Estimating historical anthropogenic global sulfur emission patterns for the period 1850-1990

NASA Astrophysics Data System (ADS)

Lefohn, Allen S.; Husar, Janja D.; Husar, Rudolf B.

It is important to establish a reliable regional emission inventory of sulfur as a function of time when assessing the possible effects of global change and acid rain. This study developed a database of annual estimates of national sulfur emissions from 1850 to 1990. A common methodology was applied across all years and countries allowing for global totals to be produced by adding estimates from all countries. The consistent approach facilitates the modification of the database and the observation of changes at national, regional, or global levels. The emission estimates were based on net production (i.e., production plus imports minus exports), sulfur content, and sulfur retention for each country's production activities. Because the emission estimates were based on the above considerations, our database offers an opportunity to independently compare our results with those estimates based on individual country estimates. Fine temporal resolution clearly shows emission changes associated with specific historical events (e.g., wars, depressions, etc.) on a regional, national, or global basis. The spatial pattern of emissions shows that the US, the USSR, and China were the main sulfur emitters (i.e., approximately 50% of the total) in the world in 1990. The USSR and the US appear to have stabilized their sulfur emissions over the past 20 yr, and the recent increases in global sulfur emissions are linked to the rapid increases in emissions from China. Sulfur emissions have been reduced in some cases by switching from high- to low-sulfur coals. Flue gas desulfurization (FGD) has apparently made important contributions to emission reductions in only a few countries, such as Germany.

Transition metal-catalyzