling approaches. We also consider

  15. The influence of sulfur and hair growth on stable isotope diet estimates for grizzly bears.

    PubMed

    Mowat, Garth; Curtis, P Jeff; Lafferty, Diana J R

    2017-01-01

    Stable isotope ratios of grizzly bear (Ursus arctos) guard hair collected from bears on the lower Stikine River, British Columbia (BC) were analyzed to: 1) test whether measuring δ34S values improved the precision of the salmon (Oncorhynchus spp.) diet fraction estimate relative to δ15N as is conventionally done, 2) investigate whether measuring δ34S values improves the separation of diet contributions of moose (Alces alces), marmot (Marmota caligata), and mountain goat (Oreamnos americanus) and, 3) examine the relationship between collection date and length of hair and stable isotope values. Variation in isotope signatures among hair samples from the same bear and year were not trivial. The addition of δ34S values to mixing models used to estimate diet fractions generated small improvement in the precision of salmon and terrestrial prey diet fractions. Although the δ34S value for salmon is precise and appears general among species and areas, sulfur ratios were strongly correlated with nitrogen ratios and therefore added little new information to the mixing model regarding the consumption of salmon. Mean δ34S values for the three terrestrial herbivores of interest were similar and imprecise, so these data also added little new information to the mixing model. The addition of sulfur data did confirm that at least some bears in this system ate marmots during summer and fall. We show that there are bears with short hair that assimilate >20% salmon in their diet and bears with longer hair that eat no salmon living within a few kilometers of one another in a coastal ecosystem. Grizzly bears are thought to re-grow hair between June and October however our analysis of sectioned hair suggested at least some hairs begin growing in July or August, not June and, that hair of wild bears may grow faster than observed in captive bears. Our hair samples may have been from the year of sampling or the previous year because samples were collected in summer when bears were

  16. The influence of sulfur and hair growth on stable isotope diet estimates for grizzly bears

    PubMed Central

    Curtis, P. Jeff; Lafferty, Diana J. R.

    2017-01-01

    Stable isotope ratios of grizzly bear (Ursus arctos) guard hair collected from bears on the lower Stikine River, British Columbia (BC) were analyzed to: 1) test whether measuring δ34S values improved the precision of the salmon (Oncorhynchus spp.) diet fraction estimate relative to δ15N as is conventionally done, 2) investigate whether measuring δ34S values improves the separation of diet contributions of moose (Alces alces), marmot (Marmota caligata), and mountain goat (Oreamnos americanus) and, 3) examine the relationship between collection date and length of hair and stable isotope values. Variation in isotope signatures among hair samples from the same bear and year were not trivial. The addition of δ34S values to mixing models used to estimate diet fractions generated small improvement in the precision of salmon and terrestrial prey diet fractions. Although the δ34S value for salmon is precise and appears general among species and areas, sulfur ratios were strongly correlated with nitrogen ratios and therefore added little new information to the mixing model regarding the consumption of salmon. Mean δ34S values for the three terrestrial herbivores of interest were similar and imprecise, so these data also added little new information to the mixing model. The addition of sulfur data did confirm that at least some bears in this system ate marmots during summer and fall. We show that there are bears with short hair that assimilate >20% salmon in their diet and bears with longer hair that eat no salmon living within a few kilometers of one another in a coastal ecosystem. Grizzly bears are thought to re-grow hair between June and October however our analysis of sectioned hair suggested at least some hairs begin growing in July or August, not June and, that hair of wild bears may grow faster than observed in captive bears. Our hair samples may have been from the year of sampling or the previous year because samples were collected in summer when bears were

  17. 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.

  18. Atmospheric transport and deposition of acidic air pollutants

    SciTech Connect

    Murphy, C.E. Jr.

    1981-01-01

    Although general principles which govern atmospheric chemistry of sulfur are understood, a purely theoretical estimation of the magnitude of the processes is not likely to be useful. Furthermore, the data base necessary to make empirical estimates does not yet exist. The sulfur budget of the atmosphere appears to be dominated by man-associated sulfur. The important processes in deposition of man-associated sulfur are wet deposition of sulfate and dry deposition of SO/sub 2/. The relative importance of sulfate and SO/sub 2/ to sulfur deposition (input to watersheds) depends on the air concentrations, and either compound may be the greater contributor depending on conditions. (PSB)

  19. Atmospheric dispersion estimates in the vicinity of buildings

    SciTech Connect

    Ramsdell, J.V. Jr.; Fosmire, C.J.

    1995-01-01

    A model describing atmospheric dispersion in the vicinity of buildings was developed for the U.S. Nuclear Regulatory Commission (NRC) in the late 1980s. That model has recently undergone additional peer review. The reviewers identified four areas of concern related to the model and its application. This report describes revisions to the model in response to the reviewers concerns. Model revision involved incorporation of explicit treatment of enhanced dispersion at low wind speeds in addition to explicit treatment of enhanced dispersion at high speeds resulting from building wakes. Model parameters are evaluated from turbulence data. Experimental diffusion data from seven reactor sites are used for model evaluation. Compared with models recommended in current NRC guidance to licensees, the revised model is less biased and shows more predictive skill. The revised model is also compared with two non-Gaussian models developed to estimate maximum concentrations in building wakes. The revised model concentration predictions are nearly the same as the predictions of the non-Gaussian models. On the basis of these comparisons of the revised model concentration predictions with experimental data and the predictions of other models, the revised model is found to be an appropriate model for estimating concentrations in the vicinity of buildings.

  20. 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...

  1. 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...

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. 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

  8. 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

  9. Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument

    NASA Astrophysics Data System (ADS)

    Novelli, Anna; Hens, Korbinian; Tatum Ernest, Cheryl; Martinez, Monica; Nölscher, Anke C.; Sinha, Vinayak; Paasonen, Pauli; Petäjä, Tuukka; Sipilä, Mikko; Elste, Thomas; Plass-Dülmer, Christian; Phillips, Gavin J.; Kubistin, Dagmar; Williams, Jonathan; Vereecken, Luc; Lelieveld, Jos; Harder, Hartwig

    2017-06-01

    We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of sulfur dioxide. SCIs also add to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of ˜ 5.0 × 104 molecules cm-3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCIs, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere.

  10. 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

  11. 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

  12. 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.

  13. Estimating the contribution of bryophytes to the atmospheric COS budget

    NASA Astrophysics Data System (ADS)

    Gimeno, Teresa; Ogee, Jerome; Wingate, Lisa

    2017-04-01

    In the past decade, global biogeochemical modellers have embraced enthusiastically the potential of carbonyl sulphide (COS) as a tracer for gross primary productivity (GPP). COS is the most abundant sulphur-containing gas in the atmosphere, it is produced mainly in the ocean and it is consumed by the biosphere, with terrestrial vegetation being the most important contributor. Plant COS uptake is proportional to photosynthetic CO2 withdraw and that is why measurements of the biosphere-atmosphere COS flux can serve a proxy for GPP. Plant COS uptake is mediated by the light-independent enzyme carbonic anhydrase that irreversibly hydrolyses COS into H2S, which is quickly utilised as a sulphur source. Currently, there are no described plant-processes with COS as a by-product and hence the atmospheric-plant COS flux is assumed unidirectional. So far, we had focused on characterizing plant COS uptake dynamics on vascular plants and previous studies are consistent with the unidirectional flux assumption. However, although early works on sulphur metabolism suggested non-vascular plants might not abide to this assumption, we lack estimates of COS uptake dynamics for non-vascular communities. Bryophytes are key constituents of biocrusts and non-vascular photoautrophic communities and in temperate and cold latitudes contribute significantly to ecosystem carbon and nutrient cycling. We expect that in these ecosystems the coupling between COS and CO2 uptake will be influenced by specific environmental cues that control gas-exchange in bryophytes. We expect tissue hydration to be the most influential driver on COS uptake. In contrast, light would constrain CO2 but not COS uptake and therefore we expect greater uncoupling of COS and CO2 in the dark than in vascular plants. We characterized COS and CO2 uptake dynamics in two broadly distributed bryophytes, with contrasting life forms and evolutionary origins: the liverwort Marchantia polymorpha and the feather moss Scleropodium

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Estimates of atmospheric O2 in the Paleoproterozoic from paleosols

    NASA Astrophysics Data System (ADS)

    Kanzaki, Yoshiki; Murakami, Takashi

    2016-02-01

    A weathering model was developed to constrain the partial pressure of atmospheric O2 (PO2) in the Paleoproterozoic from the Fe records in paleosols. The model describes the Fe behavior in a weathering profile by dissolution/precipitation of Fe-bearing minerals, oxidation of dissolved Fe(II) to Fe(III) by oxygen and transport of dissolved Fe by water flow, in steady state. The model calculates the ratio of the precipitated Fe(III)-(oxyhydr)oxides from the dissolved Fe(II) to the dissolved Fe(II) during weathering (ϕ), as a function of PO2 . An advanced kinetic expression for Fe(II) oxidation by O2 was introduced into the model from the literature to calculate accurate ϕ-PO2 relationships. The model's validity is supported by the consistency of the calculated ϕ-PO2 relationships with those in the literature. The model can calculate PO2 for a given paleosol, once a ϕ value and values of the other parameters relevant to weathering, namely, pH of porewater, partial pressure of carbon dioxide (PCO2), water flow, temperature and O2 diffusion into soil, are obtained for the paleosol. The above weathering-relevant parameters were scrutinized for individual Paleoproterozoic paleosols. The values of ϕ, temperature, pH and PCO2 were obtained from the literature on the Paleoproterozoic paleosols. The parameter value of water flow was constrained for each paleosol from the mass balance of Si between water and rock phases and the relationships between water saturation ratio and hydraulic conductivity. The parameter value of O2 diffusion into soil was calculated for each paleosol based on the equation for soil O2 concentration with the O2 transport parameters in the literature. Then, we conducted comprehensive PO2 calculations for individual Paleoproterozoic paleosols which reflect all uncertainties in the weathering-relevant parameters. Consequently, robust estimates of PO2 in the Paleoproterozoic were obtained: 10-7.1-10-5.4 atm at ∼2.46 Ga, 10-5.0-10-2.5 atm at ∼2

  20. Estimates of Ground Temperature and Atmospheric Moisture from CERES Observations

    NASA Technical Reports Server (NTRS)

    Wu, Man Li C.; Schubert, Siegfried; Einaudi, Franco (Technical Monitor)

    2000-01-01

    A method is developed to retrieve surface ground temperature (Tg) and atmospheric moisture using clear sky fluxes (CSF) from CERES-TRMM observations. In general, the clear sky outgoing long-wave radiation (CLR) is sensitive to upper level moisture (q(sub h)) over wet regions and Tg over dry regions The clear sky window flux from 800 to 1200 /cm (RadWn) is sensitive to low level moisture (q(sub j)) and Tg. Combining these two measurements (CLR and RadWn), Tg and q(sub h) can be estimated over land, while q(sub h) and q(sub t) can be estimated over the oceans. The approach capitalizes on the availability of satellite estimates of CLR and RadWn and other auxiliary satellite data. The basic methodology employs off-line forward radiative transfer calculations to generate synthetic CSF data from two different global 4-dimensional data assimilation products. Simple linear regression is used to relate discrepancies in CSF to discrepancies in Tg, q(sub h) and q(sub t). The slopes of the regression lines define sensitivity parameters that can be exploited to help interpret mismatches between satellite observations and model-based estimates of CSF. For illustration, we analyze the discrepancies in the CSF between an early implementation of the Goddard Earth Observing System Data Assimilation System (GEOS-DAS) and a recent operational version of the European Center for Medium-Range Weather Prediction data assimilation system. In particular, our analysis of synthetic total and window region SCF differences (computed from two different assimilated data sets) shows that simple linear regression employing (Delta)Tg and broad layer (Delta)q(sub l) from 500 hPa to surface and (Delta)q(sub h) from 200 to 500 hPa provides a good approximation to the full radiative transfer calculations, typically explaining more than 90% of the 6-hourly variance in the flux differences. These simple regression relations can be inverted to "retrieve" the errors in the geophysical parameters

  1. Estimates of Ground Temperature and Atmospheric Moisture from CERES Observations

    NASA Technical Reports Server (NTRS)

    Wu, Man Li C.; Schubert, Siegfried; Einaudi, Franco (Technical Monitor)

    2000-01-01

    A method is developed to retrieve surface ground temperature (T(sub g)) and atmospheric moisture using clear sky fluxes (CSF) from CERES-TRMM observations. In general, the clear sky outgoing longwave radiation (CLR) is sensitive to upper level moisture (q(sub l)) over wet regions and (T(sub g)) over dry regions The clear sky window flux from 800 to 1200/cm (RadWn) is sensitive to low level moisture (q(sub t)) and T(sub g). Combining these two measurements (CLR and RadWn), Tg and q(sub h) can be estimated over land, while q(sub h) and q(sub l) can be estimated over the oceans. The approach capitalizes on the availability of satellite estimates of CLR and RadWn and other auxiliary satellite data. The basic methodology employs off-line forward radiative transfer calculations to generate synthetic CSF data from two different global 4-dimensional data assimilation products. Simple linear regression is used to relate discrepancies in CSF to discrepancies in T(sub g), q(sub h) and q(sub l). The slopes of the regression lines define sensitivity parameters that can be exploited to help interpret mismatches between satellite observations and model-based estimates of CSF. For illustration, we analyze the discrepancies in the CSF between an early implementation of the Goddard Earth Observing System Data Assimilation System (GEOS-DAS) and a recent operational version of the European Center for Medium-Range Weather Prediction data assimilation system. In particular, our analysis of synthetic total and window region SCF differences (computed from two different assimilated data sets) shows that simple linear regression employing Delta(T(sub g)) and broad layer Delta(q(sub l) from .500 hPa to surface and Delta(q(sub h)) from 200 to .300 hPa provides a good approximation to the full radiative transfer calculations. typically explaining more than 90% of the 6-hourly variance in the flux differences. These simple regression relations can be inverted to "retrieve" the errors in the

  2. 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.

  3. 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.

  4. 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.

  5. Estimating top-of-atmosphere thermal infrared radiance using MERRA-2 atmospheric data

    NASA Astrophysics Data System (ADS)

    Kleynhans, Tania; Montanaro, Matthew; Gerace, Aaron; Kanan, Christopher

    2017-05-01

    Thermal infrared satellite images have been widely used in environmental studies. However, satellites have limited temporal resolution, e.g., 16 day Landsat or 1 to 2 day Terra MODIS. This paper investigates the use of the Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2) reanalysis data product, produced by NASA's Global Modeling and Assimilation Office (GMAO) to predict global topof-atmosphere (TOA) thermal infrared radiance. The high temporal resolution of the MERRA-2 data product presents opportunities for novel research and applications. Various methods were applied to estimate TOA radiance from MERRA-2 variables namely (1) a parameterized physics based method, (2) Linear regression models and (3) non-linear Support Vector Regression. Model prediction accuracy was evaluated using temporally and spatially coincident Moderate Resolution Imaging Spectroradiometer (MODIS) thermal infrared data as reference data. This research found that Support Vector Regression with a radial basis function kernel produced the lowest error rates. Sources of errors are discussed and defined. Further research is currently being conducted to train deep learning models to predict TOA thermal radiance

  6. Spectral Dark Subtraction: A MODTRAN-Based Algorithm for Estimating Ground Reflectance without Atmospheric Information

    NASA Technical Reports Server (NTRS)

    Freedman, Ellis; Ryan, Robert; Pagnutti, Mary; Holekamp, Kara; Gasser, Gerald; Carver, David; Greer, Randy

    2007-01-01

    Spectral Dark Subtraction (SDS) provides good ground reflectance estimates across a variety of atmospheric conditions with no knowledge of those conditions. The algorithm may be sensitive to errors from stray light, calibration, and excessive haze/water vapor. SDS seems to provide better estimates than traditional algorithms using on-site atmospheric measurements much of the time.

  7. Estimation of Atmospheric Mixing Layer Height from radiosonde data

    NASA Astrophysics Data System (ADS)

    Wang, X.; Wang, K.

    2013-12-01

    Mixing layer is the lowest layer of the troposphere where surface turbulence can reach during the daytime. Mixing layer height (MLH) is an important parameter for understanding the transport process, air pollution, weather and climate change. MLH can be determined from the radiosonde profiles of relative humidity (RH), specific humidity (q), potential temperature (θ) and atmospheric refractivity (N) by searching for the strongest gradients of these parameters within a specific height above the surface. However, substantially different MLHs have been found from different parameters. The occurrence of cloud impacts on MLHs derived in two ways: (1) clouds impact the measurements of θ and RH, resulting in spurious MLHs derived by θ and RH, (2) clouds may amplify or depress turbulence, that is MLH can be at cloud top or cloud base when it occurs. However, MLHs determined by existing methods can generally be at cloud top. To solve these problems, we propose a method to estimate MLH by integrating the information of θ, RH, q, N and discriminating different cloud impacts on MLH. We apply this method to high vertical resolution (~30 m) radiosonde data collected at the 79 stations over North America during the period of 1998 to 2008 released by the Stratospheric Processes and their Role in Climate Data Center. The results show good agreement with those from N as the information of temperature and humidity contained in N, however the impact of clouds including in the new method has increased the reliability of MLH. The new results show good agreement with independent MLH determined from Lidar observations. MLH over the North America is 1647×323 meter with a strong east-west gradient, higher MLH (generally greater than 1800 m) over the Midwest America and lower MLH (less than 1300 m) over Alaska and west coast of America. The scatter plot of climatological MLHnew with MLHθ, MLHRH, MLHq, MLHN and MLHint for the period of 1998 to 2008. Pattern of climatological MLH of our

  8. 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

  9. Coupled Inertial Navigation and Flush Air Data Sensing Algorithm for Atmosphere Estimation

    NASA Technical Reports Server (NTRS)

    Karlgaard, Christopher D.; Kutty, Prasad; Schoenenberger, Mark

    2016-01-01

    This paper describes an algorithm for atmospheric state estimation based on a coupling between inertial navigation and flush air data-sensing pressure measurements. The navigation state is used in the atmospheric estimation algorithm along with the pressure measurements and a model of the surface pressure distribution to estimate the atmosphere using a nonlinear weighted least-squares algorithm. The approach uses a high-fidelity model of atmosphere stored in table-lookup form, along with simplified models propagated along the trajectory within the algorithm to aid the solution. Thus, the method is a reduced-order Kalman filter in which the inertial states are taken from the navigation solution and atmospheric states are estimated in the filter. The algorithm is applied to data from the Mars Science Laboratory entry, descent, and landing from August 2012. Reasonable estimates of the atmosphere are produced by the algorithm. The observability of winds along the trajectory are examined using an index based on the observability Gramian and the pressure measurement sensitivity matrix. The results indicate that bank reversals are responsible for adding information content. The algorithm is applied to the design of the pressure measurement system for the Mars 2020 mission. A linear covariance analysis is performed to assess estimator performance. The results indicate that the new estimator produces more precise estimates of atmospheric states than existing algorithms.

  10. Estimating atmospheric temperature profile by an airborne microwave radiometer

    NASA Astrophysics Data System (ADS)

    Zhang, Jun; Xu, Jian; Kenntner, Mareike; Schreier, Franz; Doicu, Adrian

    2017-04-01

    As the rising atmospheric issues such as climate change, air pollution, and ozone depletion have extracted extensive attraction worldwide, observing and modeling of atmospheric quantities becomes critical to our understanding of the environment. This work focuses on the performance of an airborne passive microwave radiometer called MTP (Microwave Temperature Profiler). We aim to obtain vertically distributed atmospheric temperature from intensities measured by the instrument in terms of three frequencies and ten viewing angles. A retrieval program TIRAMISU (Temperature InveRsion Algorithm for MIcrowave SoUnding) has been utilized for processing the MTP data. To solve this severely ill-posed inverse problem, an analysis of different ways of constructing the penalty term onto the Tikhonov-type objective function is conducted. This numerical analysis can help us to better understand pros and cons of these regularization methods and to investigate the measurement capabilities of MTP.

  11. The role of crystallization-driven exsolution on the sulfur mass balance in volcanic arc magmas

    NASA Astrophysics Data System (ADS)

    Su, Y.; Huber, Christian; Bachmann, Olivier; Zajacz, Zoltán.; Wright, Heather; Vazquez, Jorge

    2016-08-01

    The release of large amounts of sulfur to the stratosphere during explosive eruptions affects the radiative balance in the atmosphere and consequentially impacts climate for up to several years after the event. Quantitative estimations of the processes that control the mass balance of sulfur between melt, crystals, and vapor bubbles is needed to better understand the potential sulfur yield of individual eruption events and the conditions that favor large sulfur outputs to the atmosphere. The processes that control sulfur partitioning in magmas are (1) exsolution of volatiles (dominantly H2O) during decompression (first boiling) and during isobaric crystallization (second boiling), (2) the crystallization and breakdown of sulfide or sulfate phases in the magma, and (3) the transport of sulfur-rich vapor (gas influx) from deeper unerupted regions of the magma reservoir. Vapor exsolution and the formation/breakdown of sulfur-rich phases can all be considered as closed-system processes where mass balance arguments are generally easier to constrain, whereas the contribution of sulfur by vapor transport (open system process) is more difficult to quantify. The ubiquitous "excess sulfur" problem, which refers to the much higher sulfur mass released during eruptions than what can be accounted for by amount of sulfur originally dissolved in erupted melt, as estimated from melt inclusion sulfur concentrations (the "petrologic estimate"), reflects the challenges in closing the sulfur mass balance between crystals, melt, and vapor before and during a volcanic eruption. In this work, we try to quantify the relative importance of closed- and open-system processes for silicic arc volcanoes using kinetic models of sulfur partitioning during exsolution. Our calculations show that crystallization-induced exsolution (second boiling) can generate a significant fraction of the excess sulfur observed in crystal-rich arc magmas. This result does not negate the important role of vapor

  12. A model for estimating air-pollutant uptake by forests: calculation of absorption of sulfur dioxide from dispersed sources

    Treesearch

    C. E., Jr. Murphy; T. R. Sinclair; K. R. Knoerr

    1977-01-01

    The computer model presented in this paper is designed to estimate the uptake of air pollutants by forests. The model utilizes submodels to describe atmospheric diffusion immediately above and within the canopy, and into the sink areas within or on the trees. The program implementing the model is general and can be used with only minor changes for any gaseous pollutant...

  13. 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%.

  14. 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.

  15. 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.

  16. Uncertainties in BC Estimations: the Role of Atmospheric Processes

    NASA Astrophysics Data System (ADS)

    Vignati, E.; Kloster, S.; Koch, D.; Bauer, S. E.; Dentener, F.; Bond, T.; Sun, H.

    2006-12-01

    Modelling physical and chemical processes involving aerosol particles remains a large source of uncertainties. To characterize the range of uncertainty in these processes on atmospheric BC concentrations, three global models (CTM-TM5, GCM ECHAM5-HAM and GISS GCM) were run using identical BC, particulate organic matter and SO2 emission inventories provided by IIASA for the year 2000. The first two models have the same aerosol dynamic module, while TM5 is also run with a bulk aerosol scheme; the GISS model uses both bulk aerosol and a method of moments aerosol microphysical schemes. We can thus specifically assess the differences in predicted BC concentrations from using the bulk approach and the two microphysical schemes. By comparing the modeled concentrations with an extensive data set of observations, distinguished by measurement methodology, season and region, we will critically evaluate the benefit of using microphysical schemes to simulate the atmospheric BC cycle.

  17. Estimation of the efficiency of atmospheric ozone aerosol sink

    NASA Astrophysics Data System (ADS)

    Sirota, Vitaly

    1993-11-01

    The interaction of ozone with oxides occurring in aerosols (Al2O3, ZnO, MgO, TiO2) at temperatures 22 divided by -63.5 degree(s)C was provided. Laboratory experiments have shown that activity of investigated oxides with respect to ozone grows under irradiation of their surface. To calculate correctly atmospheric ozone aerosol sink one must take account of both heterogeneous processes proceeding without action of light and photocatalytic ones.

  18. Equipment Design and Cost Estimation for Small Modular Biomass Systems, Synthesis Gas Cleanup, and Oxygen Separation Equipment; Task 2.3: Sulfur Primer

    SciTech Connect

    Nexant Inc.

    2006-05-01

    This deliverable is Subtask 2.3 of Task 2, Gas Cleanup Design and Cost Estimates, of NREL Award ACO-5-44027, ''Equipment Design and Cost Estimation for Small Modular Biomass Systems, Synthesis Gas Cleanup and Oxygen Separation Equipment''. Subtask 2.3 builds upon the sulfur removal information first presented in Subtask 2.1, Gas Cleanup Technologies for Biomass Gasification by adding additional information on the commercial applications, manufacturers, environmental footprint, and technical specifications for sulfur removal technologies. The data was obtained from Nexant's experience, input from GTI and other vendors, past and current facility data, and existing literature.

  19. 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.

  20. 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.

  1. 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

  2. Coupled Inertial Navigation and Flush Air Data Sensing Algorithm for Atmosphere Estimation

    NASA Technical Reports Server (NTRS)

    Karlgaard, Christopher D.; Kutty, Prasad; Schoenenberger, Mark

    2015-01-01

    This paper describes an algorithm for atmospheric state estimation that is based on a coupling between inertial navigation and flush air data sensing pressure measurements. In this approach, the full navigation state is used in the atmospheric estimation algorithm along with the pressure measurements and a model of the surface pressure distribution to directly estimate atmospheric winds and density using a nonlinear weighted least-squares algorithm. The approach uses a high fidelity model of atmosphere stored in table-look-up form, along with simplified models of that are propagated along the trajectory within the algorithm to provide prior estimates and covariances to aid the air data state solution. Thus, the method is essentially a reduced-order Kalman filter in which the inertial states are taken from the navigation solution and atmospheric states are estimated in the filter. The algorithm is applied to data from the Mars Science Laboratory entry, descent, and landing from August 2012. Reasonable estimates of the atmosphere and winds are produced by the algorithm. The observability of winds along the trajectory are examined using an index based on the discrete-time observability Gramian and the pressure measurement sensitivity matrix. The results indicate that bank reversals are responsible for adding information content to the system. The algorithm is then applied to the design of the pressure measurement system for the Mars 2020 mission. The pressure port layout is optimized to maximize the observability of atmospheric states along the trajectory. Linear covariance analysis is performed to assess estimator performance for a given pressure measurement uncertainty. The results indicate that the new tightly-coupled estimator can produce enhanced estimates of atmospheric states when compared with existing algorithms.

  3. 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

  4. 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

  5. Comparison of atmospheric parameters estimated from VLBI, GPS and microwave radiometer data.

    NASA Astrophysics Data System (ADS)

    Gradinarsky, L. P.; Haas, R.; Johansson, J. M.; Elgered, G.

    1999-03-01

    Very Long Baseline Interferometry (VLBI) is colocated with a permanent Global Positioning System (GPS) receiver and a Water Vapour Radiometer (WVR) at the Onsala Space Observatory (OSO). Both VLBI and GPS data are affected by the propagation delay of radio waves in the atmosphere, while the WVR is sensitive to the atmospheric emission close to the center of the 22 GHz water vapour emission line and provides wet delay estimates. The authors present a comparison of estimated atmospheric parameters (equivalent zenith wetdelay and linear horizontal delay gradients) derived from an independent analysis of simultaneous VLBI, GPS and WVR observations. They study and compare the estimated parameters using different elevation cut off angles for the analysis of VLBI data with those obtained from the GPS and the WVR data analyses. The parameters are estimated for 90, 180 and 360 minutes long intervals, which allows to study the averaging effect on the integrated parameters of the turbulent atmosphere.

  6. Estimating spatial veriability in atmospheric properties over remotely sensed land-surface conditions

    USDA-ARS?s Scientific Manuscript database

    This paper investigates the spatial relationships between land-surface fluxes and near-surface atmospheric properties (AP), and the potential errors in flux estimation due to homogeneous atmospheric inputs over heterogeneous landscapes. A Large Eddy Simulation (LES) model is coupled to a surface ene...

  7. Stellar atmospheric parameter estimation using Gaussian process regression

    NASA Astrophysics Data System (ADS)

    Bu, Yude; Pan, Jingchang

    2015-02-01

    As is well known, it is necessary to derive stellar parameters from massive amounts of spectral data automatically and efficiently. However, in traditional automatic methods such as artificial neural networks (ANNs) and kernel regression (KR), it is often difficult to optimize the algorithm structure and determine the optimal algorithm parameters. Gaussian process regression (GPR) is a recently developed method that has been proven to be capable of overcoming these difficulties. Here we apply GPR to derive stellar atmospheric parameters from spectra. Through evaluating the performance of GPR on Sloan Digital Sky Survey (SDSS) spectra, Medium resolution Isaac Newton Telescope Library of Empirical Spectra (MILES) spectra, ELODIE spectra and the spectra of member stars of galactic globular clusters, we conclude that GPR can derive stellar parameters accurately and precisely, especially when we use data preprocessed with principal component analysis (PCA). We then compare the performance of GPR with that of several widely used regression methods (ANNs, support-vector regression and KR) and find that with GPR it is easier to optimize structures and parameters and more efficient and accurate to extract atmospheric parameters.

  8. Using CFCs and Sulfur Hexafluoride to Improve Estimates of Ventilation Rate Changes and Anthropogenic CO2 Uptake Along CLIVAR Repeat Hydrography Sections

    NASA Astrophysics Data System (ADS)

    Bullister, J. L.; Sonnerup, R. E.; Warner, M. J.

    2008-12-01

    A number of key hydrographic sections sampled in the 1990s as part of the World Ocean Circulation Experiment (WOCE) are being re-occupied at approximately decadal intervals as part of the CLIVAR Repeat Hydrography Program. Measurements of a number of physical and chemical properties are made at full depth, closely spaced (nominally 30 nautical mile) CTD/rosette stations, with water samples collected at between 24 and 36 depths per station. Among the central goals of the program are the detection of changes in ventilation, carbon uptake and storage, dissolved oxygen and water properties on decadal time scales. Repeat measurements of dissolved chlorofluorocarbon (CFC) CFC-11 and CFC-12 concentrations show significant decadal increases. Water mass ages derived from CFCs (pCFC ages) also show substantial changes (typically increases) with time along the repeat sections. Simple models indicate that much of the observed pCFC age increases are due to the impacts of mixing in the ocean interior. Measurements of sulfur hexafluoride (SF6), a transient tracer that has been rapidly increasing in the atmosphere during the past several decades, have been included along with CFCs on some recent CLIVAR repeat sections. Because the atmospheric history of SF6 differs substantially from that of the CFCs, concurrent SF6 and CFC measurements can be used to help diagnose the impacts of mixing on pCFC ages and on decadal changes in pCFC ages. We are exploiting this twin-tracer strategy in an attempt to improve estimates of ventilation rate changes and anthropogenic CO2 uptake rates along the CLIVAR repeat sections.

  9. 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;…

  10. Modelling the atmospheric boundary layer for remotely sensed estimates of daily evaporation

    NASA Technical Reports Server (NTRS)

    Gurney, R. J.; Blyth, K.; Camillo, P. J.

    1984-01-01

    An energy and moisture balance model of the soil surface was used to estimate daily evaporation from wheat and barley fields in West Germany. The model was calibrated using remotely sensed surface temperature estimates. Complete atmospheric boundary layer models are difficult to use because of the number of parameters involved and a simplified model was used here. The resultant evaporation estimates were compared to eddy correlation evaporation estimates and good agreement was found.

  11. Time and space variability of spectral estimates of atmospheric pressure

    NASA Technical Reports Server (NTRS)

    Canavero, Flavio G.; Einaudi, Franco

    1987-01-01

    The temporal and spatial behaviors of atmospheric pressure spectra over the northern Italy and the Alpine massif were analyzed using data on surface pressure measurements carried out at two microbarograph stations in the Po Valley, one 50 km south of the Alps, the other in the foothills of the Dolomites. The first 15 days of the study overlapped with the Alpex Intensive Observation Period. The pressure records were found to be intrinsically nonstationary and were found to display substantial time variability, implying that the statistical moments depend on time. The shape and the energy content of spectra depended on different time segments. In addition, important differences existed between spectra obtained at the two stations, indicating a substantial effect of topography, particularly for periods less than 40 min.

  12. 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.

  13. The role of crystallization-driven exsolution on the sulfur mass balance in volcanic arc magmas

    USGS Publications Warehouse

    Su, Yanqing; Huber, Christian; Bachmann, Olivier; Zajacz, Zoltán; Wright, Heather M.; Vazquez, Jorge A.

    2016-01-01

    The release of large amounts of sulfur to the stratosphere during explosive eruptions affects the radiative balance in the atmosphere and consequentially impacts climate for up to several years after the event. Quantitative estimations of the processes that control the mass balance of sulfur between melt, crystals, and vapor bubbles is needed to better understand the potential sulfur yield of individual eruption events and the conditions that favor large sulfur outputs to the atmosphere. The processes that control sulfur partitioning in magmas are (1) exsolution of volatiles (dominantly H2O) during decompression (first boiling) and during isobaric crystallization (second boiling), (2) the crystallization and breakdown of sulfide or sulfate phases in the magma, and (3) the transport of sulfur-rich vapor (gas influx) from deeper unerupted regions of the magma reservoir. Vapor exsolution and the formation/breakdown of sulfur-rich phases can all be considered as closed-system processes where mass balance arguments are generally easier to constrain, whereas the contribution of sulfur by vapor transport (open system process) is more difficult to quantify. The ubiquitous “excess sulfur” problem, which refers to the much higher sulfur mass released during eruptions than what can be accounted for by amount of sulfur originally dissolved in erupted melt, as estimated from melt inclusion sulfur concentrations (the “petrologic estimate”), reflects the challenges in closing the sulfur mass balance between crystals, melt, and vapor before and during a volcanic eruption. In this work, we try to quantify the relative importance of closed- and open-system processes for silicic arc volcanoes using kinetic models of sulfur partitioning during exsolution. Our calculations show that crystallization-induced exsolution (second boiling) can generate a significant fraction of the excess sulfur observed in crystal-rich arc magmas. This result does not negate the important role of

  14. 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.

  15. Use of a Lumped Model (MAGIC) to Bound the Estimation of Potential Future Effects of Sulfur and Nitrogen Deposition on Lake Chemistry in the Adirondack Mountains

    NASA Astrophysics Data System (ADS)

    Church, M. R.

    2001-12-01

    Leaching of atmospherically deposited nitrogen from forested watersheds can acidify lakes and streams. Using a modified version of the Model of Acidification of Groundwater in Catchments, we made computer simulations of such effects for 36 lake catchments in the Adirondack Mountains of New York State. Our simulations bound the potential changes in regional-scale surface water acidification that might occur there over the next 50 years across broad scenarios of both nitrogen and sulfur deposition as well as ranges of times to watershed nitrogen saturation. Model projections indicated that nitrogen deposition may play a more important role in future acidification than has been previously considered, and may rival or exceed potential effects of sulfur deposition, depending on how rapidly watersheds might become saturated with atmospherically deposited nitrogen.

  16. 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.

  17. Estimating Top-of-Atmosphere Thermal Infrared Radiance Using MERRA-2 Atmospheric Data

    NASA Astrophysics Data System (ADS)

    Kleynhans, Tania

    Space borne thermal infrared sensors have been extensively used for environmental research as well as cross-calibration of other thermal sensing systems. Thermal infrared data from satellites such as Landsat and Terra/MODIS have limited temporal resolution (with a repeat cycle of 1 to 2 days for Terra/MODIS, and 16 days for Landsat). Thermal instruments with finer temporal resolution on geostationary satellites have limited utility for cross-calibration due to their large view angles. Reanalysis atmospheric data is available on a global spatial grid at three hour intervals making it a potential alternative to existing satellite image data. This research explores using the Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2) reanalysis data product to predict top-of-atmosphere (TOA) thermal infrared radiance globally at time scales finer than available satellite data. The MERRA-2 data product provides global atmospheric data every three hours from 1980 to the present. Due to the high temporal resolution of the MERRA-2 data product, opportunities for novel research and applications are presented. While MERRA-2 has been used in renewable energy and hydrological studies, this work seeks to leverage the model to predict TOA thermal radiance. Two approaches have been followed, namely physics-based approach and a supervised learning approach, using Terra/MODIS band 31 thermal infrared data as reference. The first physics-based model uses forward modeling to predict TOA thermal radiance. The second model infers the presence of clouds from the MERRA-2 atmospheric data, before applying an atmospheric radiative transfer model. The last physics-based model parameterized the previous model to minimize computation time. The second approach applied four different supervised learning algorithms to the atmospheric data. The algorithms included a linear least squares regression model, a non-linear support vector regression (SVR) model, a multi

  18. Fast single image haze removal via local atmospheric light veil estimation.

    PubMed

    Sun, Wei; Wang, Hao; Sun, Changhao; Guo, Baolong; Jia, Wenyan; Sun, Mingui

    2015-08-01

    In this study, a novel single-image based dehazing framework is proposed to remove haze artifacts from images through local atmospheric light estimation. We use a novel strategy based on a physical model where the extreme intensity of each RGB pixel is used to define an initial atmospheric veil (local atmospheric light veil). Across bilateral filter is applied to each veil to achieve both local smoothness and edge preservation. A transmission map and a reflection component of each RGB channel are constructed from the physical atmospheric scattering model. The proposed approach avoids adverse effects caused by the error in estimating the global atmospheric light. Experimental results on outdoor hazy images demonstrate that the proposed method produces image output with satisfactory visual quality and color fidelity. Our comparative study demonstrates a higher performance of our method over several state-of-the-art methods.

  19. Fast single image haze removal via local atmospheric light veil estimation

    PubMed Central

    Sun, Wei; Wang, Hao; Sun, Changhao; Guo, Baolong; Jia, Wenyan; Sun, Mingui

    2015-01-01

    In this study, a novel single-image based dehazing framework is proposed to remove haze artifacts from images through local atmospheric light estimation. We use a novel strategy based on a physical model where the extreme intensity of each RGB pixel is used to define an initial atmospheric veil (local atmospheric light veil). Across bilateral filter is applied to each veil to achieve both local smoothness and edge preservation. A transmission map and a reflection component of each RGB channel are constructed from the physical atmospheric scattering model. The proposed approach avoids adverse effects caused by the error in estimating the global atmospheric light. Experimental results on outdoor hazy images demonstrate that the proposed method produces image output with satisfactory visual quality and color fidelity. Our comparative study demonstrates a higher performance of our method over several state-of-the-art methods. PMID:26744548

  20. Estimating vertical fluxes of ozone within the atmospheric boundary layer

    NASA Astrophysics Data System (ADS)

    Belan, Boris D.; Antokhin, Pavel N.; Antokhina, Olga Yu.; Arshinov, Mikhail Yu.; Belan, Sergey B.; Davydov, Denis K.; Krasnov, Oleg A.; Penenko, Alexey V.; Savkin, Denis E.; Sklyadneva, Tatayna K.; Tolmahev, Gennadii N.

    2017-04-01

    Investigation of the vertical distribution of ozone within the atmospheric boundary layer (ABL) was carried out by use of AN-2 light aircraft as a research platform. Vertical fluxes of ozone and their direction from the ground to the free-tropospheric level were calculated based on the in situ measurement data. Research flights have been performed over the greenhouse gas monitoring station located in a background area (56.1-56.4 N, 84.2-84.8 E) in the vicinity of abandoned village of Berezorechka (West Siberia). The schedule of diurnal flights was as follows: the first one just after the sunrise; the second one at noon; the third one 2-3 hours after noon, when a well-developed turbulence is observed; and the last one just before the sunset. A total of 10 diurnal cycles of measurements were undertaken. Analysis of the obtained data showed that the rate of ozone influx from upper layers of the atmosphere is 3-10 times less than the ozone production rate in the ABL. Average rate of ozone influx from the free troposphere was about 1 μg m-3 h-1, but ozone production rate in the ABL was about 5 μg m-3 h-1, so the major part of ozone is formed by photochemical reactions that occur within the ABL and only 20 % of its content is determined by the influx from the free troposphere. The vertical profiles of the ozone fluxes have shown that their maximum values are observed at heights from 200 to 600 m AGL. The height of the maximum depends on the season: in winter it is lower than 200-300 m, and in summer the maximum is observed at 500-600 m. The value of the ozone flux maximum also depends on the season and varies from 1 μg m-2 s-1in winter to 4.2 μg m-2 s-1 in spring. This work was supported by the Russian Foundation for Basic Research (grant No 17-05-00374).

  1. A Vertical Diffusion Scheme to estimate the atmospheric rectifier effect

    NASA Astrophysics Data System (ADS)

    Chen, Baozhang; Chen, Jing M.; Liu, Jane; Chan, Douglas; Higuchi, Kaz; Shashkov, Alexander

    2004-02-01

    The magnitude and spatial distribution of the carbon sink in the extratropical Northern Hemisphere remain uncertain in spite of much progress made in recent decades. Vertical CO2 diffusion in the planetary boundary layer (PBL) is an integral part of atmospheric CO2 transport and is important in understanding the global CO2 distribution pattern, in particular, the rectifier effect on the distribution [Keeling et al., 1989; Denning et al., 1995]. Attempts to constrain carbon fluxes using surface measurements and inversion models are limited by large uncertainties in this effect governed by different processes. In this study, we developed a Vertical Diffusion Scheme (VDS) to investigate the vertical CO2 transport in the PBL and to evaluate CO2 vertical rectification. The VDS was driven by the net ecosystem carbon flux and the surface sensible heat flux, simulated using the Boreal Ecosystem Productivity Simulator (BEPS) and a land surface scheme. The VDS model was validated against half-hourly CO2 concentration measurements at 20 m and 40 m heights above a boreal forest, at Fraserdale (49°52'29.9''N, 81°34'12.3''W), Ontario, Canada. The amplitude and phase of the diurnal/seasonal cycles of simulated CO2 concentration during the growing season agreed closely with the measurements (linear correlation coefficient (R) equals 0.81). Simulated vertical and temporal distribution patterns of CO2 concentration were comparable to those measured at the North Carolina tower. The rectifier effect, in terms of an annual-mean vertical gradient of CO2 concentration in the atmosphere that decreases from the surface to the top of PBL, was found at Fraserdale to be about 3.56 ppmv. Positive covariance between the seasonal cycles of plant growth and PBL vertical diffusion was responsible for about 75% of the effect, and the rest was caused by covariance between their diurnal cycles. The rectifier effect exhibited strong seasonal variations, and the contribution from the diurnal cycle

  2. 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.

  3. 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.

  4. CO2 flux estimation errors associated with moist atmospheric processes

    NASA Astrophysics Data System (ADS)

    Parazoo, N. C.; Denning, A. S.; Kawa, S. R.; Pawson, S.; Lokupitiya, R.

    2012-04-01

    Vertical transport by moist sub-grid scale processes such as deep convection is a well-known source of uncertainty in CO2 source/sink inversion. However, a dynamical link between moist transport, satellite CO2 retrievals, and source/sink inversion has not yet been established. Here we examine the effect of moist processes on (1) synoptic CO2 transport by Version-4 and Version-5 NASA Goddard Earth Observing System Data Assimilation System (NASA-DAS) meteorological analyses, and (2) source/sink inversion. We find that synoptic transport processes, such as fronts and dry/moist conveyors, feed off background vertical CO2 gradients, which are modulated by sub-grid vertical transport. The implication for source/sink estimation is two-fold. First, CO2 variations contained in moist poleward moving air masses are systematically different from variations in dry equatorward moving air. Moist poleward transport is hidden from orbital sensors on satellites, causing a sampling bias, which leads directly to continental scale source/sink estimation errors of up to 0.25 PgC yr-1 in northern mid-latitudes. Second, moist processes are represented differently in GEOS-4 and GEOS-5, leading to differences in vertical CO2 gradients, moist poleward and dry equatorward CO2 transport, and therefore the fraction of CO2 variations hidden in moist air from satellites. As a result, sampling biases are amplified, causing source/sink estimation errors of up to 0.55 PgC yr-1 in northern mid-latitudes. These results, cast from the perspective of moist frontal transport processes, support previous arguments that the vertical gradient of CO2 is a major source of uncertainty in source/sink inversion.

  5. 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 ...

  6. 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

  7. Using optimal estimation method for upper atmospheric Lidar temperature retrieval

    NASA Astrophysics Data System (ADS)

    Zou, Rongshi; Pan, Weilin; Qiao, Shuai

    2016-07-01

    Conventional ground based Rayleigh lidar temperature retrieval use integrate technique, which has limitations that necessitate abandoning temperatures retrieved at the greatest heights due to the assumption of a seeding value required to initialize the integration at the highest altitude. Here we suggests the use of a method that can incorporate information from various sources to improve the quality of the retrieval result. This approach inverts lidar equation via optimal estimation method(OEM) based on Bayesian theory together with Gaussian statistical model. It presents many advantages over the conventional ones: 1) the possibility of incorporating information from multiple heterogeneous sources; 2) provides diagnostic information about retrieval qualities; 3) ability of determining vertical resolution and maximum height to which the retrieval is mostly independent of the a priori profile. This paper compares one-hour temperature profiles retrieved using conventional and optimal estimation methods at Golmud, Qinghai province, China. Results show that OEM results show a better agreement with SABER profile compared with conventional one, in some region it is much lower than SABER profile, which is a very different results compared with previous studies, further studies are needed to explain this phenomenon. The success of applying OEM on temperature retrieval is a validation for using as retrieval framework in large synthetic observation systems including various active remote sensing instruments by incorporating all available measurement information into the model and analyze groups of measurements simultaneously to improve the results.

  8. 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.

  9. Sulfur hexafluoride (SF6) emission estimates for China: an inventory for 1990-2010 and a projection to 2020.

    PubMed

    Fang, Xuekun; Hu, Xia; Janssens-Maenhout, Greet; Wu, Jing; Han, Jiarui; Su, Shenshen; Zhang, Jianbo; Hu, Jianxin

    2013-04-16

    Sulfur hexafluoride (SF6) is the most potent greenhouse gas regulated under the Kyoto Protocol, with a high global warming potential. In this study, SF6 emissions from China were inventoried for 1990-2010 and projected to 2020. Results reveal that the highest SF6 emission contribution originates from the electrical equipment sector (about 70%), followed by the magnesium production sector, the semiconductor manufacture sector and the SF6 production sector (each about 10%). Both agreements and discrepancies were found in comparisons of our estimates with previously published data. An accelerated growth rate was found for Chinese SF6 emissions during 1990-2010. Because the relative growth rate of SF6 emissions is estimated to be much higher than those of CO2, CH4, and N2O, SF6 will play an increasing role in greenhouse gas emissions in China. Global contributions from China increased rapidly from 0.9 ± 0.3% in 1990 to 22.8 ± 6.3% in 2008, making China one of the crucial contributors to the recent growth in global emissions. Under the examined Business-as-usual (BAU) Scenario, projected emissions will reach 4270 ± 1020 t in 2020, but a reduction of about 90% of the projected BAU emissions would be obtained under the Alternative Scenario.

  10. Computer realization of estimations of the atmospheric anomalies caused by gas-aerosol pollution of the near-ground atmosphere

    NASA Astrophysics Data System (ADS)

    Chistyakova, Liliya K.; Isakova, Anna I.; Smal, Oksana V.; Penin, Sergei T.; Kataev, Mikhail Y.; Kopytin, Yurii D.

    2004-02-01

    In the paper, algorithms of the techniques incorporated in subsystems of the program complex are presented for calculation and estimation of atmospheric anomalies, caused by industrial emissions in the atmosphere. The complex is included in the gas analyzer DAN-2, developed for registration of emission and absorption of optical and the microwave radiation initiated by gas-aerosol pollution in the atmosphere. The complex DAN-2 has been developed in the Institute of Atmospheric Optics of the Siberian Branch of the Russian Academy of Science. Techniques include: calculation of gas concentration in a plume of industrial emission taking into account gas-aerosol attenuation, an azimuth of the device sighting at a direction of the source and the allocated illumination of the day-time sky; numerical modeling of formation and distribution of gas-aerosol emission fields in the atmosphere with use of various models (Gaussian, Berlyand, etc); the forecast of optical noise in the atmosphere at operating hardware DAN-2 taking into account different types of underground surfaces under various hydro meteorological conditions; algorithm of restoration of the plume structure under its image. In the paper, results of testing of the specified algorithms are presented with use of the data of natural measurements of NO2 and SO2 concentration in the emission plume of the thermal power station GRES-2 in Tomsk, which were received by the complex DAN-2. Calculation of atmospheric background noise and distributions of the gas-aerosol plume has been carried out by various methods with use of these data.

  11. A Comparison of Estimates of Atmospheric Effects on Signal Propagation Using ITU Models: Initial Study Results

    NASA Astrophysics Data System (ADS)

    Morabito, D. D.

    2014-11-01

    This article provides details on a comparison performed on calculated atmospheric effects on signal propagation using different methods for the Deep Space Network (DSN) and two Near Earth Network (NEN) sites commonly used in telecommunications link budgets. Atmospheric attenuation and scintillation fading are two of the many contributors that need to be taken into account in such link budgets between transmitter and receiver. Although atmospheric noise temperature increase is another contributor (at the receiver), it is well related to atmospheric attenuation through appropriate model equations. Telecommunication engineers working NEN link budgets make use of data and models obtained from the International Telecommunication Union (ITU) in order to estimate atmospheric effects. Such effects include atmospheric attenuation (gaseous, rain, and cloud), atmospheric noise temperature contribution, and scintillation. Because most NEN links usually operate at very high margins, uncertainties in the ITU models were not much of a concern in the past as they tended to be conservative, in comparison to links of the DSN that operate at low margins and thus require more accurate statistics on atmospheric effects. Such statistics for the DSN links make use of brightness temperature measurements from multiyear water vapor radiometer (WVR) data from instruments operating at the DSN sites. Atmospheric attenuation statistics derived from WVR data are well documented and are published by the DSN. Thus, the DSN sites make a good testbed in which to cross-compare atmospheric loss statistics with those derived from ITU data and models.

  12. An adaptive technique for estimating the atmospheric density profile during the AE mission

    NASA Technical Reports Server (NTRS)

    Argentiero, P.

    1973-01-01

    A technique is presented for processing accelerometer data obtained during the AE missions in order to estimate the atmospheric density profile. A minimum variance, adaptive filter is utilized. The trajectory of the probe and probe parameters are in a consider mode where their estimates are unimproved but their associated uncertainties are permitted an impact on filter behavior. Simulations indicate that the technique is effective in estimating a density profile to within a few percentage points.

  13. Automatic parameter estimation for atmospheric turbulence mitigation techniques

    NASA Astrophysics Data System (ADS)

    Kozacik, Stephen; Paolini, Aaron; Kelmelis, Eric

    2015-05-01

    Several image processing techniques for turbulence mitigation have been shown to be effective under a wide range of long-range capture conditions; however, complex, dynamic scenes have often required manual interaction with the algorithm's underlying parameters to achieve optimal results. While this level of interaction is sustainable in some workflows, in-field determination of ideal processing parameters greatly diminishes usefulness for many operators. Additionally, some use cases, such as those that rely on unmanned collection, lack human-in-the-loop usage. To address this shortcoming, we have extended a well-known turbulence mitigation algorithm based on bispectral averaging with a number of techniques to greatly reduce (and often eliminate) the need for operator interaction. Automations were made in the areas of turbulence strength estimation (Fried's parameter), as well as the determination of optimal local averaging windows to balance turbulence mitigation and the preservation of dynamic scene content (non-turbulent motions). These modifications deliver a level of enhancement quality that approaches that of manual interaction, without the need for operator interaction. As a consequence, the range of operational scenarios where this technology is of benefit has been significantly expanded.

  14. 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.

  15. CO2 flux estimation errors associated with moist atmospheric processes

    NASA Astrophysics Data System (ADS)

    Parazoo, N. C.; Denning, A. S.; Kawa, S. R.; Pawson, S.; Lokupitiya, R.

    2012-07-01

    Vertical transport by moist sub-grid scale processes such as deep convection is a well-known source of uncertainty in CO2 source/sink inversion. However, a dynamical link between vertical transport, satellite based retrievals of column mole fractions of CO2, and source/sink inversion has not yet been established. By using the same offline transport model with meteorological fields from slightly different data assimilation systems, we examine sensitivity of frontal CO2 transport and retrieved fluxes to different parameterizations of sub-grid vertical transport. We find that frontal transport feeds off background vertical CO2 gradients, which are modulated by sub-grid vertical transport. The implication for source/sink estimation is two-fold. First, CO2 variations contained in moist poleward moving air masses are systematically different from variations in dry equatorward moving air. Moist poleward transport is hidden from orbital sensors on satellites, causing a sampling bias, which leads directly to small but systematic flux retrieval errors in northern mid-latitudes. Second, differences in the representation of moist sub-grid vertical transport in GEOS-4 and GEOS-5 meteorological fields cause differences in vertical gradients of CO2, which leads to systematic differences in moist poleward and dry equatorward CO2 transport and therefore the fraction of CO2 variations hidden in moist air from satellites. As a result, sampling biases are amplified and regional scale flux errors enhanced, most notably in Europe (0.43 ± 0.35 PgC yr-1). These results, cast from the perspective of moist frontal transport processes, support previous arguments that the vertical gradient of CO2 is a major source of uncertainty in source/sink inversion.

  16. CO2 Flux Estimation Errors Associated with Moist Atmospheric Processes

    NASA Technical Reports Server (NTRS)

    Parazoo, N. C.; Denning, A. S.; Kawa, S. R.; Pawson, S.; Lokupitiya, R.

    2012-01-01

    Vertical transport by moist sub-grid scale processes such as deep convection is a well-known source of uncertainty in CO2 source/sink inversion. However, a dynamical link between vertical transport, satellite based retrievals of column mole fractions of CO2, and source/sink inversion has not yet been established. By using the same offline transport model with meteorological fields from slightly different data assimilation systems, we examine sensitivity of frontal CO2 transport and retrieved fluxes to different parameterizations of sub-grid vertical transport. We find that frontal transport feeds off background vertical CO2 gradients, which are modulated by sub-grid vertical transport. The implication for source/sink estimation is two-fold. First, CO2 variations contained in moist poleward moving air masses are systematically different from variations in dry equatorward moving air. Moist poleward transport is hidden from orbital sensors on satellites, causing a sampling bias, which leads directly to small but systematic flux retrieval errors in northern mid-latitudes. Second, differences in the representation of moist sub-grid vertical transport in GEOS-4 and GEOS-5 meteorological fields cause differences in vertical gradients of CO2, which leads to systematic differences in moist poleward and dry equatorward CO2 transport and therefore the fraction of CO2 variations hidden in moist air from satellites. As a result, sampling biases are amplified and regional scale flux errors enhanced, most notably in Europe (0.43+/-0.35 PgC /yr). These results, cast from the perspective of moist frontal transport processes, support previous arguments that the vertical gradient of CO2 is a major source of uncertainty in source/sink inversion.

  17. Estimating Sulfur Dioxide in Volcanic Plumes Using an Ultraviolet Camera. First Results from Lascar, Ollagüe and Irruputuncu Volcanoes

    NASA Astrophysics Data System (ADS)

    Geoffroy, C. A.; Amigo, A.

    2014-12-01

    Volcanic gas fluxes give important information on both the amount of degassing and magma reservoirs. In most of magmas, water vapor (H2O) and carbon dioxide (CO2) are major components of volcanic gas. However, sulfur dioxide (SO2) is one of the targets of remote sensing due to their low concentration in the environment and easy detection by ultraviolet spectroscopy. Accordingly, plume imaging using passive ultraviolet cameras is a relatively simple method to study volcanic degassing, expeditious manner and can be used up from distances of about 10 km from source of emissions. We estimated SO2 concentrations and fluxes in volcanic plumes with the ultraviolet camera Envicam-2, developed by Nicarnica Aviation, acquired by the Geological Survey of Chile (SERNAGEOMIN). The camera has filters that allow passage of ultraviolet radiation at wavelengths of interest. For determining whether there is absorption of radiation associated with the presence of SO2 the Beer-Lambert law was used for quantifying concentrations using appropriate calibration cells. SO2 emissions to the atmosphere were estimated using wind speed as an approximation to the plume transport. In this study we reported the implementation of a new methodology for using Envicam-2 and subsequent collection of SO2 concentrations and fluxes in passive degassing volcanoes. Measurements were done at Lascar, Ollagüe and Irruputuncu volcanoes, located in northern Chile. The volcanoes were chosen because of optimal atmospheric conditions for ultraviolet imaging. Results indicate concentrations within the expected ranges for three volcanoes generally between 400-1700 ppm•m. In the case of Láscar volcano, the emission rates of SO2 range from 250 to 500 tonnes/day for a same image of the plume. In particular, wind speed was determined from scaling images and are consistent with data from regional numerical models, as well as records of the meteorological stations installed at the ALMA astronomical center, located

  18. 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.

  19. 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.

  20. MAXINE: An improved methodology for estimating maximum individual dose from chronic atmospheric radioactive releases

    SciTech Connect

    Hamby, D.M.

    1994-02-01

    An EXCEL{reg_sign} spreadsheet has been developed that, when combined with the PC version of XOQDOQ, will generate estimates of maximum individual dose from routine atmospheric releases of radionuclides. The spreadsheet, MAXINE, utilizes a variety of atmospheric dispersion factors to calculate radiation dose as recommended by the US Nuclear Regulatory Commission in Regulatory Guide 1.109 [USNRC 1977a]. The methodology suggested herein includes use of both the MAXINE spreadsheet and the PC version of XOQDOQ.

  1. Constraining the atmosphere of GJ 1214b using an optimal estimation technique

    NASA Astrophysics Data System (ADS)

    Barstow, J. K.; Aigrain, S.; Irwin, P. G. J.; Fletcher, L. N.; Lee, J.-M.

    2013-09-01

    We explore cloudy, extended H2-He atmosphere scenarios for the warm super-Earth GJ 1214b using an optimal estimation retrieval technique. This planet, orbiting an M4.5 star only 13 pc from the Earth, is of particular interest because it lies between the Earth and Neptune in size and may be a member of a new class of planet that is neither terrestrial nor gas giant. Its relatively flat transmission spectrum has so far made atmospheric characterization difficult. The Non-linear optimal Estimator for MultivariateE spectral analySIS (NEMESIS) algorithm is used to explore the degenerate model parameter space for a cloudy, H2-He-dominated atmosphere scenario. Optimal estimation is a data-led approach that allows solutions beyond the range permitted by ab initio equilibrium model atmosphere calculations, and as such prevents restriction from prior expectations. We show that optimal estimation retrieval is a powerful tool for this kind of study, and present an exploration of the degenerate atmospheric scenarios for GJ 1214b. Whilst we find a family of solutions that provide a very good fit to the data, the quality and coverage of these data are insufficient for us to more precisely determine the abundances of cloud and trace gases given an H2-He atmosphere, and we also cannot rule out the possibility of a high molecular weight atmosphere. Future ground- and space-based observations will provide the opportunity to confirm or rule out an extended H2-He atmosphere, but more precise constraints will be limited by intrinsic degeneracies in the retrieval problem, such as variations in cloud top pressure and temperature.

  2. Estimation of the atmospheric corrosion on metal containers in industrial waste disposal.

    PubMed

    Baklouti, M; Midoux, N; Mazaudier, F; Feron, D

    2001-08-17

    Solid industrial waste are often stored in metal containers filled with concrete, and placed in well-aerated warehouses. Depending on meteorological conditions, atmospheric corrosion can induce severe material damages to the metal casing, and this damage has to be predicted to achieve safe storage. This work provides a first estimation of the corrosivity of the local atmosphere adjacent to the walls of the container through a realistic modeling of heat transfer phenomena which was developed for this purpose. Subsequent simulations of condensation/evaporation of the water vapor in the atmosphere were carried out. Atmospheric corrosion rates and material losses are easily deduced. For handling realistic data and comparison, two different meteorological contexts were chosen: (1) an oceanic and damp atmosphere and (2) a drier storage location. Some conclusions were also made for the storage configuration in order to reduce the extent of corrosion phenomena.

  3. High CO2 levels in the Proterozoic atmosphere estimated from analyses of individual microfossils.

    PubMed

    Kaufman, Alan J; Xiao, Shuhai

    2003-09-18

    Solar luminosity on the early Earth was significantly lower than today. Therefore, solar luminosity models suggest that, in the atmosphere of the early Earth, the concentration of greenhouse gases such as carbon dioxide and methane must have been much higher. However, empirical estimates of Proterozoic levels of atmospheric carbon dioxide concentrations have not hitherto been available. Here we present ion microprobe analyses of the carbon isotopes in individual organic-walled microfossils extracted from a Proterozoic ( approximately 1.4-gigayear-old) shale in North China. Calculated magnitudes of the carbon isotope fractionation in these large, morphologically complex microfossils suggest elevated levels of carbon dioxide in the ancient atmosphere--between 10 and 200 times the present atmospheric level. Our results indicate that carbon dioxide was an important greenhouse gas during periods of lower solar luminosity, probably dominating over methane after the atmosphere and hydrosphere became pervasively oxygenated between 2 and 2.2 gigayears ago.

  4. Improving Estimates of Atmosphere-Ocean Greenhouse Gas Fluxes for Earth-System Modelling

    NASA Astrophysics Data System (ADS)

    Vieira, V. M. N. C. S.; Sahlee, E.; Jurus, P.; Clementi, E.; Pettersson, H.; Mateus, M.

    2016-08-01

    Accurate estimates of atmosphere-ocean balances and fluxes of greenhouse gases and aerosols are fundamental for Earth-System models forecasting the climate change, and for Earth Observation estimates of oceanic sinks and sources coupling satellite imagery with reverse modelling. The standard formulations are 24 and 36 years old, and recent alternatives have emerged. We developed a framework congregating the geophysical processes involved, customizable with alternative formulations, and that can be used as basis for novel couplers of atmospheric and oceanographic model components. We tested it with fine resolution data from the European coastal ocean. Although the solubility formulations agreed well, their minor divergences yielded differences of many tons of greenhouse gases dissolved at the ocean surface. The transfer velocities largely mismatched their estimates, in part consequence of the standard formulation not considering factors that were proved determinant at the coastal ocean. Climate Change research requires further calibration and validation of atmosphere-ocean interactions.

  5. 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.

  6. Decadal Arctic surface atmosphere/ocean heat budgets and mass transport estimates from several atmospheric and oceanic reanalyses

    NASA Astrophysics Data System (ADS)

    Chepurin, gennaday; Carton, James

    2017-04-01

    The Arctic is undergoing dramatic changes associated with the loss of seasonal and permanent ice pack. By exposing the surface ocean to the atmosphere these changes dramatically increase surface exchange processes. In contrast, increases in freshwater and heat input decreases turbulent exchanges within the ocean. In this study we present results from an examination of changing ocean heat flux, storage, and transport during the 36 year period 1980-2015. To identify changes in the surface atmosphere we examine three atmospheric reanalyses: MERRA2, ERA-I, and JRA55. Significant differences in fluxes from these reanalyses arise due to the representation of clouds and water vapor. These differences provide an indication of the uncertainties in the historical record. Next we turn to the Simple Ocean Data Assimilation version 3 (SODA3) global ocean/sea ice reanalysis system to allow us to infer the full ocean circulation from the limited set of historical record of ocean observations. SODA3 has 10 km horizontal resolution in the Arctic and assimilates the full suite of historical marine temperature and salinity observations. To account for the uncertainties in atmospheric forcing, we repeat our analysis with each of the three atmospheric reanalyses. In the first part of the talk we review the climatological seasonal surface fluxes resulting from our reanalysis system, modified for consistency with the ocean observations, and the limits of what we can learn from the historical record. Next we compare the seasonal hydrography, heat, and mass transports with direct estimates from moorings. Finally we examine the impact on the Arctic climate of the changes in sea ice cover and variability and trends of ocean/sea ice heat storage and transport and their contributions to changes in the seasonal stratification of the Arctic Ocean.

  7. Atmospheric corrections of passive microwave data for estimating land surface temperature.

    PubMed

    Liu, Zeng-Lin; Wu, Hua; Tang, Bo-Hui; Qiu, Shi; Li, Zhao-Liang

    2013-07-01

    Quantitative analysis of the atmospheric effects on observations made by the Advanced Microwave Scanning Radiometer-Earth Observing System (AMSR-E) has been performed. The differences between observed brightness temperatures at the top of the atmosphere and at the bottom of the atmosphere were analyzed using a database of simulated observations, which were configured to replicate AMSR-E data. The differences between observed brightness temperatures at the top of the atmosphere and land surface-emitted brightness temperatures were also computed. Quantitative results show that the atmosphere has different effects on brightness temperatures in different AMSR-E channels. Atmospheric effects can be neglected at 6.925 and 10.65 GHz, when the standard deviation is less than 1 K. However, at other frequencies and polarizations, atmospheric effects on observations should not be neglected. An atmospheric correction algorithm was developed at 18.7 GHz vertical polarization, based on the classic split-window algorithm used in thermal remote sensing. Land surface emission can be estimated with RMSE = 0.99 K using the proposed method. Using the known land surface emissivity, Land Surface Temperature (LST) can be retrieved. The RMSE of retrieved LST is 1.17 K using the simulated data.

  8. 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.

  9. 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

  10. 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

  11. Inverse estimation of radon flux distribution for East Asia using measured atmospheric radon concentration.

    PubMed

    Hirao, S; Hayashi, R; Moriizumi, J; Yamazawa, H; Tohjima, Y; Mukai, H

    2015-11-01

    In this study, the (222)Rn flux density distribution at surface was estimated in East Asia with the Bayesian synthesis inversion using measurement data and a long-range atmospheric (222)Rn transport model. Surface atmospheric (222)Rn concentrations measured at Hateruma Island in January 2008 were used. The estimated (222)Rn flux densities were generally higher than the prior ones. The area-weighted mean (222)Rn flux density for East Asia in January 2008 was estimated to be 44.0 mBq m(-2) s(-1). The use of the estimated (222)Rn flux density improved the discrepancy of the model-calculated concentrations with the measurements at Hateruma Island.

  12. Estimation of the statistical characteristics of signals on a background of atmospheric radio noise

    NASA Astrophysics Data System (ADS)

    Kabanov, V. V.

    1987-09-01

    A method for the detection and estimation of a signal on a background of atmospheric radio noise (ARN) with unknown characteristics is proposed which is based on the presence or absence of zeros in the characteristic functions (CFs) of the signal and ARN. The zero-position estimation makes it possible to verify statistical hypotheses, and to determine the parameters of the signal CF model and the signal statistical characteristics.

  13. 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.

  14. The Ability of Atmospheric Data to Reduce Disagreements in Wetland Methane Flux Estimates over North America

    NASA Astrophysics Data System (ADS)

    Miller, S. M.; Andrews, A. E.; Benmergui, J. S.; Commane, R.; Dlugokencky, E. J.; Janssens-Maenhout, G.; Melton, J. R.; Michalak, A. M.; Sweeney, C.; Worthy, D. E. J.

    2015-12-01

    Existing estimates of methane fluxes from wetlands differ in both magnitude and distribution across North America. We discuss seven different bottom-up methane estimates in the context of atmospheric methane data collected across the US and Canada. In the first component of this study, we explore whether the observation network can even detect a methane pattern from wetlands. We find that the observation network can identify a methane pattern from Canadian wetlands but not reliably from US wetlands. Over Canada, the network can even identify spatial patterns at multi-provence scales. Over the US, by contrast, anthropogenic emissions and modeling errors obscure atmospheric patterns from wetland fluxes. In the second component of the study, we then use these observations to reconcile disagreements in the magnitude, seasonal cycle, and spatial distribution of existing estimates. Most existing estimates predict fluxes that are too large with a seasonal cycle that is too narrow. A model known as LPJ-Bern has a spatial distribution most consistent with atmospheric observations. By contrast, a spatially-constant model outperforms the distribution of most existing flux estimates across Canada. The results presented here provide several pathways to reduce disagreements among existing wetland flux estimates across North America.

  15. A Useful Tool for Atmospheric Correction and Surface Temperature Estimation of Landsat Infrared Thermal Data

    NASA Astrophysics Data System (ADS)

    Rivalland, Vincent; Tardy, Benjamin; Huc, Mireille; Hagolle, Olivier; Marcq, Sébastien; Boulet, Gilles

    2016-04-01

    Land Surface temperature (LST) is a critical variable for studying the energy and water budgets at the Earth surface, and is a key component of many aspects of climate research and services. The Landsat program jointly carried out by NASA and USGS has been providing thermal infrared data for 40 years, but no associated LST product has been yet routinely proposed to community. To derive LST values, radiances measured at sensor-level need to be corrected for the atmospheric absorption, the atmospheric emission and the surface emissivity effect. Until now, existing LST products have been generated with multi channel methods such as the Temperature/Emissivity Separation (TES) adapted to ASTER data or the generalized split-window algorithm adapted to MODIS multispectral data. Those approaches are ill-adapted to the Landsat mono-window data specificity. The atmospheric correction methodology usually used for Landsat data requires detailed information about the state of the atmosphere. This information may be obtained from radio-sounding or model atmospheric reanalysis and is supplied to a radiative transfer model in order to estimate atmospheric parameters for a given coordinate. In this work, we present a new automatic tool dedicated to Landsat thermal data correction which improves the common atmospheric correction methodology by introducing the spatial dimension in the process. The python tool developed during this study, named LANDARTs for LANDsat Automatic Retrieval of surface Temperature, is fully automatic and provides atmospheric corrections for a whole Landsat tile. Vertical atmospheric conditions are downloaded from the ERA Interim dataset from ECMWF meteorological organization which provides them at 0.125 degrees resolution, at a global scale and with a 6-hour-time step. The atmospheric correction parameters are estimated on the atmospheric grid using the commercial software MODTRAN, then interpolated to 30m resolution. We detail the processing steps

  16. Estimation of Atmospheric Path Delays in TerraSAR-X Data using Models vs. Measurements

    PubMed Central

    Jehle, Michael; Perler, Donat; Small, David; Schubert, Adrian; Meier, Erich

    2008-01-01

    Spaceborne synthetic aperture radar (SAR) measurements of the Earth's surface depend on electromagnetic waves that are subject to atmospheric path delays, in turn affecting geolocation accuracy The atmosphere influences radar signal propagation by modifying its velocity and direction, effects which can be modeled. We use TerraSAR-X (TSX) data to investigate improvements in the knowledge of the scene geometry. To precisely estimate atmospheric path delays, we analyse the signal return of four corner reflectors with accurately surveyed positions (based on differential GPS), placed at different altitudes yet with nearly identical slant ranges to the sensor. The comparison of multiple measurements with path delay models under these geometric conditions also makes it possible to evaluate the corrections for the atmospheric path delay made by the TerraSAR processor and to propose possible improvements. PMID:27873997

  17. Comparison of Mars Atmospheric Density Estimates from Models to Measurements from Mars Global Surveyor (MGS) Data

    NASA Technical Reports Server (NTRS)

    Justh, Hilary L.; Justus, C. G.

    2009-01-01

    A recent study (Desai, 2008) has shown that the actual landing sites of Mars Pathfinder, the Mars Exploration Rovers (Spirit and Opportunity) and the Phoenix Mars Lander have been further downrange than predicted by models prior to landing Desai's reconstruction of their entries into the Martian atmosphere showed that the models consistently predicted higher densities than those found upon entry, descent and landing. Desai's results have raised a question as to whether there is a systemic problem within Mars atmospheric models. Proposal is to compare Mars atmospheric density estimates from Mars atmospheric models to measurements made by Mars Global Surveyor (MGS). Comparison study requires the completion of several tasks that would result in a greater understanding of reasons behind the discrepancy found during recent landings on Mars and possible solutions to this problem.

  18. Estimation of Atmospheric Path Delays in TerraSAR-X Data using Models vs. Measurements.

    PubMed

    Jehle, Michael; Perler, Donat; Small, David; Schubert, Adrian; Meier, Erich

    2008-12-19

    Spaceborne synthetic aperture radar (SAR) measurements of the Earth's surface depend on electromagnetic waves that are subject to atmospheric path delays, in turn affecting geolocation accuracy. The atmosphere influences radar signal propagation by modifying its velocity and direction, effects which can be modeled. We use TerraSAR-X (TSX) data to investigate improvements in the knowledge of the scene geometry. To precisely estimate atmospheric path delays, we analyse the signal return of four corner reflectors with accurately surveyed positions (based on differential GPS), placed at different altitudes yet with nearly identical slant ranges to the sensor. The comparison of multiple measurements with path delay models under these geometric conditions also makes it possible to evaluate the corrections for the atmospheric path delay made by the TerraSAR processor and to propose possible improvements.

  19. An assessment of prewhitening in estimating power spectra of atmospheric turbulence at long wavelengths

    NASA Technical Reports Server (NTRS)

    Keisler, S. R.; Rhyne, R. H.

    1976-01-01

    Synthetic time histories were generated and used to assess the effects of prewhitening on the long wavelength portion of power spectra of atmospheric turbulence. Prewhitening is not recommended when using the narrow spectral windows required for determining power spectral estimates below the 'knee' frequency, that is, at very long wavelengths.

  20. Channel estimation for OFDM system in atmospheric optical communication based on compressive sensing

    NASA Astrophysics Data System (ADS)

    Zhao, Qingsong; Hao, Shiqi; Geng, Hongjian; Sun, Han

    2015-10-01

    Orthogonal frequency division multiplexing (OFDM) technique applied to the atmospheric optical communication can improve data transmission rate, restrain pulse interference, and reduce effect of multipath caused by atmospheric scattering. Channel estimation, as one of the important modules in OFDM, has been investigated thoroughly and widely with great progress. In atmospheric optical communication system, channel estimation methods based on pilot are common approaches, such as traditional least-squares (LS) algorithm and minimum mean square error (MMSE) algorithm. However, sensitivity of the noise effects and high complexity of computation are shortcomings of LS algorithm and MMSE algorithm, respectively. Here, a new method based on compressive sensing is proposed to estimate the channel state information of atmospheric optical communication OFDM system, especially when the condition is closely associated with turbulence. Firstly, time-varying channel model is established under the condition of turbulence. Then, in consideration of multipath effect, sparse channel model is available for compressive sensing. And, the pilot signal is reconstructed with orthogonal matching tracking (OMP) algorithm, which is used for reconstruction. By contrast, the work of channel estimation is completed by LS algorithm as well. After that, simulations are conducted respectively in two different indexes -signal error rate (SER) and mean square error (MSE). Finally, result shows that compared with LS algorithm, the application of compressive sensing can improve the performance of SER and MSE. Theoretical analysis and simulation results show that the proposed method is reasonable and efficient.

  1. Optimal Atmospheric Correction for Above-Ground Forest Biomass Estimation with the ETM+ Remote Sensor.

    PubMed

    Nguyen, Hieu Cong; Jung, Jaehoon; Lee, Jungbin; Choi, Sung-Uk; Hong, Suk-Young; Heo, Joon

    2015-07-31

    The reflectance of the Earth's surface is significantly influenced by atmospheric conditions such as water vapor content and aerosols. Particularly, the absorption and scattering effects become stronger when the target features are non-bright objects, such as in aqueous or vegetated areas. For any remote-sensing approach, atmospheric correction is thus required to minimize those effects and to convert digital number (DN) values to surface reflectance. The main aim of this study was to test the three most popular atmospheric correction models, namely (1) Dark Object Subtraction (DOS); (2) Fast Line-of-sight Atmospheric Analysis of Spectral Hypercubes (FLAASH) and (3) the Second Simulation of Satellite Signal in the Solar Spectrum (6S) and compare them with Top of Atmospheric (TOA) reflectance. By using the k-Nearest Neighbor (kNN) algorithm, a series of experiments were conducted for above-ground forest biomass (AGB) estimations of the Gongju and Sejong region of South Korea, in order to check the effectiveness of atmospheric correction methods for Landsat ETM+. Overall, in the forest biomass estimation, the 6S model showed the bestRMSE's, followed by FLAASH, DOS and TOA. In addition, a significant improvement of RMSE by 6S was found with images when the study site had higher total water vapor and temperature levels. Moreover, we also tested the sensitivity of the atmospheric correction methods to each of the Landsat ETM+ bands. The results confirmed that 6S dominates the other methods, especially in the infrared wavelengths covering the pivotal bands for forest applications. Finally, we suggest that the 6S model, integrating water vapor and aerosol optical depth derived from MODIS products, is better suited for AGB estimation based on optical remote-sensing data, especially when using satellite images acquired in the summer during full canopy development.

  2. Optimal Atmospheric Correction for Above-Ground Forest Biomass Estimation with the ETM+ Remote Sensor

    PubMed Central

    Nguyen, Hieu Cong; Jung, Jaehoon; Lee, Jungbin; Choi, Sung-Uk; Hong, Suk-Young; Heo, Joon

    2015-01-01

    The reflectance of the Earth’s surface is significantly influenced by atmospheric conditions such as water vapor content and aerosols. Particularly, the absorption and scattering effects become stronger when the target features are non-bright objects, such as in aqueous or vegetated areas. For any remote-sensing approach, atmospheric correction is thus required to minimize those effects and to convert digital number (DN) values to surface reflectance. The main aim of this study was to test the three most popular atmospheric correction models, namely (1) Dark Object Subtraction (DOS); (2) Fast Line-of-sight Atmospheric Analysis of Spectral Hypercubes (FLAASH) and (3) the Second Simulation of Satellite Signal in the Solar Spectrum (6S) and compare them with Top of Atmospheric (TOA) reflectance. By using the k-Nearest Neighbor (kNN) algorithm, a series of experiments were conducted for above-ground forest biomass (AGB) estimations of the Gongju and Sejong region of South Korea, in order to check the effectiveness of atmospheric correction methods for Landsat ETM+. Overall, in the forest biomass estimation, the 6S model showed the bestRMSE’s, followed by FLAASH, DOS and TOA. In addition, a significant improvement of RMSE by 6S was found with images when the study site had higher total water vapor and temperature levels. Moreover, we also tested the sensitivity of the atmospheric correction methods to each of the Landsat ETM+ bands. The results confirmed that 6S dominates the other methods, especially in the infrared wavelengths covering the pivotal bands for forest applications. Finally, we suggest that the 6S model, integrating water vapor and aerosol optical depth derived from MODIS products, is better suited for AGB estimation based on optical remote-sensing data, especially when using satellite images acquired in the summer during full canopy development. PMID:26263996

  3. 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.

  4. Sulfur deposition and cycling in two forests of the Georgia Piedmont

    SciTech Connect

    Cappellato, R. )

    1994-06-01

    Because of the increase in SO[sub 2] emissions in Georgia since the late 70's, a study was undertaken in adjacent deciduous and coniferous forests to estimate the atmospheric input and above-ground cycling of sulfur. During this study, which was conducted in 1988-89, total annual sulfur input to these forests was 17 kg/ha, which was comparable to sulfur inputs to other sites in the eastern United States. Dry deposition accounted for more than 50% of the total atmospheric sulfur input, and SO[sub 2] was the major source of dry deposition of the canopy. Net flux of sulfur in (throughfall flux minus precipitation flux) under the deciduous canopy was 1.8 times higher than that under the conferous canopy. Although the net sulfur throughfall flux was very similar to the total sulfur dry deposition in the deciduous forest, the net sulfur throughfall was only about half of the total sulfur dry deposition. The lower throughfall sulfur flux in the coniferous forest was attributed to retention of SO[sub 2] by the canopy. Lower sulfur concentration in needles from the litterfall (0.68 mg/g) than in needles from the canopy (1.38 mg/g) indicates that sulfur could be accumulating in coniferous wood. Total annual sulfur deposition to the forest floor by throughfall, stemflow, and litterfall was 2.3 and 1.3 times greater than the sulfur required by the deciduous and coniferous forests, respectively, for annual wood and foliage production.

  5. Estimation of absolute water surface temperature based on atmospherically corrected thermal infrared multispectral scanner digital data

    NASA Technical Reports Server (NTRS)

    Anderson, James E.

    1986-01-01

    Airborne remote sensing systems, as well as those on board Earth orbiting satellites, sample electromagnetic energy in discrete wavelength regions and convert the total energy sampled into data suitable for processing by digital computers. In general, however, the total amount of energy reaching a sensor system located at some distance from the target is composed not only of target related energy, but, in addition, contains a contribution originating from the atmosphere itself. Thus, some method must be devised for removing or at least minimizing the effects of the atmosphere. The LOWTRAN-6 Program was designed to estimate atmospheric transmittance and radiance for a given atmospheric path at moderate spectral resolution over an operational wavelength region from 0.25 to 28.5 microns. In order to compute the Thermal Infrared Multispectral Scanner (TIMS) digital values which were recorded in the absence of the atmosphere, the parameters derived from LOWTRAN-6 are used in a correction equation. The TIMS data were collected at 1:00 a.m. local time on November 21, 1983, over a recirculating cooling pond for a power plant in southeastern Mississippi. The TIMS data were analyzed before and after atmospheric corrections were applied using a band ratioing model to compute the absolute surface temperature of various points on the power plant cooling pond. The summarized results clearly demonstrate the desirability of applying atmospheric corrections.

  6. Estimated effects of the vertical structure of atmospheric mass on the time-variable geoid

    NASA Astrophysics Data System (ADS)

    Swenson, Sean; Wahr, John

    2002-09-01

    The GRACE satellite mission is designed to map the Earth's gravity field at a resolution of a few hundred kilometers every 30 days beginning in 2002. At these timescales, much of the change in the gravity field may be attributed to processes involving the redistribution of water on the surface of the Earth. Contributions from continental water storage, the oceans, and the atmosphere will all be present in the time-varying gravity solutions. Isolating the hydrological and oceanographic signals will first require the removal of the atmospheric component of the gravity field estimates provided by GRACE. The vertical distribution of mass in the atmosphere is typically neglected when calculating the atmospheric gravity signal. We examine the accuracy of this approximation, as well as the accuracies of models which determine idealized atmospheric vertical structure from surface values of temperature and pressure. Using isobaric geopotential height data from a global forecast center to characterize the true atmospheric density distribution, we compute an exact atmospheric gravity signal with which to compare the gravity signal of each of these models. In addition, we examine the effects of including the aspherical component of the Earth's shape when calculating the atmospheric component of the gravity field. Because gravity estimates from GRACE will have limited spatial resolution, we average our results over regions of 200 to 500 km. At these length scales, our results show that using models based solely on surface data can introduce errors in the time variable surface mass signal inferred from GRACE as large as a few millimeters equivalent water thickness, with a global RMS of about 1 mm.

  7. Application of watershed deposition tool to estimate from CMAQ simulations the atmospheric deposition of nitrogen to Tampa Bay and its watershed.

    PubMed

    Poor, Noreen D; Pribble, J Raymond; Schwede, Donna B

    2013-01-01

    The US. Environmental Protection Agency (EPA) has developed the Watershed Deposition Tool (WDT) to calculate from the Community Multiscale Air Quality (CMAQ) model output the nitrogen, sulfur and mercury deposition rates to watersheds and their sub-basins. The CMAQ model simulates from first principles the transport, transformation, and removal of atmospheric pollutants. We applied WDT to estimate the atmospheric deposition of reactive nitrogen (N) to Tampa Bay and its watershed. For 2002 and within the boundaries of Tampa Bay's watershed, modeled atmospheric deposition rates averaged 13.3 kg N ha(-1) yr(-1) and ranged from 6.24 kg N ha(-1) yr(-1) at the bay's boundary with Gulf of Mexico to 21.4 kg N ha(-1) yr(-1) near Tampa's urban core, based on a 12-km x 12-km grid cell size. CMAQ-predicted loading rates were 1,080 metric tons N yr(-1) to Tampa Bay and 8,280 metric tons N yr(-1) to the land portion of its watershed. If we assume a watershed-to-bay transfer rate of 18% for indirect loading, our estimates of the 2002 direct and indirect loading rates to Tampa Bay were 1,080 metric tons N and 1,490 metric tons N, respectively, for an atmospheric loading of 2,570 metric tons N or 71% of the total N loading to Tampa Bay. To evaluate the potential impact of the US. EPA Clean Air Interstate Rule (CAIR, replaced with Cross-State Air Pollution Rule), Tier 2 Vehicle and Gasoline Sulfur Rules, Heavy Duty Highway Rule, and Non-Road Diesel Rule, we compared CMAQ outputs between 2020 and 2002 simulations, with only the emissions inventories changed. The CMAQ-projected change in atmospheric loading rates between these emissions inventories was 857 metric tons N to Tampa Bay, or about 24% of the 2002 loading of 3,640 metric tons N to Tampa Bay from all sources. Air quality modeling reveals that atmospheric deposition of reactive nitrogen (N) contributes a significant fraction to Tampa Bay's total N loading from external sources. Regulatory drivers that lower nitrogen oxide

  8. Improved estimates of ventilation rate changes and CO2 uptake in the Pacific Ocean using chlorofluorocarbons and sulfur hexafluoride

    NASA Astrophysics Data System (ADS)

    Sonnerup, Rolf E.; Bullister, John L.; Warner, Mark J.

    2008-12-01

    Depth profiles of dissolved sulfur hexafluoride (SF6) were measured at 10 stations during the 2006 Climate Variability and Predictability (CLIVAR) Repeat Hydrography reoccupation of the 1991 World Ocean Circulation Experiment P16 section along 152°W between 14°S and 52°N. Ventilation ages calculated from the partial pressure of SF6 (pSF6 ages) were generally 6-10 years younger than those calculated from concurrent CFC-12 partial pressures (pCFC-12 ages). A one-dimensional parameterization of transit time distributions is utilized to demonstrate the potential of SF6, as a complement to the CFCs, to constrain the impact of mixing on the tracer-derived ages. The two-tracer approach provides an estimate of the mixing-induced tendency of pCFC-12 ages to change with time by correcting their bias to younger ages in older waters and their bias to older ages in younger waters. Model scenarios that match both the 2006 pSF6 and pCFC-12 ages predict a mixing-induced increase in pCFC-12 ages of 6-10 years between the 1991 and 2006 occupations of P16, similar to the increase in pCFC-12 ages observed. Model scenarios tuned to the pCFC-12 and pSF6 ages from 2006 are used to calculate anthropogenic CO2 along the section and yield slightly smaller anthropogenic CO2 burdens than calculated solely from the pCFC-12 ages in waters with pCFC-12 ages >36 years in 2006.

  9. The atmospheric CH4 increase since the Last Glacial Maximum. I - Source estimates

    NASA Technical Reports Server (NTRS)

    Chappellaz, Jerome A.; Fung, Inez Y.; Thompson, Anne M.

    1993-01-01

    An estimate of the distribution of wetland area and associated CH4 emission is presented for the Last Glacial Maximum (LGM, 18 kyr BP, kiloyear Before Present) and the Pre-Industrial Holocene (PIH, 9000-200 years BP). The wetland source, combined with estimates of the other biogenic sources and sink, yields total source strengths of 120 and 180 Tg CH4/yr for LGM and PIH respectively. These source strengths are shown to be consistent with source estimates inferred from a photochemical model, and point to changes in wetland CH4 source as a major factor driving the atmospheric CH4 increase from LGM to PIH.

  10. The atmospheric CH4 increase since the Last Glacial Maximum. I - Source estimates

    NASA Technical Reports Server (NTRS)

    Chappellaz, Jerome A.; Fung, Inez Y.; Thompson, Anne M.

    1993-01-01

    An estimate of the distribution of wetland area and associated CH4 emission is presented for the Last Glacial Maximum (LGM, 18 kyr BP, kiloyear Before Present) and the Pre-Industrial Holocene (PIH, 9000-200 years BP). The wetland source, combined with estimates of the other biogenic sources and sink, yields total source strengths of 120 and 180 Tg CH4/yr for LGM and PIH respectively. These source strengths are shown to be consistent with source estimates inferred from a photochemical model, and point to changes in wetland CH4 source as a major factor driving the atmospheric CH4 increase from LGM to PIH.

  11. Atmospheric channel transfer function estimation from experimental free-space optical communications data

    NASA Astrophysics Data System (ADS)

    Reinhardt, Colin N.; Tsintikidis, Dimitris; Hammel, Stephen; Kuga, Yasuo; Ritcey, James A.; Ishimaru, Akira

    2012-03-01

    Using an 850-nanometer-wavelength free-space optical (FSO)communications system of our own design, we acquired field data for the transmitted and received signals in fog at Point Loma, CA for a range of optical depths within the multiple-scattering regime. Statistical estimators for the atmospheric channel transfer function and the related coherency function were computed directly from the experimental data. We interpret the resulting channel transfer function estimates in terms of the physics of the atmospheric propagation channel and fog aerosol particle distributions. We investigate the behavior of the estimators using both real field-test data and simulated propagation data. We compare the field-data channel transfer function estimates against the outputs from a computationally-intensive radiative-transfer theory model-based approach, which we also developed previously for the FSO multiple-scattering atmospheric channel. Our results show that the data-driven channel transfer function estimates are in close agreement with the radiative transfer modeling, and provide comparable receiver signal detection performance improvements while being significantly less time and computationally-intensive.

  12. Estimating annual precipitation for the Colorado River Basin using oceanic-atmospheric oscillations

    NASA Astrophysics Data System (ADS)

    Kalra, Ajay; Ahmad, Sajjad

    2012-06-01

    Estimating long-lead time precipitation under the stress of increased climatic variability is a challenging task in the field of hydrology. A modified Support Vector Machine (SVM) based framework is proposed to estimate annual precipitation using oceanic-atmospheric oscillations. Oceanic-atmospheric oscillations, consisting of Pacific Decadal Oscillation (PDO), North Atlantic Oscillation (NAO), Atlantic Multidecadal Oscillation (AMO), and El Niño-Southern Oscillation (ENSO) for a period of 1900-2008, are used to generate annual precipitation estimates with a 1 year lead time. The SVM model is applied to 17 climate divisions encompassing the Colorado River Basin in the western United States. The overall results revealed that the annual precipitation in the Colorado River Basin is significantly influenced by oceanic-atmospheric oscillations. The long-term precipitation predictions for the Upper Colorado River Basin can be successfully obtained using a combination of PDO, NAO, and AMO indices, whereas coupling AMO and ENSO results in improved precipitation predictions for the Lower Colorado River Basin. The results also show that the SVM model provides better precipitation estimates compared to the Artificial Neural Network and Multivariate Linear Regression models. The annual precipitation estimates obtained using the modified SVM modeling framework may assist water managers in statistically understanding the hydrologic response in relation to large scale climate patterns within the Colorado River Basin.

  13. Using smog chambers to estimate the toxic effects of reactive atmospheric mixtures

    NASA Astrophysics Data System (ADS)

    Doyle, Melanie Lynn

    , understanding which products induce the greatest overall effect is particularly helpful when regulating ambient pollutants. In the final part, a preconditioning method was developed to ascertain if repeated ozone exposures modify the respiratory effects induced by subsequent challenges to atmospheric mixtures. Combined, these results characterize and estimate the toxic potential of a realistic, complex, reacting, polluted atmosphere.

  14. [Quantitative estimation source of urban atmospheric CO2 by carbon isotope composition].

    PubMed

    Liu, Wei; Wei, Nan-Nan; Wang, Guang-Hua; Yao, Jian; Zeng, You-Shi; Fan, Xue-Bo; Geng, Yan-Hong; Li, Yan

    2012-04-01

    To effectively reduce urban carbon emissions and verify the effectiveness of currently project for urban carbon emission reduction, quantitative estimation sources of urban atmospheric CO2 correctly is necessary. Since little fractionation of carbon isotope exists in the transportation from pollution sources to the receptor, the carbon isotope composition can be used for source apportionment. In the present study, a method was established to quantitatively estimate the source of urban atmospheric CO2 by the carbon isotope composition. Both diurnal and height variations of concentrations of CO2 derived from biomass, vehicle exhaust and coal burning were further determined for atmospheric CO2 in Jiading district of Shanghai. Biomass-derived CO2 accounts for the largest portion of atmospheric CO2. The concentrations of CO2 derived from the coal burning are larger in the night-time (00:00, 04:00 and 20:00) than in the daytime (08:00, 12:00 and 16:00), and increase with the increase of height. Those derived from the vehicle exhaust decrease with the height increase. The diurnal and height variations of sources reflect the emission and transport characteristics of atmospheric CO2 in Jiading district of Shanghai.

  15. Linearly Supporting Feature Extraction for Automated Estimation of Stellar Atmospheric Parameters

    NASA Astrophysics Data System (ADS)

    Li, Xiangru; Lu, Yu; Comte, Georges; Luo, Ali; Zhao, Yongheng; Wang, Yongjun

    2015-05-01

    We describe a scheme to extract linearly supporting (LSU) features from stellar spectra to automatically estimate the atmospheric parameters {{T}{\\tt{eff} }}, log g, and [Fe/H]. “Linearly supporting” means that the atmospheric parameters can be accurately estimated from the extracted features through a linear model. The successive steps of the process are as follow: first, decompose the spectrum using a wavelet packet (WP) and represent it by the derived decomposition coefficients; second, detect representative spectral features from the decomposition coefficients using the proposed method Least Absolute Shrinkage and Selection Operator (LARS)bs; third, estimate the atmospheric parameters {{T}{\\tt{eff} }}, log g, and [Fe/H] from the detected features using a linear regression method. One prominent characteristic of this scheme is its ability to evaluate quantitatively the contribution of each detected feature to the atmospheric parameter estimate and also to trace back the physical significance of that feature. This work also shows that the usefulness of a component depends on both the wavelength and frequency. The proposed scheme has been evaluated on both real spectra from the Sloan Digital Sky Survey (SDSS)/SEGUE and synthetic spectra calculated from Kurucz's NEWODF models. On real spectra, we extracted 23 features to estimate {{T}{\\tt{eff} }}, 62 features for log g, and 68 features for [Fe/H]. Test consistencies between our estimates and those provided by the Spectroscopic Parameter Pipeline of SDSS show that the mean absolute errors (MAEs) are 0.0062 dex for log {{T}{\\tt{eff} }} (83 K for {{T}{\\tt{eff} }}), 0.2345 dex for log g, and 0.1564 dex for [Fe/H]. For the synthetic spectra, the MAE test accuracies are 0.0022 dex for log {{T}{\\tt{eff} }} (32 K for {{T}{\\tt{eff} }}), 0.0337 dex for log g, and 0.0268 dex for [Fe/H].

  16. A sparse reconstruction method for the estimation of multi-resolution emission fields via atmospheric inversion

    DOE PAGES

    Ray, J.; Lee, J.; Yadav, V.; ...

    2015-04-29

    Atmospheric inversions are frequently used to estimate fluxes of atmospheric greenhouse gases (e.g., biospheric CO2 flux fields) at Earth's surface. These inversions typically assume that flux departures from a prior model are spatially smoothly varying, which are then modeled using a multi-variate Gaussian. When the field being estimated is spatially rough, multi-variate Gaussian models are difficult to construct and a wavelet-based field model may be more suitable. Unfortunately, such models are very high dimensional and are most conveniently used when the estimation method can simultaneously perform data-driven model simplification (removal of model parameters that cannot be reliably estimated) and fitting.more » Such sparse reconstruction methods are typically not used in atmospheric inversions. In this work, we devise a sparse reconstruction method, and illustrate it in an idealized atmospheric inversion problem for the estimation of fossil fuel CO2 (ffCO2) emissions in the lower 48 states of the USA. Our new method is based on stagewise orthogonal matching pursuit (StOMP), a method used to reconstruct compressively sensed images. Our adaptations bestow three properties to the sparse reconstruction procedure which are useful in atmospheric inversions. We have modified StOMP to incorporate prior information on the emission field being estimated and to enforce non-negativity on the estimated field. Finally, though based on wavelets, our method allows for the estimation of fields in non-rectangular geometries, e.g., emission fields inside geographical and political boundaries. Our idealized inversions use a recently developed multi-resolution (i.e., wavelet-based) random field model developed for ffCO2 emissions and synthetic observations of ffCO2 concentrations from a limited set of measurement sites. We find that our method for limiting the estimated field within an irregularly shaped region is about a factor of 10 faster than conventional approaches. It also

  17. Biases in atmospheric CO2 estimates from correlated meteorology modeling errors

    NASA Astrophysics Data System (ADS)

    Miller, S. M.; Hayek, M. N.; Andrews, A. E.; Fung, I.; Liu, J.

    2015-03-01

    Estimates of CO2 fluxes that are based on atmospheric measurements rely upon a meteorology model to simulate atmospheric transport. These models provide a quantitative link between the surface fluxes and CO2 measurements taken downwind. Errors in the meteorology can therefore cause errors in the estimated CO2 fluxes. Meteorology errors that correlate or covary across time and/or space are particularly worrisome; they can cause biases in modeled atmospheric CO2 that are easily confused with the CO2 signal from surface fluxes, and they are difficult to characterize. In this paper, we leverage an ensemble of global meteorology model outputs combined with a data assimilation system to estimate these biases in modeled atmospheric CO2. In one case study, we estimate the magnitude of month-long CO2 biases relative to CO2 boundary layer enhancements and quantify how that answer changes if we either include or remove error correlations or covariances. In a second case study, we investigate which meteorological conditions are associated with these CO2 biases. In the first case study, we estimate uncertainties of 0.5-7 ppm in monthly-averaged CO2 concentrations, depending upon location (95% confidence interval). These uncertainties correspond to 13-150% of the mean afternoon CO2 boundary layer enhancement at individual observation sites. When we remove error covariances, however, this range drops to 2-22%. Top-down studies that ignore these covariances could therefore underestimate the uncertainties and/or propagate transport errors into the flux estimate. In the second case study, we find that these month-long errors in atmospheric transport are anti-correlated with temperature and planetary boundary layer (PBL) height over terrestrial regions. In marine environments, by contrast, these errors are more strongly associated with weak zonal winds. Many errors, however, are not correlated with a single meteorological parameter, suggesting that a single meteorological proxy is

  18. 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.

  19. Atmospheric conditions affecting seeing at St. Catherine: Estimation of operational time for NRIAG new telescope

    NASA Astrophysics Data System (ADS)

    Mekhaimr, Sayed A.

    2017-06-01

    The study of the prevailing atmospheric conditions is an essential part of any site testing for a new telescope establishment. In this article, the meteorological parameters that affect the astronomical seeing at St. Catherine region, where a two candidate sites are located, are studied based on the available climate data. The complex topographical features of the region cause some differences between the weather at the nearest meteorological station and that at the candidate sites. This issue is illustrated through high resolution atmospheric modeling for short period (six days) as a case study. Finally, a preliminary estimation of operational hours for the telescope at the candidate sites is calculated.

  20. Adjoint-Based Methods for Estimating CO2 Sources and Sinks from Atmospheric Concentration Data

    NASA Technical Reports Server (NTRS)

    Andrews, Arlyn E.

    2003-01-01

    Work to develop adjoint-based methods for estimating CO2 sources and sinks from atmospheric concentration data was initiated in preparation for last year's summer institute on Carbon Data Assimilation (CDAS) at the National Center for Atmospheric Research in Boulder, CO. The workshop exercises used the GSFC Parameterized Chemistry and Transport Model and its adjoint. Since the workshop, a number of simulations have been run to evaluate the performance of the model adjoint. Results from these simulations will be presented, along with an outline of challenges associated with incorporating a variety of disparate data sources, from sparse, but highly precise, surface in situ observations to less accurate, global future satellite observations.

  1. Adjoint-Based Methods for Estimating CO2 Sources and Sinks from Atmospheric Concentration Data

    NASA Technical Reports Server (NTRS)

    Andrews, Arlyn E.

    2003-01-01

    Work to develop adjoint-based methods for estimating CO2 sources and sinks from atmospheric concentration data was initiated in preparation for last year's summer institute on Carbon Data Assimilation (CDAS) at the National Center for Atmospheric Research in Boulder, CO. The workshop exercises used the GSFC Parameterized Chemistry and Transport Model and its adjoint. Since the workshop, a number of simulations have been run to evaluate the performance of the model adjoint. Results from these simulations will be presented, along with an outline of challenges associated with incorporating a variety of disparate data sources, from sparse, but highly precise, surface in situ observations to less accurate, global future satellite observations.

  2. 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

  3. Laboratory evaluation of microwave absorption properties under simulated conditions for planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.

    1984-01-01

    The microwave absorbing properties of gaseous sulfuric acid (H2SO4) under Venus atmospheric conditions are investigated. The results are applied to measurements from Mariner 5, Mariner 10, and Pioneer/Venus Radio Occultation experiments, to determine abundancies of gaseous sulfuric acid in the Venus atmosphere. The microwave properties of the vapors accompanying liquid H2SO4 are studied to estimate the vapor pressure in an atmospheric model.

  4. Limitation of Ground-based Estimates of Solar Irradiance Due to Atmospheric Variations

    NASA Technical Reports Server (NTRS)

    Wen, Guoyong; Cahalan, Robert F.; Holben, Brent N.

    2003-01-01

    The uncertainty in ground-based estimates of solar irradiance is quantitatively related to the temporal variability of the atmosphere's optical thickness. The upper and lower bounds of the accuracy of estimates using the Langley Plot technique are proportional to the standard deviation of aerosol optical thickness (approx. +/- 13 sigma(delta tau)). The estimates of spectral solar irradiance (SSI) in two Cimel sun photometer channels from the Mauna Loa site of AERONET are compared with satellite observations from SOLSTICE (Solar Stellar Irradiance Comparison Experiment) on UARS (Upper Atmospheric Research Satellite) for almost two years of data. The true solar variations related to the 27-day solar rotation cycle observed from SOLSTICE are about 0.15% at the two sun photometer channels. The variability in ground-based estimates is statistically one order of magnitude larger. Even though about 30% of these estimates from all Level 2.0 Cimel data fall within the 0.4 to approx. 0.5% variation level, ground-based estimates are not able to capture the 27-day solar variation observed from SOLSTICE.

  5. A Green Planet versus a Desert World: Estimating the Effect of Vegetation Extremes on the Atmosphere.

    NASA Astrophysics Data System (ADS)

    Fraedrich, Klaus; Kleidon, Axel; Lunkeit, Frank

    1999-10-01

    The effect of vegetation extremes on the general circulation is estimated by two atmospheric GCM simulations using global desert and forest boundary conditions over land. The difference between the climates of a `green planet' and a `desert world' is dominated by the changes of the hydrological cycle, which is intensified substantially. Enhanced evapotranspiration over land reduces the near-surface temperatures; enhanced precipitation leads to a warmer mid- and upper troposphere extending from the subtropics (induced by ITCZ, monsoon, and Hadley cell dynamics) to the midlatitudes (over the cyclogenesis area of Northern Hemisphere storm tracks). These regional changes of the surface water and energy balances, and of the atmospheric circulation, have potential impact on the ocean and the atmospheric greenhouse.

  6. Radar Estimations of Atmospheric Winds in the Troposphere and Lower Stratosphere

    NASA Astrophysics Data System (ADS)

    Sheppard, Emory Lamar

    This dissertation deals with the estimation of atmospheric flow field parameters using the spaced antenna (SA) and spatial interferometer (SI) methods. In the first section, a computer simulation of scattering from inhomogeneities in the refractive index is used to compare the SA and SI methods for measuring winds in clear air both with and without turbulent fading. The results show that the SA analysis which is carried out in the time domain and the SI analysis which is carried out in the frequency domain are equivalent in terms of the information that the two methods yield. A data analysis method equivalent to full correlation analysis, which can be carried out in the frequency domain, is presented. The method is applied to model-generated data in order to extract the typical full correlation analysis output parameters such as the apparent and true velocities. The results obtained are consistent with the model input parameters. In the second section a statistical comparison of the SA and SI methods for estimating horizontal winds in the troposphere and the lower stratosphere is presented. The data analyzed were obtained with the Middle and Upper (MU) atmosphere radar from 1910 LT on June 29, 1990, through 0950 LT on July 2, 1990. At all heights, velocity estimates based on frequency domain data are within 4% of those based on time domain data. We conclude that frequency domain techniques provide an alternate method for estimating true horizontal velocity. Nevertheless, it is not clear that they offer any significant advantage over time domain methods. In fact, the results obtained indicate that the SI method for estimating horizontal velocity may be slightly more difficult to apply in practice. The final section presents an analytical evaluation of SA-based instrumental setups with the potential for estimating the vertical component of atmospheric vorticity from a single-radar location. Methods considered are the oblique spaced antenna (OAS) method and a modified

  7. Estimating Bacteria Emissions from Inversion of Atmospheric Transport: Sensitivity to Modelled Particle Characteristics

    SciTech Connect

    Burrows, Susannah M.; Rayner, Perter; Butler, T.; Lawrence, M.

    2013-06-04

    Model-simulated transport of atmospheric trace components can be combined with observed concentrations to obtain estimates of ground-based sources using various inversion techniques. These approaches have been applied in the past primarily to obtain source estimates for long-lived trace gases such as CO2. We consider the application of similar techniques to source estimation for atmospheric aerosols, by using as a case study the estimation of bacteria emissions from different ecosystem regions in the global atmospheric chemistry and climate model ECHAM5/MESSy-Atmospheric Chemistry (EMAC). Simulated particle concentrations in the tropopause region and at high latitudes, as well as transport of particles to tundra and land ice regions are shown to be highly sensitive to scavenging in mixed-phase clouds, which is poorly characterized in most global climate models. This may be a critical uncertainty in correctly simulating the transport of aerosol particles to the Arctic. Source estimation via Monte Carlo Markov Chain is applied to a suite of sensitivity simulations and the global mean emissions are estimated. We present an analysis of the partitioning of uncertainties in the global mean emissions that are attributable to particle size, CCN activity, the ice nucleation scavenging ratios for mixed-phase and cold clouds, and measurement error. Uncertainty due to CCN activity or to a 1 um error in particle size is typically between 10% and 40% of the uncertainty due to data uncertainty, as measured by the 5%-ile to 95%-ile range of the Monte Carlo ensemble. Uncertainty attributable to the ice nucleation scavenging ratio in mized-phase clouds is as high as 10% to 20% of the data uncertainty. Taken together, the four model 20 parameters examined contribute about half as much to the uncertainty in the estimated emissions as do the measurements. This was a surprisingly large contribution from model uncertainty in light of the substantial data uncertainty, which ranges from 81

  8. State and Parameter Estimation for a Coupled Ocean--Atmosphere Model

    NASA Astrophysics Data System (ADS)

    Ghil, M.; Kondrashov, D.; Sun, C.

    2006-12-01

    The El-Nino/Southern-Oscillation (ENSO) dominates interannual climate variability and plays, therefore, a key role in seasonal-to-interannual prediction. Much is known by now about the main physical mechanisms that give rise to and modulate ENSO, but the values of several parameters that enter these mechanisms are an important unknown. We apply Extended Kalman Filtering (EKF) for both model state and parameter estimation in an intermediate, nonlinear, coupled ocean--atmosphere model of ENSO. The coupled model consists of an upper-ocean, reduced-gravity model of the Tropical Pacific and a steady-state atmospheric response to the sea surface temperature (SST). The model errors are assumed to be mainly in the atmospheric wind stress, and assimilated data are equatorial Pacific SSTs. Model behavior is very sensitive to two key parameters: (i) μ, the ocean-atmosphere coupling coefficient between SST and wind stress anomalies; and (ii) δs, the surface-layer coefficient. Previous work has shown that δs determines the period of the model's self-sustained oscillation, while μ measures the degree of nonlinearity. Depending on the values of these parameters, the spatio-temporal pattern of model solutions is either that of a delayed oscillator or of a westward propagating mode. Estimation of these parameters is tested first on synthetic data and allows us to recover the delayed-oscillator mode starting from model parameter values that correspond to the westward-propagating case. Assimilation of SST data from the NCEP-NCAR Reanalysis-2 shows that the parameters can vary on fairly short time scales and switch between values that approximate the two distinct modes of ENSO behavior. Rapid adjustments of these parameters occur, in particular, during strong ENSO events. Ways to apply EKF parameter estimation efficiently to state-of-the-art coupled ocean--atmosphere GCMs will be discussed.

  9. Estimates of atmospheric deposition of submicron particle-associated combustion derived organic contaminants to Chesapeake Bay

    SciTech Connect

    Leister, D.L. |; Baker, J.E.

    1994-12-31

    Once emitted into the atmosphere, combustion derived organic contaminants partition between gaseous and particle phases. In order to estimate the wet and dry removal of contaminants from the atmospheric to surface waters, it is necessary to measure gaseous and particle-associated contaminant concentrations because the deposition mechanisms of each phase differ. The authors estimate dry and wet depositional fluxes of polycyclic aromatic hydrocarbons (PAH) as a function of large and small particles to provide insight to the contribution of small particles to the overall atmospheric flux of organic contaminants to surface waters. Utilizing data gathered from concurrent measurements of 10 PAHs associated with particles in rain an in the atmosphere adjacent to Chesapeake Bay, and from PAH particle-size distribution data recently collected at Egbert, Ontario, calculated non-crustal PAH dry particle fluxes range from 40 to as high as 160 ng/m{sup 2}/month. Despite the lower estimated deposition velocity for noncrustal particles relative to that for partially crustal particles, non-crustal PAH particle fluxes are about a factor of five larger than those calculated for particles with a partial crustal component. Monthly wet fluxes of submicron particles range from 12 to 260 ng/m{sup 2}/month and in contrast to dry periods, are similar to those for large particles. Their calculations suggest that the atmospheric loading of submicron particle associated PAHs on an annual basis during dry and wet periods are significant due to the high concentrations of contaminants in this size range in both air and rain.

  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. Constraining Methane Flux Estimates Using Atmospheric Observations of Methane and 1^3C in Methane

    NASA Astrophysics Data System (ADS)

    Mikaloff Fletcher, S. E.; Tans, P. P.; Miller, J. B.; Bruhwiler, L. M.

    2002-12-01

    Understanding the budget of methane is crucial to predicting climate change and managing earth's carbon reservoirs. Methane is responsible for approximately 15% of the anthropogenic greenhouse forcing and has a large impact on the oxidative capacity of Earth's atmosphere due to its reaction with hydroxyl radical. At present, many of the sources and sinks of methane are poorly understood due in part to the large spatial and temporal variability of the methane flux. Model simulations of methane mixing ratios using most process-based source estimates typically over-predict the latitudinal gradient of atmospheric methane relative to the observations; however, the specific source processes responsible for this discrepancy have not been identified definitively. The aim of this work is to use the isotopic signatures of the sources to attribute these discrepancies to a source process or group of source processes and create global and regional budget estimates that are in agreement with both the atmospheric observations of methane and 1^3C in methane. To this end, observations of isotopic ratios of 1^3C in methane and isotopic signatures of methane source processes are used in conjunction with an inverse model of the methane budget. Inverse modeling is a top-down approach which uses observations of trace gases in the atmosphere, an estimate of the spatial pattern of trace gas fluxes, and a model of atmospheric transport to estimate the sources and sinks. The atmospheric transport was represented by the TM3 three-dimensional transport model. The GLOBALVIEW 2001 methane observations were used along with flask measurements of 1^3C in methane at six of the CMDL-NOAA stations by INSTAAR. Initial results imply interesting differences from previous methane budget estimates. For example, the 1^3C isotope observations in methane call for an increase in southern hemisphere sources with a bacterial isotopic signature such as wetlands, rice paddies, termites, and ruminant animals. The

  13. Accurate group velocity estimation for unmanned aerial vehicle-based acoustic atmospheric tomography.

    PubMed

    Rogers, Kevin J; Finn, Anthony

    2017-02-01

    Acoustic atmospheric tomography calculates temperature and wind velocity fields in a slice or volume of atmosphere based on travel time estimates between strategically located sources and receivers. The technique discussed in this paper uses the natural acoustic signature of an unmanned aerial vehicle as it overflies an array of microphones on the ground. The sound emitted by the aircraft is recorded on-board and by the ground microphones. The group velocities of the intersecting sound rays are then derived by comparing these measurements. Tomographic inversion is used to estimate the temperature and wind fields from the group velocity measurements. This paper describes a technique for deriving travel time (and hence group velocity) with an accuracy of 0.1% using these assets. This is shown to be sufficient to obtain highly plausible tomographic inversion results that correlate well with independent SODAR measurements.

  14. Geodesy by radio interferometry - Effects of atmospheric modeling errors on estimates of baseline length

    NASA Technical Reports Server (NTRS)

    Davis, J. L.; Herring, T. A.; Shapiro, I. I.; Rogers, A. E. E.; Elgered, G.

    1985-01-01

    Analysis of very long baseline interferometry data indicates that systematic errors in prior estimates of baseline length, of order 5 cm for approximately 8000-km baselines, were due primarily to mismodeling of the electrical path length of the troposphere and mesosphere ('atmospheric delay'). Here observational evidence for the existence of such errors in the previously used models for the atmospheric delay is discussed, and a new 'mapping' function for the elevation angle dependence of this delay is developed. The delay predicted by this new mapping function differs from ray trace results by less than approximately 5 mm, at all elevations down to 5 deg elevation, and introduces errors into the estimates of baseline length of less than about 1 cm, for the multistation intercontinental experiment analyzed here.

  15. Atmospheric channel transfer function estimation from experimental free-space optical communications data

    NASA Astrophysics Data System (ADS)

    Reinhardt, Colin N.; Kuga, Yasuo; Ritcey, James A.; Ishimaru, Akira; Hammel, Stephen; Tsintikidis, Dimitris

    2011-09-01

    The performance of terrestrial free-space optical communications systems is severely impaired by atmospheric aerosol particle distributions where the particle size is on the order of the operating wavelength. For optical and near-infrared wavelengths, fog droplets cause multiple-scattering and absorption effects which rapidly degrade received symbol detection performance as the optical depth parameter increases (visibility decreases). Using a custom free-space optical communications system we measured field data in fog within the optical multiple-scattering regime. We investigate the behavior of the estimated channel transfer function using both real field-test data and simulated propagation data based on field-test conditions. We then compare the channel transfer function estimates against the predictions computed using a radiative-transfer theory model-based approach which we also developed previously for the free-space optical atmospheric channel.

  16. Ocean-Atmosphere State Estimation and Targeted Observing using Coupled Model Ensembles

    DTIC Science & Technology

    2013-09-30

    1 Ocean-Atmosphere State Estimation and Targeted Observing using Coupled Model Ensembles Craig H. Bishop, PI Naval Research Laboratory...Targeted Observing using Coupled Model Ensembles 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e...forecast error covariance model for this coupled system is based solely on ensemble covariances because the pre-existing covariance model does not

  17. Considerations on Estimating Upper Bounds of Neutron Doses Equivalents to Military Participants at Atmospheric Nuclear Tests

    DTIC Science & Technology

    2007-04-01

    Tissue kerma for monoenergetic neutrons of energy up to 14 MeV and contributions from different interactions that produce charged ionizing particles...fluence for each energy group obtained from calculations for monoenergetic neutrons similar to calculations in Figure 2-I, and the energy dependence of the...Considerations on Estimating Upper Bounds of Neutron Dose Equivalents to Military Partici pants at Atmospheric Nuclear Tests Approved for public release

  18. Sea ice-atmospheric interaction: Application of multispectral satellite data in polar surface energy flux estimates

    NASA Technical Reports Server (NTRS)

    Steffen, Konrad; Key, J.; Maslanik, J.; Schweiger, A.

    1993-01-01

    This is the third annual report on: Sea Ice-Atmosphere Interaction - Application of Multispectral Satellite Data in Polar Surface Energy Flux Estimates. The main emphasis during the past year was on: radiative flux estimates from satellite data; intercomparison of satellite and ground-based cloud amounts; radiative cloud forcing; calibration of the Advanced Very High Resolution Radiometer (AVHRR) visible channels and comparison of two satellite derived albedo data sets; and on flux modeling for leads. Major topics covered are arctic clouds and radiation; snow and ice albedo, and leads and modeling.

  19. Estimating Dust and Water Ice Content of the Martian Atmosphere From THEMIS Data

    NASA Technical Reports Server (NTRS)

    Bandfield, Joshua

    2007-01-01

    Researchers at JPL and Arizona State University conducted a comparative study of three candidate algorithms for estimating components of the Martian atmosphere, using raw (uncalibrated) data collected by the Thermal Emission Imaging System (THEMIS). THEMIS is an instrument onboard the Mars Odyssey spacecraft that acquires image data in five visible and nine infrared (IR) wavelength bands. The algorithms under study used data collected from eight of the nine IR bands to estimate the dust and water ice content of the atmosphere. Such an algorithm could be used in onboard data processing to trigger other algorithms that search for features of scientific interest and to reduce the volume of data transmitted to Earth. The algorithms studied were based on regression models. In the study, the optical depths estimated by these algorithms were compared with optical depths estimated in ground-based processing using fully calibrated data from both THEMIS and the Thermal Emission Spectrometer (TES). TES is an instrument onboard the Mars Global Surveyor spacecraft that also observes the planet at infrared wavelengths, but at a lower spatial resolution than THEMIS does. Of the algorithms studied, the one that performed best was based on a Gaussian Support Vector Machine regression model. The test results indicated that this algorithm, operating on the raw data, had error rates that were within the uncertainty associated with the estimates obtained by the groundbased analysis of the fully calibrated data. This level of fidelity demonstrates that these algorithms are sufficiently accurate for use in an onboard setting.

  20. Radiance and atmosphere propagation-based method for the target range estimation

    NASA Astrophysics Data System (ADS)

    Cho, Hoonkyung; Chun, Joohwan

    2012-06-01

    Target range estimation is traditionally based on radar and active sonar systems in modern combat system. However, the performance of such active sensor devices is degraded tremendously by jamming signal from the enemy. This paper proposes a simple range estimation method between the target and the sensor. Passive IR sensors measures infrared (IR) light radiance radiating from objects in dierent wavelength and this method shows robustness against electromagnetic jamming. The measured target radiance of each wavelength at the IR sensor depends on the emissive properties of target material and is attenuated by various factors, in particular the distance between the sensor and the target and atmosphere environment. MODTRAN is a tool that models atmospheric propagation of electromagnetic radiation. Based on the result from MODTRAN and measured radiance, the target range is estimated. To statistically analyze the performance of proposed method, we use maximum likelihood estimation (MLE) and evaluate the Cramer-Rao Lower Bound (CRLB) via the probability density function of measured radiance. And we also compare CRLB and the variance of and ML estimation using Monte-Carlo.

  1. CarbonTracker-CH4: an assimilation system for estimating emissions of atmospheric methane

    NASA Astrophysics Data System (ADS)

    Bruhwiler, L.; Dlugokencky, E.; Masarie, K.; Ishizawa, M.; Andrews, A.; Miller, J.; Sweeney, C.; Tans, P.; Worthy, D.

    2014-08-01

    We describe an assimilation system for atmospheric methane (CH4), CarbonTracker-CH4, and demonstrate the diagnostic value of global or zonally averaged CH4 abundances for evaluating the results. We show that CarbonTracker-CH4 is able to simulate the observed zonal average mole fractions and capture inter-annual variability in emissions quite well at high northern latitudes (53-90° N). In contrast, CarbonTracker-CH4 is less successful in the tropics where there are few observations and therefore misses significant variability and is more influenced by prior flux estimates. CarbonTracker-CH4 estimates of total fluxes at high northern latitudes are about 81 ± 7 Tg CH4 yr-1, about 12 Tg CH4 yr-1 (13%) lower than prior estimates, a result that is consistent with other atmospheric inversions. Emissions from European wetlands are decreased by 30%, a result consistent with previous work by Bergamaschi et al. (2005); however, unlike their results, emissions from wetlands in boreal Eurasia are increased relative to the prior estimate. Although CarbonTracker-CH4 does not estimate an increasing trend in emissions from high northern latitudes for 2000 through 2010, significant inter-annual variability in high northern latitude fluxes is recovered. Exceptionally warm growing season temperatures in the Arctic occurred in 2007, a year that was also anonymously wet. Estimated emissions from natural sources were greater than the decadal average by 4.4 ± 3.8 Tg CH4 yr-1 in 2007. CarbonTracker-CH4 estimates for temperate latitudes are only slightly increased over prior estimates, but about 10 Tg CH4 yr-1 is redistributed from Asia to North America. This difference exceeds the estimated uncertainty for North America (±3.5 Tg CH4 yr-1). We used time invariant prior flux estimates, so for the period from 2000 to 2006, when the growth rate of global atmospheric CH4 was very small, the assimilation does not produce increases in natural or anthropogenic emissions in contrast to bottom

  2. Estimating European historical production, consumption and atmospheric emissions of decabromodiphenyl ether.

    PubMed

    Earnshaw, Mark R; Jones, Kevin C; Sweetman, Andy J

    2013-03-01

    A European scale production, consumption and environmental emissions inventory is produced for decabromodiphenyl ether (DecaBDE) for the period 1970-2020. A dynamic substance flow analysis model of DecaBDE is developed and emission of the main congener, BDE-209, to environmental compartments is estimated. From 1970 to 2010, it is estimated that a total of 185,000-250,000 tonnes of DecaBDE was consumed in Europe. Consumption peaked in the late 1990s at approximately 9,000 tonnes/year and has declined by ~30% in 2010. Predicted BDE-209 atmospheric emissions peak in 2004 at 10 tonnes/year. The waste management phase of the BDE-209 life cycle is responsible for the majority of atmospheric emissions via volatilisation and particle bound emissions from landfills, whilst leakage from Sewerage systems is the major source of emissions to the hydrosphere. Use of sewage sludge from wastewater treatment works as an agricultural fertiliser is the most important pathway of BDE-209 to soil. Although DecaBDE consumption has declined in recent years, the stock in use for 2010 remains considerable (60,000 tonnes) and is likely to act as a source of atmospheric emissions for several decades. Uncertainties exist in these estimations and more field or experimental data is needed to clarify the significance of certain emission pathways, in particular, emissions from landfill sites.

  3. The effect of copper on the estimation of sulfur fugacity from the composition of pyrrhotite: an experimental evaluation

    NASA Astrophysics Data System (ADS)

    Mengason, M. J.; Piccoli, P. M.; Candela, P. A.

    2009-12-01

    Sulfur fugacity is a critical intensive variable, important to the study of volcanic and plutonic rocks, and experimental systems. In a pioneering study, Toulmin and Barton (1964; GCA 28, 641) derived an equation, based on experimental data, for the relationship between fS2, temperature, and the composition of pyrrhotite (po), a common magmatic sulfide. The binary po solid solution (FeS-S2) was the object of their study; however, po frequently contains in excess of 1 wt. % Cu, and therefore further work has been required to account for the effect of additional phase components in po on the estimation of fS2 by this technique. In order to have consistent results from both Cu-free, and Cu-bearing po, one must properly formulate the Cu-bearing phase component of the po. Toward this end, we have designed a novel series of experiments that allow us to evaluate the relationship between the composition of Cu-Fe sulfides and fS2. Results of these experiments have been used to develop a simple method for the determination of the fS2 from Cu-bearing po and the equations of Toulmin and Barton. The experiments were performed in evacuated sealed silica tubes. Starting materials included pairs of separated reference (Cu-free), and Cu-bearing po in the presence of a common S2 gas phase (and therefore the same fS2). Experiments consisted of silica tubes loaded with mixtures of synthetic po and bornite separated by ~ 1mm thick silica discs, creating vertically stacked chambers. The chambers prevent contact of the separate condensed phase charges, but allow for gas transfer. Samples were heated in a vertical quench furnace at 1050°C for 16 to 24 hours followed by 5 days at 1000°C, concluding with a drop quench into a water bath. The experiments spanned 4 log units (bar) fS2 and the Cu-bearing po had Cu concentrations that ranged from 4.5 to 7.3 wt. %. The data were processed using three methods for incorporating Cu into the calculation, with effectiveness evaluated by deviations

  4. Regional river sulfur runoff

    SciTech Connect

    Husar, R.B.; Husar, J.D.

    1985-01-20

    The water and sulfur runoff data for 54 large river basins were assembled, covering 65% of the nondesert land area of the world. The sulfur concentration ranges from 0.5 mg S/L for the West African rivers Niger and Volta to 100 mg S/L in the Colorado River; the world average is 3.2 mg S/L. The concentrations in central and eastern Europe as well as central and eastern North America exceed 8 mg S/L. The sulfur runoff density is also highest in the river basins over these industrialized regions, exceeding 2 g S/m/sup 2//yr. However, high sulfur runoff density in excess of 3 g S/m/sup 2//yr is also measured over the Pacific islands New Zealand and New Guinea and the archipelagos of Indonesia and the Philippines. The natural background sulfur runoff was estimated by assuming that South America, Africa, Australia, and the Pacific Islands are unperturbed by man and that the average river sulfur concentration is in the range 1--3 mg S/L. Taking these background concentration values, the man-induced sulfur runoff for Europe ranges between 2 and 8 times the natural flow, and over North America, man's contribution ranges between 1 and 5 times the natural runoff. The global sulfur flow from nondesert land to the oceans and the Caspian Sea is estimated as 131 Tg S/yr, of which 46--85 Tg S/yr is attributed to natural causes. The regional river sulfur runoff pattern discussed in this paper does not have enough spatial resolution to be directly applicable to studies of the environmental effects of man-induced sulfur flows. However, it points to the continental-size regions where those perturbations are most evident and to the magnitude of the perturbations as expressed in units of the natural flows.

  5. Regional river sulfur runoff

    NASA Astrophysics Data System (ADS)

    Husar, Rudolf B.; Husar, Janja Djukic

    1985-01-01

    The water and sulfur runoff data for 54 large river basins were assembled, covering 65% of the nondesert land area of the world. The sulfur concentration ranges from 0.5 mg S/L for the West African rivers Niger and Volta to 100 mg S/L in the Colorado River; the world average is 3.2 mg S/L. The concentrations in central and eastern Europe as well as central and eastern North America exceed 8 mg S/L. The sulfur runoff density is also highest in the river basins over these industrialized regions, exceeding 2 g S/m2/yr. However, high sulfur runoff density in excess of 3 g S/m2/yr is also measured over the Pacific islands New Zealand and New Guinea and the archipelagos of Indonesia and the Philippines. The natural background sulfur runoff was estimated by assuming that South America, Africa, Australia, and the Pacific Islands are unperturbed by man and that the average river sulfur concentration is in the range 1-3 mg S/L. Taking these background concentration values, the man-induced sulfur runoff for Europe ranges between 2 and 8 times the natural flow, and over North America, man's contribution ranges between 1 and 5 times the natural runoff. The global sulfur flow from nondesert land to the oceans and the Caspian Sea is estimated as 131 Tg S/yr, of which 46-85 Tg S/yr is attributed to natural causes. The regional river sulfur runoff pattern discussed in this paper does not have enough spatial resolution to be directly applicable to studies of the environmental effects of man-induced sulfur flows. However, it points to the continental-size regions where those perturbations are most evident and to the magnitude of the perturbations as expressed in units of the natural flows.

  6. Use of personal-indoor-outdoor sulfur concentrations to estimate the infiltration factor and outdoor exposure factor for individual homes and persons.

    PubMed

    Wallace, Lance; Williams, Ron

    2005-03-15

    A study of personal, indoor, and outdoor exposure to PM2.5 and associated elements has been carried out for 37 residents of the Research Triangle Park area in North Carolina. Participants were selected from persons expected to be at elevated risk from exposure to particles, and included 29 persons with hypertension and 8 cardiac patients with implanted defibrillators. Participants were monitored for 7 consecutive days in each of four seasons. One goal of the study was to estimate the contribution of outdoor PM2.5 to indoor concentrations. This depends on the infiltration factor Finf, the fraction of outdoor PM2.5 remaining airborne after penetrating indoors. After confirming with our measurements the findings of previous studies that sulfur has few indoor sources, we estimated an average Finf for each house based on indoor/outdoor sulfur ratios. These estimates ranged from 0.26 to 0.87, with a median value of 0.55. Since these estimates apply only to particles of size similar to that of sulfur particles (0.06-0.5 microm diameter), and since larger particles (0.5-2.5 microm) have lower penetration rates and higher deposition rates, these estimates are likely to be higher than the true infiltration factors for PM2.5 as a whole. In summer when air conditioners were in use, the sulfur-based infiltration factor was at its lowest (averaging 0.50) for most homes, whereas the average Finf for the other three seasons was 0.62-0.63. Using the daily estimated infiltration factor for each house, we calculated the contribution of outdoor PM2.5 to indoor air concentrations. The indoor-generated contributions to indoor PM2.5 had a wider range (0-33 microg/m3) than the outdoor contributions (5-22 microg/m3). However, outdoor contributions exceeded the indoor-generated contributions in 27 of 36 homes. A second goal of the study was to determine the contribution of outdoor particles to personal exposure. This is determined by the "outdoor exposure factor" Fpex, the fraction of

  7. Perfluorocarbons in the global atmosphere: b) Emission estimates using inversions of atmospheric observations of tetrafluoromethane, hexafluoroethane, and octafluoropropane

    NASA Astrophysics Data System (ADS)

    Ganesan, A. L.; Muhle, J.; Rigby, M. L.; Miller, B. R.; Salameh, P. K.; Harth, C. M.; Greally, B. R.; O'Doherty, S. J.; Trudinger, C. M.; Porter, L. W.; Steele, P.; Krummel, P. B.; Petrenko, V. V.; Simmonds, P. G.; Fraser, P. J.; Prinn, R. G.; Weiss, R. F.

    2009-12-01

    The perfluorocarbons (PFCs) are long-lived potent greenhouse gases with mixing ratios that have been steadily increasing in the modern measurement record that extends from the 1970s. We present optimized emissions from 1973-present of three perfluorocarbons: tetrafluoromethane (CF4), hexafluoroethane (C2F6) and octafluoropropane (C3F8). The dominant sources of the PFCs are primary aluminum and semiconductor production. CF4 also has a significant pre-industrial abundance from the build-up of very small natural emissions. The inversions were performed with atmospheric measurements made by the Advanced Global Atmospheric Gases Experiment (AGAGE) network as well as using stored samples from the Commonwealth Scientific and Industrial Research Organization (CSIRO) Southern Hemisphere archive and from several Northern Hemisphere sources. Inverse estimates of surface flux were derived from the measurements using a discrete Kalman filter, the annual pulse method of Chen and Prinn (J. Geophys. Res., 111, D10307, doi:10.1029/2005JD006058), and a 2D 12-box chemical transport model. CF4 emissions have decreased from ~20 Gg/yr in 1981 to the present value of ~11 Gg/yr. Conversely, C2F6 and C3F8 exhibit an early increase in emissions, peaking much later around 2000 at ~3 Gg/yr and ~1 Gg/yr, respectively, and subsequently declining. The incongruity in the emission profiles is discussed in the context of different relative emissions of CF4 and the other measured PFCs from the two main sources, efforts by the aluminum industry to reduce the emission factor of CF4 (kg CF4 /ton Al), and published emission inventories. In all cases, over 90% of emissions are from the Northern Hemisphere.

  8. Ice core sulfur and methanesulfonic acid (MSA) records from southern Greenland document North American and European air pollution and suggest a decline in regional biogenic sulfur emissions.

    NASA Astrophysics Data System (ADS)

    Pasteris, D. R.; McConnell, J. R.; Burkhart, J. F.; Saltzman, E. S.

    2014-12-01

    Sulfate aerosols have an important cooling effect on the Earth because they scatter sunlight back to space and form cloud condensation nuclei. However, understanding of the atmospheric sulfur cycle is incomplete, leading to uncertainty in the assessment of past, present and future climate forcing. Here we use annually resolved observations of sulfur and methanesulfonic acid (MSA) concentration in an array of precisely dated Southern Greenland ice cores to assess the history of sulfur pollution emitted from North America and Europe and the history of biogenic sulfate aerosol derived from the North Atlantic Ocean over the last 250 years. The ice core sulfur time series is found to closely track sulfur concentrations in North American and European precipitation since records began in 1965, and also closely tracks estimated sulfur emissions since 1850 within the air mass source region as determined by back trajectory analysis. However, a decline to near-preindustrial sulfur concentrations in the ice cores after 1995 that is not so extensive in the source region emissions indicates that there has been a change in sulfur cycling over the last 150 years. The ice core MSA time series shows a decline of 60% since the 1860s, and is well correlated with declining sea ice concentrations around Greenland, suggesting that the phytoplankton source of biogenic sulfur has declined due to a loss of marginal sea ice zone habitat. Incorporating the implied decrease in biogenic sulfur in our analysis improves the match between the ice core sulfur record and the source region emissions throughout the last 150 years, and solves the problem of the recent return to near-preindustrial levels in the Greenland ice. These findings indicate that the transport efficiency of sulfur air pollution has been relatively stable through the industrial era and that biogenic sulfur emissions in the region have declined.

  9. Is it possible to estimate atmospheric deposition of heavy metals by analysis of terrestrial mosses?

    PubMed

    Aboal, J R; Fernández, J A; Boquete, T; Carballeira, A

    2010-11-15

    Here we present a critical review of diverse research studies involving estimation of atmospheric deposition of heavy metals from the concentrations of the contaminants in terrestrial moss. The findings can be summarized as follows: i) significant correlations between the concentrations of contaminants in moss and bulk deposition were observed in only 40.1% of the cases in which the relationship was studied and in only 14.1% of the cases, the coefficient of correlation was >0.7; ii) some method-related problems were identified (i.e. small sample sizes, elimination of some data from the regression analyses, large distances between the moss sampling sites and the bulk precipitation collectors, differences in times of exposure of the moss samples and collection times for the bulk precipitation), so that the results of the studies may not be completely valid, and iii) evidence was found in the relevant literature that moss does not actually integrate the atmospheric deposition received. We also discuss the reason why, in accordance with the published data, bulk deposition cannot be correctly estimated by determination of the final concentrations of contaminants in the organism, such as the existence of different sources of contamination, the physicochemical characteristics of the sources of deposition, physicochemical processes to which the organism is subjected and the biological processes that take place in the moss. Taking into account the above findings, it was concluded that, except for certain elements and specific cases (i.e. Pb and Cd), atmospheric deposition of elements cannot be accurately estimated from the concentrations of metals and metalloids in moss tissues. However, the analysis of moss does provide information about the presence of contaminants in the atmosphere, their spatial and temporal patterns of distribution and how they are taken up by live organisms. Use of mosses is therefore recommended as a complementary (rather than an alternative

  10. Uncertainties associated with the estimation of mass balances and gaussian parameters from atmospheric tracer studies

    SciTech Connect

    Sackinger, P.A.; Reible, D.D.; Shair, F.H.

    1982-07-01

    Data resulting from two atmospheric tracer experiments in the land-sea breeze winds in Los Angeles, CA are used to compare the observed and released amounts of tracer (a mass balance). The mass balance calculation indicated that essentially all of the tracer transported to sea during the land breeze was transpoted back across the shore during the subsequent sea breeze. A methodology for calculating a mass balance and the associated uncertainties is presented. The experimental and calculation procedures presented allowed mass balance estimates with less uncertainty than is present in individual measurements of concentration or mixing height. Similarly, a methodology for calculating dispersion parameters for the gaussian plume model from tracer data is discussed and applied to the results of two atmospheric tracer studies conducted during the afternoon sea breeze in the Santa Barbara Channel of California. The method presented involves the integral definitions of the statistical quantities. By considering only tracer concentrations greater than 10% of the maximum concentration, and by considering sufficiently many data points, the uncertainty associated with the parameter estimation was again less than the relative uncertainties in any individual data point. These studies were primarily designed to relate the uncertainties in estimates of mass balances and in estimations of gaussian parameters to the uncertainties inherent within field data.

  11. Multiple Proxy Estimates of Atmospheric CO2 from an Early Paleocene Rainforest

    NASA Astrophysics Data System (ADS)

    Kowalczyk, J.; Royer, D. L.; Miller, I.; Franks, P.

    2016-12-01

    As atmospheric CO2 continues to increase, we enter a climate state whose analogue in terms of CO2 concentration is found millions of years ago. Knowledge of this ancient climate is only accessible via proxy reconstructions. However, many proxy methods suffer from large uncertainties and/or systematic biases. This is illustrated in a compilation of atmospheric CO2 estimates over the Cenozoic from different proxy methods that shows two-fold scatter for many time-slices (Beerling and Royer, 2011, Nature Geoscience 4: 418 - 420). It is unclear how much of this scatter is due to true CO2 variation and how much is due to proxy model biases. Therefore, to increase understanding of and confidence in proxy methods, multi-proxy comparison studies are greatly needed. Here we present results from one such comparison study, the first of its kind for land-based proxies. Using plant fossils from the unusually diverse early Paleocene (64.5 Ma) Castle Rock rainforest, we generate CO2 estimates from four proxy methods: the traditional stomatal index, two newer models based on gas-exchange in C3 plants, and a model based on liverwort photosynthesis. Median estimates range from 470 to 832 ppm, indicating that much of the scatter in the Beerling and Royer (2011) compilation could be due to proxy model biases. We also present sensitivity analyses for the multi-parameter proxy methods, providing a helpful guide to model users by highlighting parameters that contribute most to uncertainty in estimated CO2.

  12. Estimating the lower ionosphere height and lightning location using multimode “tweek” atmospherics

    NASA Astrophysics Data System (ADS)

    Shvets, A. V.; Serdiuk, T. M.; Gorishnyaya, Y. V.; Hobara, Y.; Hayakawa, M.

    2014-02-01

    There is proposed a new method of estimating the effective ionospheric height of the Earth-ionosphere waveguide and the propagation distance of tweek-atmospherics. It is based on the compensation of waveguide frequency dispersion of a tweek signal, which enables us to improve the accuracy of deducing the cutoff frequencies, especially in the presence of noise. An approach to solve the inverse problem is suggested that reduces the task of finding both the source range and the waveguide cutoff frequencies by using the multimode characteristics of tweeks to an issue of one-dimensional optimization. Based on the numerical modeling of multimode tweek-atmospherics in the Earth-ionosphere waveguide with exponential vertical conductivity profile of the lower ionosphere, it was shown that the accuracy of estimating the effective waveguide height by the new method is good as about 100-400 m for the first and higher order modes. It then allows us to estimate the parameters of vertical conductivity profile of the lower ionosphere for a wide range of source distances from a few hundred to a few thousand kilometers, as long as two or more tweek harmonics can be detected. Preliminary analysis of experimental tweek records show a decrease of the effective height with increasing the mode number, and the scale height of the exponential vertical conductivity profile for the isotropic lower ionosphere model is estimated to be in a range of 0.4-2.5 km.

  13. Estimates of atmospheric CO2 in the Neoarchean-Paleoproterozoic from paleosols

    NASA Astrophysics Data System (ADS)

    Kanzaki, Yoshiki; Murakami, Takashi

    2015-06-01

    Atmospheric CO2 levels reflect Earth's surface temperatures directly, and have been discussed especially in association with the faint young Sun and Snowball Earth in the Precambrian. In addition, atmospheric O2 levels in the Precambrian have been estimated from paleosols, fossil weathering profiles, based on the estimates of atmospheric CO2 levels. Nevertheless, atmospheric CO2 levels in the Neoarchean and the Paleoproterozoic have remained as a debatable topic. In order to precisely estimate atmospheric CO2 levels in the Neoarchean-Paleoproterozoic, we developed a new method that calculates CO2 levels from the chemical compositions of paleosols. The new method (i) calculates the cation concentrations in porewaters at the time of weathering from those of paleosols, (ii) describes the relationships between partial pressure of atmospheric CO2 (PCO2), pH and cation concentrations based on the charge balance between the cations and anions including carbonate species in porewaters, and (iii) finally calculates PCO2 levels at a given temperature constraining pH by thermodynamics of weathering secondary-minerals. By applying the new method to modern weathering profiles, we obtained a good agreement between the calculated and observed PCO2 levels. The weathering rate deduced from the new method was proportional to PCO2 with fractional dependence of 0.18 and the apparent activation energy of weathering was 40-55 kJ mol-1, which is consistent with the laboratory and field results. The application to modern weathering and the formulated characteristics of weathering strongly indicate that the new method is valid and robust. The new method was then applied to eight paleosols formed in the Neoarchean-Paleoproterozoic. We made constraints on the local temperatures, at which the paleosols were formed, mainly by the temperature and solute-concentration relationships in the literature, because they should have been different between the paleosols and from the average global

  14. Impact of meteorological inflow uncertainty on tracer transport and source estimation in urban atmospheres

    DOE PAGES

    Lucas, Donald D.; Gowardhan, Akshay; Cameron-Smith, Philip; ...

    2015-08-08

    Here, a computational Bayesian inverse technique is used to quantify the effects of meteorological inflow uncertainty on tracer transport and source estimation in a complex urban environment. We estimate a probability distribution of meteorological inflow by comparing wind observations to Monte Carlo simulations from the Aeolus model. Aeolus is a computational fluid dynamics model that simulates atmospheric and tracer flow around buildings and structures at meter-scale resolution. Uncertainty in the inflow is propagated through forward and backward Lagrangian dispersion calculations to determine the impact on tracer transport and the ability to estimate the release location of an unknown source. Ourmore » uncertainty methods are compared against measurements from an intensive observation period during the Joint Urban 2003 tracer release experiment conducted in Oklahoma City.« less

  15. Towards estimation of atmospheric tidal effects on the ionosphere via data assimilation

    NASA Astrophysics Data System (ADS)

    Solomentsev, Dmitry; Cherniak, Yakov; Titov, Anton; Khattatov, Boris; Khattatov, Vyacheslav

    2015-11-01

    The impact of atmospheric tides on the night time ionosphere is now being a subject of the extensive research within the scientific community. The plausible effect has been observed using the multiple space-borne instruments (e.g. COSMIC/FORMOSAT-3 constellation, TIMED GUVI and NASA IMAGE). Along with the observations, several modelling attempts has been undertaken to prove or refute the interrelation between the atmospheric tides and the wave-four longitudinal night time ionosphere structure. The scope of the current article is to assess the data assimilation ionosphere model capabilities in representing the longitudinal effect in the night time ionosphere induced by the DE3 atmospheric tide. Along with this, the core physics-based model capabilities in estimating the same effect are presented and discussed. For the current research, two periods were taken into consideration: the autumn equinox of the years 2006 and 2012. In the current article the data assimilation and physics-based models calculation results are presented and discussed along with the models' error estimation and analysis.

  16. Emission rate estimation through data assimilation of gamma dose measurements in a Lagrangian atmospheric dispersion model.

    PubMed

    Tsiouri, V; Kovalets, I; Andronopoulos, S; Bartzis, J G

    2012-01-01

    This paper presents an efficient algorithm for estimating the unknown emission rate of radionuclides in the atmosphere following a nuclear accident. The algorithm is based on assimilation of gamma dose rate measured data in a Lagrangian atmospheric dispersion model. Such models are used in the framework of nuclear emergency response systems (ERSs). It is shown that the algorithm is applicable in both deterministic and stochastic modes of operation of the dispersion model. The method is evaluated by computational simulations of a 3-d field experiment on atmospheric dispersion of ⁴¹Ar emitted routinely from a research reactor. Available measurements of fluence rate (photons flux) in air are assimilated in the Lagrangian dispersion model DIPCOT and the ⁴¹Ar emission rate is estimated. The statistical analysis shows that the model-calculated emission rates agree well with the real ones. In addition the model-predicted fluence rates at the locations of the sensors, which were not used in the data assimilation procedure are in better agreement with the measurements. The first evaluation results of the method presented in this study show that the method performs satisfactorily and therefore it is applicable in nuclear ERSs provided that more comprehensive validation studies will be performed.

  17. Modified ensemble Kalman filter for nuclear accident atmospheric dispersion: prediction improved and source estimated.

    PubMed

    Zhang, X L; Su, G F; Yuan, H Y; Chen, J G; Huang, Q Y

    2014-09-15

    Atmospheric dispersion models play an important role in nuclear power plant accident management. A reliable estimation of radioactive material distribution in short range (about 50 km) is in urgent need for population sheltering and evacuation planning. However, the meteorological data and the source term which greatly influence the accuracy of the atmospheric dispersion models are usually poorly known at the early phase of the emergency. In this study, a modified ensemble Kalman filter data assimilation method in conjunction with a Lagrangian puff-model is proposed to simultaneously improve the model prediction and reconstruct the source terms for short range atmospheric dispersion using the off-site environmental monitoring data. Four main uncertainty parameters are considered: source release rate, plume rise height, wind speed and wind direction. Twin experiments show that the method effectively improves the predicted concentration distribution, and the temporal profiles of source release rate and plume rise height are also successfully reconstructed. Moreover, the time lag in the response of ensemble Kalman filter is shortened. The method proposed here can be a useful tool not only in the nuclear power plant accident emergency management but also in other similar situation where hazardous material is released into the atmosphere.

  18. Can we estimate the fog-top height from atmospheric turbulent measurements at surface?

    NASA Astrophysics Data System (ADS)

    Román-Cascón, Carlos; Yagüe, Carlos; Steeneveld, Gert-Jan; Sastre, Mariano; Arrillaga, Jon A.; Maqueda, Gregorio

    2016-04-01

    The knowledge of the fog-top height (fog thickness) can be very meaningful for aircraft maneuvers, data assimilation/validation of Numerical Weather Prediction models or nowcasting of fog dissipation. However, its value is usually difficult to determine and it is sometimes approximated with satellite data, ground remote-sensing instruments or atmospheric soundings. These instruments are expensive and their data not always available. In this work, we show how the fog-top height shows a linear correlation with atmospheric turbulent variables measured close to the surface. This relation is statistically calculated from observational data of several radiation-fog events at two research sites: The Research Centre for the Lower Atmosphere (CIBA) in Spain and the Cabauw Experimental Site for Atmospheric Research (CESAR) in The Netherlands. Thus, surface friction velocity and buoyancy heat flux are presented as potential indicators of fog thickness. These methods are also evaluated over a long-lasting radiation-fog event at CESAR. The proposed methods could be operationally implemented for providing a continuous estimation of fog-top height through the deployment of a sonic anemometer close to the surface.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. CarbonTracker-CH4: an assimilation system for estimating emissions of atmospheric methane

    NASA Astrophysics Data System (ADS)

    Bruhwiler, L. M.; Dlugokencky, E.; Masarie, K.; Ishizawa, M.; Andrews, A.; Miller, J.; Sweeney, C.; Tans, P.; Worthy, D.

    2014-01-01

    We describe an assimilation system for atmospheric methane (CH4), CarbonTracker-CH4, and demonstrate the diagnostic value of global or zonally averaged CH4 abundances for evaluating the results. We show that CarbonTracker-CH4 is able to simulate the observed zonal average mole fractions and capture inter-annual variability in emissions quite well at high northern latitudes (53-90° N). CarbonTracker-CH4 estimates of total fluxes at high northern latitudes are about 81 Tg CH4 yr-1, about 12 Tg CH4 yr-1 (13%) lower than prior estimates, a result that is consistent with other atmospheric inversions. Emissions from European wetlands are decreased by 30%, a result consistent with previous; however, emissions from wetlands in Boreal Eurasia are increased relative to the prior estimate. Although CarbonTracker-CH4 does not estimate increases in emissions from high northern latitudes for 2000 through 2010, significant inter-annual variability in high northern latitude fluxes is recovered. During the exceptionally warm Arctic summer of 2007, estimated emissions were greater than the decadal average by 4.4 Tg CH4 yr-1. In 2008, temperatures returned to more normal values over Arctic North America while they stayed above normal over Arctic Eurasia. CarbonTracker-CH4 estimates were 2.4 Tg CH4 yr-1 higher than the decadal average, and the anomalous emissions occurred over Arctic Eurasia, suggesting that the data allow discrimination between these two source regions. Also, the emission estimates respond to climate variability without having the system constrained by climate parameters. CarbonTracker-CH4 estimates for temperate latitudes are only slightly increased over prior estimates, but about 10 Tg CH4 yr-1 is redistributed from Asia to North America. We used time invariant prior flux estimates, so for the period from 2000 to 2006, when the growth rate of global atmospheric CH4 was very small, the assimilation does not produce increases in natural or anthropogenic emissions in

  4. Decadal trends in regional CO2 fluxes estimated from atmospheric inversions

    NASA Astrophysics Data System (ADS)

    Saeki, T.; Patra, P. K.

    2016-12-01

    Top-down approach (or atmospheric inversion) using atmospheric transport models and CO2 observations are an effective way to optimize surface fluxes at subcontinental scales and monthly time intervals. We used the CCSR/NIES/FRCGC AGCM-based Chemistry Transport Model (JAMSTEC's ACTM) and atmospheric CO2 concentrations at NOAA, CSIRO, JMA, NIES, NIES-MRI sites from Obspack GLOBALVIEW-CO2 data product (2013) for estimating CO2 fluxes for the period of 1990-2011. Carbon fluxes were estimated for 84 partitions (54 lands + 30 oceans) of the globe by using a Bayesian synthesis inversion framework. A priori fluxes are (1) atmosphere-ocean exchange from Takahashi et al. (2009), (2) 3-hourly terrestrial biosphere fluxes (annually balanced) from CASA model, and (3) fossil fuel fluxes from CDIAC global totals and EDGAR4.2 spatial distributions. Four inversion cases have been tested with 1) 21 sites (sites which have real data fraction of 90 % or more for 1989-2012), 2) 21 sites + CONTRAIL data, 3) 66 sites (over 70 % coverage), and 4) 157 sites. As a result of time-dependent inversions, mean total flux (excluding fossil fuel) for the period 1990-2011 is estimated to be -3.09 ±0.16 PgC/yr (mean and standard deviation of the four cases), where land (incl. biomass burning and land use change) and ocean absorb an average rate of -1.80 ±0.18 and -1.29 ±0.08 PgC/yr, respectively. The average global total sink from 1991-2000 to 2001-2010 increases by about 0.5 PgC/yr, mainly due to the increase in northern and tropical land sinks (Africa, Boreal Eurasia, East Asia and Europe), while ocean sinks show no clear trend. Inversion with CONTRAIL data estimates large positive flux anomalies in late 1997 associated with the 1997/98 El-Nino, while inversion without CONTARIL data between Japan and Australia fails to estimate such large anomalies. Acknowledgements. This work is supported by the Environment Research and Technology Development Fund (2-1401) of the Ministry of the Environment

  5. 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.

  6. Static stability of the Jovian atmospheres estimated from moist adiabatic profiles

    NASA Astrophysics Data System (ADS)

    Sugiyama, Ko-ichiro; Odaka, Masatsugu; Kuramoto, Kiyoshi; Hayashi, Yoshi-Yuki

    2006-02-01

    The dependency of static stability N2 of the Jovian atmospheres on the abundances of condensible elements is considered by calculating the moist adiabatic profiles. An optimal minimization method of the Gibbs free energy is utilized to obtain equilibrium compositions in order to cover a variety of basic elements. It is shown that CH4 is one of the dominant contributors to producing a stable layer in the Uranian atmosphere. On Jupiter, R. K. Achterberg and A. P. Ingersoll (1989) have shown that, at low water abundances, N2 is proportional to the H2O abundance. In the present study, we show that this relationship does not hold when the H2O abundance is larger than approximately 5 × solar. A rough estimation of wave speed indicates that the abundance of 10 × solar is marginal to explain the SL9-induced wave speed as that of an internal gravity wave.

  7. Comparison of CO2 fluxes estimated using atmospheric and oceanic inversions, and role of fluxes and their interannual variability in simulating atmospheric CO2 concentrations

    NASA Astrophysics Data System (ADS)

    Patra, P. K.; Mikaloff Fletcher, S. E.; Ishijima, K.; Maksyutov, S.; Nakazawa, T.

    2006-07-01

    We use a time-dependent inverse (TDI) model to estimate regional sources and sinks of atmospheric CO2 from 64 and then 22 regions based on atmospheric CO2 observations at 87 stations. The air-sea fluxes from the 64-region atmospheric-CO2 inversion are compared with fluxes from an analogous ocean inversion that uses ocean interior observations of dissolved inorganic carbon (DIC) and other tracers and an ocean general circulation model (OGCM). We find that, unlike previous atmospheric inversions, our flux estimates in the southern hemisphere are generally in good agreement with the results from the ocean inversion, which gives us added confidence in our flux estimates. In addition, a forward tracer transport model (TTM) is used to simulate the observed CO2 concentrations using (1) estimates of fossil fuel emissions and a priori estimates of the terrestrial and oceanic fluxes of CO2, and (2) two sets of TDI model corrected fluxes. The TTM simulations of TDI model corrected fluxes show improvements in fitting the observed interannual variability in growth rates and seasonal cycles in atmospheric CO2. Our analysis suggests that the use of interannually varying (IAV) meteorology and a larger observational network have helped to capture the regional representation and interannual variabilities in CO2 fluxes realistically.

  8. Chlorophyll Concentration Estimates for Coastal Waters using Pixel-Based Atmospheric Correction of Landsat Images

    NASA Astrophysics Data System (ADS)

    Kouba, E.; Xie, H.

    2014-12-01

    Ocean color analysis is more challenging for coastal regions than the global ocean due the effects of optical brightness, shallow and turbid water, higher phytoplankton growth rates, and the complex geometry of coastal bays and estuaries. Also, one of the key atmospheric correction assumptions (zero water leaving radiance in the near infrared) is not valid for these complex conditions. This makes it difficult to estimate the spectral radiance noise caused by atmospheric aerosols, which can vary rapidly with time and space. This project evaluated using Landsat-7 ETM+ observations over a set of coastal bays, and allowing atmospheric correction calculations to vary with time and location as much as practical. Precise satellite orbit vector data was combined with operational weather and climate data to create interpolated arrays of atmospheric profiles which varied with time and location, allowing separate calculation of the Rayleigh and aerosol radiance corrections for all pixels. The resulting normalized water-leaving radiance values were compared with chlorophyll fluorescence measurements made at five in-situ stations inside a set of Texas coastal bays: the Mission-Aransas National Estuarine Research Reserve. Curve-fitting analysis showed it was possible to estimate chlorophyll surface area concentrations by using ETM+ water-leaving radiance values and a third-order polynomial equation. Two pairs of ETM+ bands were identified as inputs (Bands 1 and 3, and the Log10 values of Bands 3 and 4), both achieving R2 of 0.69. Additional research efforts were recommended to obtain additional data, identify better curve fitting equations, and potentially extend the radiative transfer model into the water column.

  9. Chlorophyll concentration estimates for coastal water using pixel-based atmospheric correction of Landsat images

    NASA Astrophysics Data System (ADS)

    Kouba, Eric

    Ocean color analysis is more challenging for coastal regions than the global ocean due the effects of optical brightness, shallow and turbid water, higher phytoplankton growth rates, and the complex geometry of coastal bays and estuaries. Also, one of the key atmospheric correction assumptions (zero water leaving radiance in the near infrared) is not valid for these complex conditions. This makes it difficult to estimate the spectral radiance noise caused by atmospheric aerosols, which can vary rapidly with time and space. This study conducts pixel-based atmospheric correction of Landsat-7 ETM+ images over the Texas coast. Precise satellite orbit data, operational weather data, and climate data are combined to create interpolated arrays of viewing angles and atmospheric profiles. These arrays vary with time and location, allowing calculation of the Rayleigh and aerosol radiances separately for all pixels. The resulting normalized water-leaving radiances are then compared with in situ chlorophyll fluorescence measurements from five locations inside a set of Texas coastal bays: the Mission-Aransas National Estuarine Research Reserve. Curve-fitting analysis shows it is possible to estimate chlorophyll-a surface area concentrations by using ETM+ water-leaving radiance values and a third-order polynomial equation. Two pairs of ETM+ bands are identified as inputs (Bands 1 and 3, and the Log10 values of Bands 3 and 4), both achieving good performance (R2 of 0.69). Further research efforts are recommended to obtain additional data, identify better curve fitting equations, and potentially extend the radiative transfer model into the water column.

  10. Estimation of methane fluxes in the high northern latitudes from a Bayesian atmospheric inversion

    NASA Astrophysics Data System (ADS)

    Thompson, R.; Stohl, A.; Lund myhre, C.; Sasakawa, M.; Machida, T.; Aalto, T.; Dlugokencky, E. J.; Worthy, D. E. J.

    2015-12-01

    Methane (CH4) is the second most important anthropogenic greenhouse gas after CO2. Globally, atmospheric CH4 concentrations have increased since direct measurements began, in the early 1980s, but then stabilized from the mid 1990s to the mid 2000s. Since 2007, the atmospheric CH4 growth rate has become positive again causing concern that it may be the response to climate feedbacks, especially in the Arctic, where there is a potential for a large release of CH4 to the atmosphere under warmer conditions. Such feedbacks include high latitude wetlands, permafrost and the destabilization of methane hydrates. We present CH4 emission estimates for the high northern latitudes (i.e., north of 50°N) from 2005 to 2012 using atmospheric mole fraction observations in a Bayesian inversion framework. This framework is based on the Lagrangian Particle Dispersion model, FLEXPART, run with ECMWF meteorological analyses. Emissions were optimized monthly and on a spatial grid of variable resolution. Background mixing ratios were found by coupling FLEXPART to output from the optimized Eulerian chemistry transport model, TM5. Meteorological models tend to overestimate the boundary layer heights (BLH) in the Arctic, especially in winter, which can lead to biases in the estimated fluxes. Therefore, we explored a number of data selection criteria to avoid assimilating data at times when significant errors in BLH were likely. Overall, the inversion found higher emissions in Northern Eurasia and North America compared to the prior in both summer and winter. The inversion fluxes also displayed considerable inter-annual variability, which appears to be related to climate variability.

  11. Biogenic sulfur emissions and aerosols over the tropical South Atlantic 1: Dimethylsulfide in seawater and in the atmospheric boundary layer

    SciTech Connect

    Andreae, T.W.; Andreae, M.O.; Schebeske, G.

    1994-11-01

    We measured dimethylsulfide (DMS) in air (DMS(sub a)) and surface seawater (DMS(sub w)) on board the R/V Meteor during February-March 1991 on the tropical South Atlantic. Samples for the determination of DMS(sub a) were taken through a fluorinated ethylene/propylene Teflon inlet at about 33 m above sea level, preconcentrated by adsorption onto gold wool in quartz tubes, and analyzed by gas chromotography with flame photometric detection. The DMS(sub a) instrument is fully automated, providing improved precision, and processes up to four samples per hour. Over most of the cruise track, which followed the 19 deg S parallel between Brazil and Africa, DMS(sub w) was significantly correlated to climatologically averaged chlorophyll concentrations obtained from coastal zone color scanner data, suggesting that remote sensing may be useful for estimating seawater DMS levels at least in some ocean regions. The cruise track proceeded from waters of low productivity (off the coast of Brazil and in the subtropical gyre) to higher productivity (the Benguela Current and the upwelling region off Namibia and Angola); meteorological conditions were steady with consistent easterly winds. DMS values for air and water were low (about 50 ppt and 1-2 nmol/L, respectively) in the areas of low productivity and increased simultaneously (about 100-300 ppt and 3-15 nmol/l) as productivity increased. DMS sea-to-air fluxes (average 7.3) were calculated based on different parameterizations; for the study region the differences between the results obtained from the different models were minor. DMS(sub a) was strongly correlated to its emission flux from the sea surface as estimated from DMS(sub w) and meteorological parameters. This suggests that the air/sea transfer parameterizations used are suitable for providing estimates of DMS flux from the oceans.

  12. Atmosphere-Truth Z-R Rainfall Estimates: A Fresh Approach to an Old Problem

    NASA Astrophysics Data System (ADS)

    Henz, J. F.

    2010-12-01

    Common modeling practice for basin calibration uses rainfall fields developed by the statistical use of surface rain gauge observed data or the direct application of NEXRAD National Weather Service WSR-88D Doppler radar Storm Total Rainfall or 1-hr rainfall estimations. Each of these approaches has significant limitations. Rain gages often lack sufficient spatial coverage to measure true storm intensity or the distribution of rainfall in a basin. The NWS WSR-88D Doppler radar algorithms are constantly being improved but still fail to deliver consistent rainfall estimates. Significant problems are caused by an under-estimation of warm coalescence rains and an over-estimation of rainfall in both dry environments and storms with hail contamination. Finally, storm updraft areas are frequently counted as raining portions of the storm producing immediate errors. The statistical techniques often under-estimate rainfall when the heavy rain core of the storm misses the rain gauges or if high winds cause an under-catchment of rainfall. Gauge-adjusted rainfall estimates are also dependant on the core of the storm being observed by a gauge. Statistical approaches often under-estimate rainfall producing insufficient runoff to drive the observed flooding runoffs. The Atmosphere-Truth ZR (ATZR) technique uses an atmosphere-truthed algorithm to produce highly accurate estimates of surface rainfall from Doppler radar data. This approach relies on using a cloud physics approach to determine the atmosphere’s ability to produce 15-min to hourly rain rates. The atmsopheric rainfall is utilizes surface, boundary layer and cloud layer observations of temperature and moisture from conventional National Weather Service observations. The depth of the thunderstorm updraft region that exceeds 0C is used with the precipitable water index and updraft speeds to provide estimates of 15-min to hourly rainfall rates from radar reflectivity areas in the storm greather than 50 dBZ. Rainfall rates

  13. Correcting atmospheric effects in thermal ground observations for hyperspectral emissivity estimation

    NASA Astrophysics Data System (ADS)

    Timmermans, Joris; Buitrago, Maria

    2014-05-01

    Knowledge of Land surface temperature is of crucial importance in energy balance studies and environmental modeling. Accurate retrieval of land surface temperature (LST) demands detailed knowledge of the land surface emissivity. Measured radiation by remote sensing sensors to land surface temperature can only be performed using a-priori knowledge of the emissivity. Uncertainties in the retrieval of this emissivity can cause huge errors in LST estimations. The retrieval of emissivity (and LST) is per definition an underdetermined inversion, as only one observation is made while two variables are to be estimated. Several researches have therefore been performed on measuring emissivity, such as the normalized emissivity method, the temperature-emissivity separation (TES) using the minimum and maximum difference of emissivity and the use of vegetation indices. In each of these approaches atmospherically corrected radiance measurements by remote sensing sensors are correlated to ground measurements. Usually these ground measurements are performed with the ground equivalent of the remote sensing sensors; the CIMEL 312-2 has the same spectral bands as ASTER. This way parameterizations acquired this way are only usable for specific sensors and need to be redone for newer sensors. Recently hyperspectral thermal radiometers, such as the MIDAC, have been developed that can solve this problem. By using hyperspectral observations of emissivity, together with sensor simulators, ground measurements of different satellite sensor can be simulated. This facilitates the production of validation data for the different TES algorithms. However before such measurements can be performed extra steps of processing need to be performed. Atmospheric correction becomes more important in hyperspectral observations than for broadband observations, as energy levels measured per band is lower. As such the atmosphere has a relative larger contribution if bandwidths become smaller. The goal of this

  14. 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

  15. Methane fluxes in the high northern latitudes estimated using a Bayesian atmospheric inversion

    NASA Astrophysics Data System (ADS)

    Thompson, Rona; Stohl, Andreas; Myhre, Cathrine Lund; Sasakawa, Motoki; Machida, Toshinobu; Aalto, Tuula; Dlugokencky, Edward; Worthy, Douglas; Skorokhod, Andrey

    2016-04-01

    Methane (CH4) is the second most important anthropogenic greenhouse gas after CO2. Atmospheric CH4 increased from pre-industrial concentrations of around 850 ppb (parts-per-billion) to 1773 ppb in the late 1990s and then remained approximately stable until the mid 2000s. However, since 2006 atmospheric CH4 has begun to increase again. The reasons for the stabilization and subsequent increase are likely to be a combination of changes in anthropogenic emissions such as from fossil fuels, as well as natural wetland sources. While global atmospheric inversions indicate that natural wetland sources in the tropics and subtropics have contributed to the recent increase, land surface and ecosystem models generally indicate no increase in these sources. Another potential source for the change in CH4 concentration could be wetlands in the high northern latitudes, which comprise about 44% of global wetland area. These latitudes are also undergoing rapid warming, which will impact wetland emissions of CH4. We present CH4 fluxes for the high northern latitudes (>50°N) from 2005 to 2012 estimated from a Bayesian atmospheric inversion. The inversion incorporates observations from 17 in-situ and 6 discrete-sample sites across North America and Northern Eurasia. Atmospheric transport is based on the Lagrangian particle dispersion model, FLEXPART, run with ECMWF meteorological analyses. Emissions were optimized monthly and on a spatial grid of variable resolution (from 1°×1° to 4°×4°). Background concentrations were estimated by coupling FLEXPART to monthly global 2-D fields of CH4 concentration from a bivariate interpolation of smoothed data from the NOAA ESRL network. We estimate the total mean North American flux (>50°N) to be 18 -- 27 Tg y-1, and the total mean Northern Eurasian flux (>50°N) to be 55 -- 66 Tg y-1, both substantially higher than the prior (based on LPX-Bern for wetland and EDGAR-4.2FT2010 for anthropogenic fluxes). We also find a small trend in the

  16. Estimating tropospheric phase delay in SAR interferograms using Global Atmospheric Models

    NASA Astrophysics Data System (ADS)

    Doin, M.; Lasserre, C.; Peltzer, G.; Cavalie, O.; Doubre, C.

    2008-12-01

    The main limiting factor on the accuracy of Interferometric SAR (InSAR) measurements comes from phase propagation delays through the Earth's troposphere. The delay can be divided into a stratified component, which correlates with the topography and often dominates the tropospheric signal in InSAR data, and a turbulent component. The stratified delay can be expressed as a function of atmospheric pressure P, temperature T, and water vapor partial pressure e vertical profiles. We compare the stratified delay computed using results from global atmospheric models with the topography-dependent signal observed in interferograms covering three test areas in different geographic and climatic environments: Lake Mead, Nevada, USA, the Haiyuan fault area, Gansu, China, and Afar, Republic of Djibouti. For each site we compute a multi-year series of interferograms. The phase-elevation ratio is estimated for each interferogram and the series is inverted to form a timeline of delay-elevation ratios characterizing each epoch of data acquisition. InSAR derived ratios are in good agreement with the ratios computed from global atmospheric models. This agreement shows that both estimations of the delay-elevation ratio can be used to perform a first order correction of the InSAR phase. Seasonal variations of the atmosphere significantly affect the phase delay throughout the year, aliasing the results of time series inversions using temporal smoothing or data stacking when the acquisitions are not evenly distributed in time. This is particularly critical when the spatial shape of the signal of interest correlates with topography. In the Lake Mead area, the irregular temporal sampling of our SAR data results in an interannual bias of amplitude ~2~cm on range change estimates. In the Haiyuan Fault area, the coarse and uneven data sampling results in a bias of up to ~0.5~cm/yr on the line of sight velocity across the fault. In the Afar area, the seasonal signal exceeds the deformation

  17. An attempt at estimating Paris area CO2 emissions from atmospheric concentration measurements

    NASA Astrophysics Data System (ADS)

    Bréon, F. M.; Broquet, G.; Puygrenier, V.; Chevallier, F.; Xueref-Rémy, I.; Ramonet, M.; Dieudonné, E.; Lopez, M.; Schmidt, M.; Perrussel, O.; Ciais, P.

    2014-04-01

    Atmospheric concentration measurements are used to adjust the daily to monthly budget of CO2 emissions from the AirParif inventory of the Paris agglomeration. We use 5 atmospheric monitoring sites including one at the top of the Eiffel tower. The atmospheric inversion is based on a Bayesian approach, and relies on an atmospheric transport model with a spatial resolution of 2 km with boundary conditions from a global coarse grid transport model. The inversion tool adjusts the CO2 fluxes (anthropogenic and biogenic) with a temporal resolution of 6 h, assuming temporal correlation of emissions uncertainties within the daily cycle and from day to day, while keeping the a priori spatial distribution from the emission inventory. The inversion significantly improves the agreement between measured and modelled concentrations. However, the amplitude of the atmospheric transport errors is often large compared to the CO2 gradients between the sites that are used to estimate the fluxes, in particular for the Eiffel tower station. In addition, we sometime observe large model-measurement differences upwind from the Paris agglomeration, which confirms the large and poorly constrained contribution from distant sources and sinks included in the prescribed CO2 boundary conditions These results suggest that (i) the Eiffel measurements at 300 m above ground cannot be used with the current system and (ii) the inversion shall rely on the measured upwind-downwind gradients rather than the raw mole fraction measurements. With such setup, realistic emissions are retrieved for two 30 day periods. Similar inversions over longer periods are necessary for a proper evaluation of the results.

  18. On-line estimation of error covariance parameters for atmospheric data assimilation

    NASA Technical Reports Server (NTRS)

    Dee, Dick P.

    1995-01-01

    A simple scheme is presented for on-line estimation of covariance parameters in statistical data assimilation systems. The scheme is based on a maximum-likelihood approach in which estimates are produced on the basis of a single batch of simultaneous observations. Simple-sample covariance estimation is reasonable as long as the number of available observations exceeds the number of tunable parameters by two or three orders of magnitude. Not much is known at present about model error associated with actual forecast systems. Our scheme can be used to estimate some important statistical model error parameters such as regionally averaged variances or characteristic correlation length scales. The advantage of the single-sample approach is that it does not rely on any assumptions about the temporal behavior of the covariance parameters: time-dependent parameter estimates can be continuously adjusted on the basis of current observations. This is of practical importance since it is likely to be the case that both model error and observation error strongly depend on the actual state of the atmosphere. The single-sample estimation scheme can be incorporated into any four-dimensional statistical data assimilation system that involves explicit calculation of forecast error covariances, including optimal interpolation (OI) and the simplified Kalman filter (SKF). The computational cost of the scheme is high but not prohibitive; on-line estimation of one or two covariance parameters in each analysis box of an operational bozed-OI system is currently feasible. A number of numerical experiments performed with an adaptive SKF and an adaptive version of OI, using a linear two-dimensional shallow-water model and artificially generated model error are described. The performance of the nonadaptive versions of these methods turns out to depend rather strongly on correct specification of model error parameters. These parameters are estimated under a variety of conditions, including

  19. On-line estimation of error covariance parameters for atmospheric data assimilation

    NASA Technical Reports Server (NTRS)

    Dee, Dick P.

    1995-01-01

    A simple scheme is presented for on-line estimation of covariance parameters in statistical data assimilation systems. The scheme is based on a maximum-likelihood approach in which estimates are produced on the basis of a single batch of simultaneous observations. Simple-sample covariance estimation is reasonable as long as the number of available observations exceeds the number of tunable parameters by two or three orders of magnitude. Not much is known at present about model error associated with actual forecast systems. Our scheme can be used to estimate some important statistical model error parameters such as regionally averaged variances or characteristic correlation length scales. The advantage of the single-sample approach is that it does not rely on any assumptions about the temporal behavior of the covariance parameters: time-dependent parameter estimates can be continuously adjusted on the basis of current observations. This is of practical importance since it is likely to be the case that both model error and observation error strongly depend on the actual state of the atmosphere. The single-sample estimation scheme can be incorporated into any four-dimensional statistical data assimilation system that involves explicit calculation of forecast error covariances, including optimal interpolation (OI) and the simplified Kalman filter (SKF). The computational cost of the scheme is high but not prohibitive; on-line estimation of one or two covariance parameters in each analysis box of an operational bozed-OI system is currently feasible. A number of numerical experiments performed with an adaptive SKF and an adaptive version of OI, using a linear two-dimensional shallow-water model and artificially generated model error are described. The performance of the nonadaptive versions of these methods turns out to depend rather strongly on correct specification of model error parameters. These parameters are estimated under a variety of conditions, including

  20. 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

  1. A simple algorithm to estimate the effective regional atmospheric parameters for thermal-inertia mapping

    USGS Publications Warehouse

    Watson, K.; Hummer-Miller, S.

    1981-01-01

    A method based solely on remote sensing data has been developed to estimate those meteorological effects which are required for thermal-inertia mapping. It assumes that the atmospheric fluxes are spatially invariant and that the solar, sky, and sensible heat fluxes can be approximated by a simple mathematical form. Coefficients are determined from least-squares method by fitting observational data to our thermal model. A comparison between field measurements and the model-derived flux shows the type of agreement which can be achieved. An analysis of the limitations of the method is also provided. ?? 1981.

  2. To estimation of the fluxes of carbon dioxide in the Lake Baikal water-atmosphere system

    NASA Astrophysics Data System (ADS)

    Pestunov, D. A.; Panchenko, Mikhail V.; Domysheva, V. M.; Belan, Boris D.

    2004-12-01

    Separate many-day series of measurements of the carbon dioxide concentration were carried out at the stationary site of the Limnological Institute SB RAS near village Bol"shie Koty in July, August and October 2003. The CO2 fluxes from the water surface are estimated. Maximum amplitude of the diurnal variations of the CO2 concentration in the chamber in August was 100 ppmV, and minimum was 45 ppmV. Comparison with the results of measurements in the atmosphere and the data on the CO2 content in the near-surface water of Lake Baikal is performed.

  3. Impact of meteorological inflow uncertainty on tracer transport and source estimation in urban atmospheres

    NASA Astrophysics Data System (ADS)

    Lucas, Donald D.; Gowardhan, Akshay; Cameron-Smith, Philip; Baskett, Ronald L.

    2016-10-01

    A computational Bayesian inverse technique is used to quantify the effects of meteorological inflow uncertainty on tracer transport and source estimation in a complex urban environment. We estimate a probability distribution of meteorological inflow by comparing wind observations to Monte Carlo simulations from the Aeolus model. Aeolus is a computational fluid dynamics model that simulates atmospheric and tracer flow around buildings and structures at meter-scale resolution. Uncertainty in the inflow is propagated through forward and backward Lagrangian dispersion calculations to determine the impact on tracer transport and the ability to estimate the release location of an unknown source. Our uncertainty methods are compared against measurements from an intensive observation period during the Joint Urban 2003 tracer release experiment conducted in Oklahoma City. The best estimate of the inflow at 50 m above ground for the selected period has a wind speed and direction of 4.6-2.5+2.0 m s-1 and 158.0-23+16 , where the uncertainty is a 95% confidence range. The wind speed values prescribed in previous studies differ from our best estimate by two or more standard deviations. Inflow probabilities are also used to weight backward dispersion plumes and produce a spatial map of likely tracer release locations. For the Oklahoma City case, this map pinpoints the location of the known release to within 20 m. By evaluating the dispersion patterns associated with other likely release locations, we further show that inflow uncertainty can explain the differences between simulated and measured tracer concentrations.

  4. Neural Partial Differentiation for Aircraft Parameter Estimation Under Turbulent Atmospheric Conditions

    NASA Astrophysics Data System (ADS)

    Kuttieri, R. A.; Sinha, M.

    2012-07-01

    An approach based on neural partial differentiation is suggested for aircraft parameter estimation using the flight data gathered under turbulent atmospheric conditions. The classical methods such as output error and equation error methods suffer from severe convergence issues; resulting in biased, inaccurate, and inconsistent estimates. Though filter error method yields better estimates while dealing with the flight data having process noise, it has few demerits like computational overheads and it allows estimation of a single set of process noise distribution matrix. The proposed neural method does not face any such problem of the classical methods. Moreover, the neural method does not require parameter initialization and a priori knowledge of the model structure. The neural network maps the aircraft state and control variables into the output variables corresponding to aerodynamic forces and moments. The parameter estimation, pertaining to lateral-directional motion, of the research aircraft de Havilland DHC-2 with simulated process noise, is presented. The results obtained using the neural partial differentiation are compared with the nominal values given in literature and with the classical methods. The neural method yields the aerodynamic derivatives very close to the nominal values and having quite low standard deviation. The neural methodology is also validated by comparing actual output variables with the neural predicted and neural reconstructed variables.

  5. 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

  6. Estimating trends in atmospheric water vapor and temperature time series over Germany

    NASA Astrophysics Data System (ADS)

    Alshawaf, Fadwa; Balidakis, Kyriakos; Dick, Galina; Heise, Stefan; Wickert, Jens

    2017-08-01

    Ground-based GNSS (Global Navigation Satellite System) has efficiently been used since the 1990s as a meteorological observing system. Recently scientists have used GNSS time series of precipitable water vapor (PWV) for climate research. In this work, we compare the temporal trends estimated from GNSS time series with those estimated from European Center for Medium-Range Weather Forecasts (ECMWF) reanalysis (ERA-Interim) data and meteorological measurements. We aim to evaluate climate evolution in Germany by monitoring different atmospheric variables such as temperature and PWV. PWV time series were obtained by three methods: (1) estimated from ground-based GNSS observations using the method of precise point positioning, (2) inferred from ERA-Interim reanalysis data, and (3) determined based on daily in situ measurements of temperature and relative humidity. The other relevant atmospheric parameters are available from surface measurements of meteorological stations or derived from ERA-Interim. The trends are estimated using two methods: the first applies least squares to deseasonalized time series and the second uses the Theil-Sen estimator. The trends estimated at 113 GNSS sites, with 10 to 19 years temporal coverage, vary between -1.5 and 2.3 mm decade-1 with standard deviations below 0.25 mm decade-1. These results were validated by estimating the trends from ERA-Interim data over the same time windows, which show similar values. These values of the trend depend on the length and the variations of the time series. Therefore, to give a mean value of the PWV trend over Germany, we estimated the trends using ERA-Interim spanning from 1991 to 2016 (26 years) at 227 synoptic stations over Germany. The ERA-Interim data show positive PWV trends of 0.33 ± 0.06 mm decade-1 with standard errors below 0.03 mm decade-1. The increment in PWV varies between 4.5 and 6.5 % per degree Celsius rise in temperature, which is comparable to the theoretical rate of the Clausius

  7. Measurement of Sulfur Isotope Ratios in Micrometer-Sized Aerosol Samples by NanoSIMS

    NASA Astrophysics Data System (ADS)

    Winterholler, B.; Hoppe, P.; Foley, S.; Andreae, M. O.

    2005-12-01

    The isotopic composition of sulfur in the atmosphere is highly variable and source dependent. Sulfur isotopic ratios are a well established tool for identifying sources of sulfur in the environment, estimating emission factors, and tracing the spread of sulfur from anthropogenic point sources in terrestrial ecosystems. Conventional mass spectrometry needs a minimum of 1 micromol of sulfur to perform one analysis. In the case of atmospheric aerosol particles the results of such an analysis averages the isotopic compositions of millions of aerosol particles, and thus normally includes several different types of sulfur aerosol. The new Cameca NanoSIMS 50 ion microprobe technique permits analysis of individual aerosol particles with volumes down to 0.3 cubic micron and a precision for delta34S of 3-10 (2 sigma). As a result, this technique is able to introduce a new scale into the study of the atmospheric sulfur cycle. Linking the chemical, mineralogical, morphological and isotopic information of individual particles will allow a better understanding of external and internal mixing states by analyzing more than one spot on coarse mode particles. Moreover it will improve source identification by complementing the chemical and isotopic information. First samples have been collected from the Sahara desert, an urban site in central Europe, and a costal site in Western Ireland and show the potentials of this new technique.

  8. Atmospheric deposition and re-emission of mercury estimated in a prescribed forest-fire experiment in Florida, USA

    Treesearch

    Ralph J. DiCosty; Mac A. Callaham; John A. Stanturf

    2006-01-01

    Prescribed fires are likely to re-emit atmospherically deposited mercury (Hg), and comparison of soil Hg storage in areas affected by prescribed fire to that in similar unburned areas may provide cross-validating estimates of atmospheric Hg deposition. Prescribed fires are common in the southeastern United States (US), a region of relatively high Hg deposition compared...

  9. Hydrate sulfuric acid after sulfur implantation in water ice

    NASA Astrophysics Data System (ADS)

    Strazzulla, G.; Baratta, G. A.; Leto, G.; Gomis, O.

    2007-12-01

    For many years an ongoing research program performed at our laboratory has had the aim to investigate the implantation of reactive ions in ices relevant to planetology by using IR spectroscopy. We present new results obtained by implanting 200 keV sulfur ions into water ice at 80 K. We have looked at the formation of sulfur-bearing molecules such as sulfuric acid, sulfur dioxide and hydrogen sulfide. We find that hydrated sulfuric acid is formed with high yield ( 0.65±0.1 molecules/ion). An upper limit to the production yield of SO 2 ( Y⩽0.025 molecules/ion) has been estimated; no hydrogen sulfide has been detected. The formation of hydrogen peroxide is confirmed. Ozone is not detected. The results are discussed relevant to the inquiry on the radiolytic sulfur cycle considered responsible for the formation of sulfur-bearing molecules on the surfaces of the Galilean satellites. We demonstrate that sulfur implantation efficiently forms hydrated sulfuric acid whose observed abundance is explained as caused by an exogenic process. It is more difficult to say if the observed sulfur dioxide is quantitatively supported by only sulfur implantation; additional experimental studies are necessary along with direct observations, especially at UV wavelengths such as those that could be performed by instruments on board Hubble Space Telescope or by the forthcoming World Space Observatory (WSO/UV).

  10. Biomass burning in Asia : annual and seasonal estimates and atmospheric emissions.

    SciTech Connect

    Streets, D. G.; Yarber, K. F.; Woo, J.-H.; Carmichael, G. R.; Decision and Information Sciences; Univ. of Iowa

    2003-10-15

    Estimates of biomass burning in Asia are developed to facilitate the modeling of Asian and global air quality. A survey of national, regional, and international publications on biomass burning is conducted to yield consensus estimates of 'typical' (i.e., non-year-specific) estimates of open burning (excluding biofuels). We conclude that 730 Tg of biomass are burned in a typical year from both anthropogenic and natural causes. Forest burning comprises 45% of the total, the burning of crop residues in the field comprises 34%, and 20% comes from the burning of grassland and savanna. China contributes 25% of the total, India 18%, Indonesia 13%, and Myanmar 8%. Regionally, forest burning in Southeast Asia dominates. National, annual totals are converted to daily and monthly estimates at 1{sup o} x 1{sup o} spatial resolution using distributions based on AVHRR fire counts for 1999--2000. Several adjustment schemes are applied to correct for the deficiencies of AVHRR data, including the use of moving averages, normalization, TOMS Aerosol Index, and masks for dust, clouds, landcover, and other fire sources. Good agreement between the national estimates of biomass burning and adjusted fire counts is obtained (R{sup 2} = 0.71--0.78). Biomass burning amounts are converted to atmospheric emissions, yielding the following estimates: 0.37 Tg of SO{sub 2}, 2.8 Tg of NO{sub x}, 1100 Tg of CO{sub 2}, 67 Tg of CO, 3.1 Tg of CH{sub 4}, 12 Tg of NMVOC, 0.45 Tg of BC, 3.3 Tg of OC, and 0.92 Tg of NH{sub 3}. Uncertainties in the emission estimates, measured as 95% confidence intervals, range from a low of {+-}65% for CO{sub 2} emissions in Japan to a high of {+-}700% for BC emissions in India.

  11. Forest biomass estimation with hemispherical photography for multiple forest types and various atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Clark, Joshua Andrew

    The importance of accurately identifying inventories of domestic energy, including forest biomass, has increasingly become a priority of the US government and its citizens as the cost of fossil fuels has risen. It is useful to identify which of these resources can be processed and transported at the lowest cost for both private and public landowners. Accurate spatial inventories of forest biomass can help landowners allocate resources to maximize forest biomass utilization and provide information regarding current forest health (e.g., forest fire potential, insect susceptibility, wildlife habitat range). This research has indicated that hemispherical photography (HP) may be an accurate and low cost sensing technique for forest biomass measurements. In this dissertation: (1) It is shown that HP gap fraction measurements and both above ground biomass and crown biomass have a linear relationship. (2) It is demonstrated that careful manipulation of images improves gap fraction estimates, even under unfavorable atmospheric conditions. (3) It is shown that estimates of Leaf Area Index (LAI), based on transformations of gap fraction measurements, are the best estimator for both above ground forest biomass and crown biomass. (4) It is shown that many factors negatively influence the utility of HP for biomass estimation. (5) It is shown that biomass of forests stands with regular spacing is not modeled well using HP. As researchers continue to explore different methods for forest biomass estimation, HP is likely to remain as a viable technique, especially if LAI can be accurately estimated. However, other methods should be compared with HP, particularly for stands where LAI is poorly estimated by HP.

  12. The Surface-Forced Overturning of the North Atlantic: Estimates from Modern Era Atmospheric Reanalysis Datasets

    NASA Astrophysics Data System (ADS)

    Grist, Jeremy; Josey, Simon; Marsh, Robert; Kwon, Young-Oh; Bingham, Rory; Blaker, Adam

    2014-05-01

    Estimates of the recent mean and time varying water mass transformation rates associated with North Atlantic surface-forced overturning are presented. The estimates are derived from heat and freshwater surface fluxes and sea surface temperature fields from six atmospheric reanalyses (JRA, NCEP-1, NCEP-2, ERA-I, CFSR and MERRA) together with sea surface salinity fields from two globally gridded data sets (World Ocean Atlas and EN3). The resulting twelve estimates of the 1979-2007 mean surface-forced streamfunction all depict a sub-polar cell, with maxima north of 45oN, near σ = 27.5 kgm-3, and a sub-tropical cell between 20oN and 40oN, near σ = 26.1 kgm-3. The mean magnitude of the sub-polar cell varies between 12-18 Sv, consistent with estimates of the overturning circulation from sub-surface observations. Analysis of the thermal and haline components of the surface density fluxes indicate large differences in the inferred low latitude circulation are largely due to the biases in reanalysis net heat flux fields, which range in the global mean from -13 Wm-2 to 19 Wm-2. The different estimates of temporal variability in the sub-polar cell are well correlated with each other. This suggests the uncertainty associated with the choice of reanalysis product does not critically limit the ability of the method to infer the variability in the sub-polar overturning. In contrast, the different estimates of sub-tropical variability are poorly correlated with each other, and only a subset of them capture a significant fraction of the variability in independently estimated North Atlantic Sub-Tropical Mode Water volume.

  13. Improving North American gross primary production (GPP) estimates using atmospheric measurements of carbonyl sulfide (COS)

    NASA Astrophysics Data System (ADS)

    Chen, Huilin; Montzka, Steve; Andrews, Arlyn; Sweeney, Colm; Jacobson, Andy; Miller, Ben; Masarie, Ken; Jung, Martin; Gerbig, Christoph; Campbell, Elliott; Abu-Naser, Mohammad; Berry, Joe; Baker, Ian; Tans, Pieter

    2013-04-01

    Understanding the responses of gross primary production (GPP) to climate change is essential for improving our prediction of climate change. To this end, it is important to accurately partition net ecosystem exchange of carbon into GPP and respiration. Recent studies suggest that carbonyl sulfide is a useful tracer to provide a constraint on GPP, based on the fact that both COS and CO2 are simultaneously taken up by plants and the quantitative correlation between GPP and COS plant uptake. We will present an assessment of North American GPP estimates from the Simple Biosphere (SiB) model, the Carnegie-Ames-Stanford Approach (CASA) model, and the MPI-BGC model through atmospheric transport simulations of COS in a receptor oriented framework. The newly upgraded Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT) will be employed to compute the influence functions, i.e. footprints, to link the surface fluxes to the concentration changes at the receptor observations. The HYSPLIT is driven by the 3-hourly archived NAM 12km meteorological data from NOAA NCEP. The background concentrations are calculated using empirical curtains along the west coast of North America that have been created by interpolating in time and space the observations at the NOAA/ESRL marine boundary layer stations and from aircraft vertical profiles. The plant uptake of COS is derived from GPP estimates of biospheric models. The soil uptake and anthropogenic emissions are from Kettle et al. 2002. In addition, we have developed a new soil flux map of COS based on observations of molecular hydrogen (H2), which shares a common soil uptake term but lacks a vegetative sink. We will also improve the GPP estimates by assimilating atmospheric observations of COS in the receptor oriented framework, and then present the assessment of the improved GPP estimates against variations of climate variables such as temperature and precipitation.

  14. A comparison of state-level estimation techniques for utility atmospheric emission factors

    SciTech Connect

    Schrock, D.; Baechler, M.

    1995-10-01

    Atmospheric emission factors provide a link between the electricity saved in buildings and the associated decrease in fossil fuel use in the electric supply sector. Understanding this link is important to meet the requirements of Section 1605(b) of the Energy Policy act of 1992, which established the voluntary program for reporting reductions in greenhouse gases. As part of the development process for Section 1605(b), several national workshops were held by the US Department of Energy (DOE) and the Energy Information Administration (EIA). Workshop participants expressed the need for DOE to supply default atmospheric emission facets. Based upon the response from the workshop participants, it was decided that emission factors would be aggregated to the state level (e.g., California, Connecticut, etc.). Emission factors for electricity generation are generally quantified as a quantity of impact to an amount of fuel used to produce the emission. In the electric supply sector, factors are often expressed in units of pounds or tons of emission per megawatt-hours (MWh) of electricity produced. In this paper, the authors examine and compare the estimates from three methodologies for developing state-level emission facets. In addition, they compare the results to those obtained using emissions data calculated by the EIA. Although the examples presented in this paper depict the development of state-level factors, the same methodologies can be applied by an individual utility to generate utility-specific atmospheric emission factors.

  15. Estimation of atmospheric sea salt dry deposition: Wind speed and particle size dependence

    NASA Astrophysics Data System (ADS)

    McDonald, R. L.; Unni, C. K.; Duce, R. A.

    1982-02-01

    Cascade impactor and bulk filter samples of atmospheric sea salt were collected at wind speeds from 3.4 to 10 m/s at coastal tower sites in the Florida Keys and Enewetak Atoll as part of the SEAREX (Sea Air Exchange) Program. Simultaneous dry deposition measurements were made to polyethylene plates. The samples were analyzed for Na as an indicator of sea salt. If the observed atmospheric sea salt particle mass distributions are corrected for the reduced collection efficiency of large particles, the observed dry deposition rates agree well with rates estimated from atmospheric sea salt particle concentrations and theoretical particle deposition velocities derived from gravitational settling velocities or from the equations of Slinn and Slinn (1980, 1981) for deposition to smooth, solid surfaces as well as natural water surfaces. The results emphasize the fact that even though large particles may represent only a small fraction of the total mass of sea salt over the ocean, they can dominate the dry deposition rates of the sea salt aerosol.

  16. Spaceborne estimate of atmospheric CO2 column by use of the differential absorption method: error analysis.

    PubMed

    Dufour, Emmanuel; Bréon, François-Marie

    2003-06-20

    For better knowledge of the carbon cycle, there is a need for spaceborne measurements of atmospheric CO2 concentration. Because the gradients are relatively small, the accuracy requirements are better than 1%. We analyze the feasibility of a CO2-weighted-column estimate, using the differential absorption technique, from high-resolution spectroscopic measurements in the 1.6- and 2-microm CO2 absorption bands. Several sources of uncertainty that can be neglected for other gases with less stringent accuracy requirements need to be assessed. We attempt a quantification of errors due to the radiometric noise, uncertainties in the temperature, humidity and surface pressure uncertainty, spectroscopic coefficients, and atmospheric scattering. Atmospheric scattering is the major source of error [5 parts per 10 (ppm) for a subvisual cirrus cloud with an assumed optical thickness of 0.03], and additional research is needed to properly assess the accuracy of correction methods. Spectroscopic data are currently a major source of uncertainty but can be improved with specific ground-based sunphotometry measurements. The other sources of error amount to several ppm, which is less than, but close to, the accuracy requirements. Fortunately, these errors are mostly random and will therefore be reduced by proper averaging.

  17. Inconsistencies in sea level pressure trends between different atmospheric products. Impact on sea level trend estimation

    NASA Astrophysics Data System (ADS)

    Gomis, D.; Jordà, G.

    2012-04-01

    Long term climate datasets are of great importance to understand the processes behind climate variability, to evaluate the performance of climate models and to identify signals of climate change. Among the different atmospheric variables, sea level pressure (SLP) is the basic dynamical variable and is the most widely analyzed quantity. From the ocean perspective, SLP is of crucial importance for a dynamical interpretation of sea level records. In order to isolate the contribution to sea level variability of circulation and heat and freshwater contents, a common practice is to remove the sea level fluctuations induced by SLP. At seasonal and longer time scales, sea level is expected to react as an inverted barometer (IB) to changes in SLP. Therefore, provided that accuracy of available SLP data is high enough, the atmospheric contribution to sea level variability can be isolated and removed from sea level records. This is routinely done for tide gauge records, altimetry or sea level reconstructions. Different atmospheric gridded products spanning the last decades are nowadays available. On the one hand, there are historical SLP datasets where observations from land stations and ocean observations have been interpolated into a regular grid. On the other hand, there are reanalyses where an atmospheric model is run assimilating the historical data. Both kind of products have been extensively used in recent years either directly (i.e. to analyse the SLP evolution) or indirectly (i.e. through the removal of IB effect on sea level records). However, it is well known that the quality of those products may not be homogeneous on time. In this contribution, we compare long term SLP trends from different atmospheric products (reanalysis and gridded historical datasets), and evaluate the uncertainties introduced by them in the sea level trend estimations. The results show that discrepancies between datasets can induce an uncertainty up to 0.5 mm/yr for the period 1958-2001 on

  18. 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.

  19. 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.

  20. Sea ice-atmosphere interaction. Application of multispectral satellite data in polar surface energy flux estimates

    NASA Technical Reports Server (NTRS)

    Steffen, Konrad; Key, Jeff; Maslanik, Jim; Haefliger, Marcel; Fowler, Chuck

    1992-01-01

    Satellite data for the estimation of radiative and turbulent heat fluxes is becoming an increasingly important tool in large-scale studies of climate. One parameter needed in the estimation of these fluxes is surface temperature. To our knowledge, little effort has been directed to the retrieval of the sea ice surface temperature (IST) in the Arctic, an area where the first effects of a changing climate are expected to be seen. The reason is not one of methodology, but rather our limited knowledge of atmospheric temperature, humidity, and aerosol profiles, the microphysical properties of polar clouds, and the spectral characteristics of the wide variety of surface types found there. We have developed a means to correct for the atmospheric attenuation of satellite-measured clear sky brightness temperatures used in the retrieval of ice surface temperature from the split-window thermal channels of the advanced very high resolution radiometer (AVHRR) sensors on-board three of the NOAA series satellites. These corrections are specified for three different 'seasons' and as a function of satellite viewing angle, and are expected to be applicable to the perennial ice pack in the central Arctic Basin.

  1. An adaptive Bayesian inference algorithm to estimate the parameters of a hazardous atmospheric release

    NASA Astrophysics Data System (ADS)

    Rajaona, Harizo; Septier, François; Armand, Patrick; Delignon, Yves; Olry, Christophe; Albergel, Armand; Moussafir, Jacques

    2015-12-01

    In the eventuality of an accidental or intentional atmospheric release, the reconstruction of the source term using measurements from a set of sensors is an important and challenging inverse problem. A rapid and accurate estimation of the source allows faster and more efficient action for first-response teams, in addition to providing better damage assessment. This paper presents a Bayesian probabilistic approach to estimate the location and the temporal emission profile of a pointwise source. The release rate is evaluated analytically by using a Gaussian assumption on its prior distribution, and is enhanced with a positivity constraint to improve the estimation. The source location is obtained by the means of an advanced iterative Monte-Carlo technique called Adaptive Multiple Importance Sampling (AMIS), which uses a recycling process at each iteration to accelerate its convergence. The proposed methodology is tested using synthetic and real concentration data in the framework of the Fusion Field Trials 2007 (FFT-07) experiment. The quality of the obtained results is comparable to those coming from the Markov Chain Monte Carlo (MCMC) algorithm, a popular Bayesian method used for source estimation. Moreover, the adaptive processing of the AMIS provides a better sampling efficiency by reusing all the generated samples.

  2. Military Participants at U.S. Atmospheric Nuclear Weapons Testing— Methodology for Estimating Dose and Uncertainty

    PubMed Central

    Till, John E.; Beck, Harold L.; Aanenson, Jill W.; Grogan, Helen A.; Mohler, H. Justin; Mohler, S. Shawn; Voillequé, Paul G.

    2014-01-01

    Methods were developed to calculate individual estimates of exposure and dose with associated uncertainties for a sub-cohort (1,857) of 115,329 military veterans who participated in at least one of seven series of atmospheric nuclear weapons tests or the TRINITY shot carried out by the United States. The tests were conducted at the Pacific Proving Grounds and the Nevada Test Site. Dose estimates to specific organs will be used in an epidemiological study to investigate leukemia and male breast cancer. Previous doses had been estimated for the purpose of compensation and were generally high-sided to favor the veteran's claim for compensation in accordance with public law. Recent efforts by the U.S. Department of Defense (DOD) to digitize the historical records supporting the veterans’ compensation assessments make it possible to calculate doses and associated uncertainties. Our approach builds upon available film badge dosimetry and other measurement data recorded at the time of the tests and incorporates detailed scenarios of exposure for each veteran based on personal, unit, and other available historical records. Film badge results were available for approximately 25% of the individuals, and these results assisted greatly in reconstructing doses to unbadged persons and in developing distributions of dose among military units. This article presents the methodology developed to estimate doses for selected cancer cases and a 1% random sample of the total cohort of veterans under study. PMID:24758578

  3. Sulfur compounds in coal

    NASA Technical Reports Server (NTRS)

    Attar, A.; Corcoran, W. H.

    1977-01-01

    The literature on the chemical structure of the organic sulfur compounds (or functional groups) in coal is reviewed. Four methods were applied in the literature to study the sulfur compounds in coal: direct spectrometric and chemical analysis, depolymerization in drastic conditions, depolymerization in mild conditions, and studies on simulated coal. The data suggest that most of the organic sulfur in coal is in the form of thiophenic structures and aromatic and aliphatic sulfides. The relative abundance of the sulfur groups in bituminous coal is estimated as 50:30:20%, respectively. The ratio changes during processing and during the chemical analysis. The main effects are the transformation during processing of sulfides to the more stable thiophenic compounds and the elimination of hydrogen sulfide.

  4. Sulfur compounds in coal

    NASA Technical Reports Server (NTRS)

    Attar, A.; Corcoran, W. H.

    1977-01-01

    The literature on the chemical structure of the organic sulfur compounds (or functional groups) in coal is reviewed. Four methods were applied in the literature to study the sulfur compounds in coal: direct spectrometric and chemical analysis, depolymerization in drastic conditions, depolymerization in mild conditions, and studies on simulated coal. The data suggest that most of the organic sulfur in coal is in the form of thiophenic structures and aromatic and aliphatic sulfides. The relative abundance of the sulfur groups in bituminous coal is estimated as 50:30:20%, respectively. The ratio changes during processing and during the chemical analysis. The main effects are the transformation during processing of sulfides to the more stable thiophenic compounds and the elimination of hydrogen sulfide.

  5. A sparse reconstruction method for the estimation of multiresolution emission fields via atmospheric inversion

    DOE PAGES

    Ray, J.; Lee, J.; Yadav, V.; ...

    2014-08-20

    We present a sparse reconstruction scheme that can also be used to ensure non-negativity when fitting wavelet-based random field models to limited observations in non-rectangular geometries. The method is relevant when multiresolution fields are estimated using linear inverse problems. Examples include the estimation of emission fields for many anthropogenic pollutants using atmospheric inversion or hydraulic conductivity in aquifers from flow measurements. The scheme is based on three new developments. Firstly, we extend an existing sparse reconstruction method, Stagewise Orthogonal Matching Pursuit (StOMP), to incorporate prior information on the target field. Secondly, we develop an iterative method that uses StOMP tomore » impose non-negativity on the estimated field. Finally, we devise a method, based on compressive sensing, to limit the estimated field within an irregularly shaped domain. We demonstrate the method on the estimation of fossil-fuel CO2 (ffCO2) emissions in the lower 48 states of the US. The application uses a recently developed multiresolution random field model and synthetic observations of ffCO2 concentrations from a limited set of measurement sites. We find that our method for limiting the estimated field within an irregularly shaped region is about a factor of 10 faster than conventional approaches. It also reduces the overall computational cost by a factor of two. Further, the sparse reconstruction scheme imposes non-negativity without introducing strong nonlinearities, such as those introduced by employing log-transformed fields, and thus reaps the benefits of simplicity and computational speed that are characteristic of linear inverse problems.« less

  6. Estimating Terrestrial Wood Biomass from Observed Concentrations of Atmospheric Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Schaefer, K. M.; Peters, W.; Carvalhais, N.; van der Werf, G.; Miller, J.

    2008-12-01

    We estimate terrestrial disequilibrium state and wood biomass from observed concentrations of atmospheric CO2 using the CarbonTracker system coupled to the SiBCASA biophysical model. Starting with a priori estimates of carbon flux from the land, ocean, and fossil fuels, CarbonTracker estimates net carbon sources and sinks from 2000 to 2007 that are optimally consistent with observed CO2 concentrations. The a priori terrestrial Net Primary Productivity (NPP) and heterotrophic respiration (Rh) from SiBCASA assume steady state conditions for initial biomass, implying mature ecosystems with no disturbances where growth balances decay and the long-term, net carbon flux is zero. In reality, harvest, fires, and other disturbances reduce available biomass for decay, thus reducing Rh and resulting in a long-term carbon sink. The disequilibrium state is the ratio of Rh estimated from CarbonTracker to the steady state Rh from SiBCASA. Wood is the largest carbon pool in forest ecosystems and the dominant source of dead organic matter to the soil and litter pools. With much faster turnover times, the soil and litter pools reach equilibrium relative to the wood pool long before the wood pool itself reaches equilibrium. We take advantage of this quasi-steady state to estimate the size of the wood pool that will produce an Rh that corresponds to the net carbon sink from CarbonTracker. We then compare this estimated wood biomass to regional maps of observed above ground wood biomass from the US Forest Inventory Analysis.

  7. Uncertainty of Coupled Soil-Vegetation-Atmosphere Modelling Methods for Estimating Groundwater Recharge

    NASA Astrophysics Data System (ADS)

    Xie, Y.; Cook, P. G.; Simmons, C. T.; Partington, D.; Crosbie, R.; Batelaan, O.

    2016-12-01

    Coupled soil-vegetation-atmosphere models have become increasingly popular for estimating groundwater recharge, because of the integration of carbon, energy and water balances. The carbon and energy balances act to constrain the water balance and as a result should reduce the uncertainty of groundwater recharge estimates. However, the addition of carbon and energy balances also introduces a large number of plant physiological parameters which complicates the estimation of groundwater recharge. Moreover, this method often relies on existing pedotransfer functions to derive soil water retention curve parameters and saturated hydraulic conductivity from soil attribute data. The choice of a pedotransfer function is usually subjective and several pedotransfer functions may be fit for the purpose. These different pedotransfer functions (and thus the uncertainty of soil water retention curve parameters and saturated hydraulic conductivity) are likely to increase the prediction uncertainty of recharge estimates. In this study, we aim to assess the potential uncertainty of groundwater recharge when using a coupled soil-vegetation-atmosphere modelling method. The widely used WAter Vegetation Energy and Solute (WAVES) modelling code was used to perform simulations of different water balances in order to estimate groundwater recharge in the Campaspe catchment in southeast Australia. We carefully determined the ranges of the vegetation parameters based upon a literature review. We also assessed a number of existing pedotransfer functions and selected the four most appropriate. Then the Monte Carlo analysis approach was employed to examine potential uncertainties introduced by different types of errors. Preliminary results suggest that for a mean rainfall of about 500 mm/y and annual pasture vegetation, the estimated recharge may range from 10 to 150 mm/y due to the uncertainty in vegetation parameters. This upper bound of the recharge range may double to 300 mm/y if different

  8. 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...

  9. Estimation of organophosphoric acid triesters in soft polyurethane foam using a concentrated sulfuric acid dissolution technique and gas chromatography with flame photometric detection.

    PubMed

    Nagase, Makoto; Toba, Mineki; Kondo, Hiroyuki; Yasuhara, Akio; Hasebe, Kiyoshi

    2003-12-01

    A concentrated sulfuric acid dissolution technique and a GC method are described for the estimation of tributyl phosphate, tris(2-chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, triphenyl phosphate and tris(butoxyethyl) phosphate in soft polyurethane foam. A soft polyurethane foam sample containing organophosphoric acid triesters was dissolved in concentrated sulfuric acid. The solution was added to water, where only the polyurethane was separated out. The pH of the solution was adjusted, and organophosphoric acid triesters were extracted with toluene. After purification, the compounds were determined by GC. The detection limits of the organophosphoric acid triesters were 0.3 - 0.9 microg g(-1). The recoveries of the organophosphoric acid triesters from a 0.05 g sample of soft polyurethane foam were 80.0 - 90.0%, when the spiked amounts were 0.25 - 1 microg. The compounds were detected from soft polyurethane foam at the level of 0.4 - 23.3 microg g(-1).

  10. Estimate of Top-of-Atmosphere Albedo for a Molecular Atmosphere over Ocean using Clouds and the Earth's Radiant Energy System (CERES) Measurements

    NASA Technical Reports Server (NTRS)

    Kato, S.; Loeb, N. G.; Rutledge, C. K.

    2002-01-01

    The shortwave broadband albedo at the top of a molecular atmosphere over ocean between 40deg N and 40deg S is estimated using radiance measurements from the Clouds and the Earth's Radiant Energy System (CERES) instrument and the Visible Infrared Scanner (VIRS) aboard the Tropical Rainfall Measuring Mission (TRMM) satellite. The albedo monotonically increases from 0.059 at a solar zenith angle of 10deg to 0.107 at a solar zenith angle of 60deg. The estimated uncertainty in the albedo is 3.5 x 10(exp -3) caused by the uncertainty in CERES-derived irradiances, uncertainty in VIRS-derived aerosol optical thicknesses, variations in ozone and water vapor, and variations in surface wind speed. The estimated uncertainty is similar in magnitude to the standard deviation of 0.003 that is derived from 72 areas divided by 20deg latitude by 20deg longitude grid boxes. The empirically estimated albedo is compared with the modeled albedo using a radiative transfer model combined with an ocean surface bidirectional reflectivity model. The modeled albedo with standard tropical atmosphere is 0.061 and 0.111 at the solar zenith angles of 10deg and 60deg, respectively. This empirically estimated albedo can be used to estimate the direct radiative effect of aerosols at the top of the atmosphere over oceans.

  11. Estimate of Top-of-Atmosphere Albedo for a Molecular Atmosphere over Ocean using Clouds and the Earth's Radiant Energy System (CERES) Measurements

    NASA Technical Reports Server (NTRS)

    Kato, S.; Loeb, N. G.; Rutledge, C. K.

    2002-01-01

    The shortwave broadband albedo at the top of a molecular atmosphere over ocean between 40deg N and 40deg S is estimated using radiance measurements from the Clouds and the Earth's Radiant Energy System (CERES) instrument and the Visible Infrared Scanner (VIRS) aboard the Tropical Rainfall Measuring Mission (TRMM) satellite. The albedo monoton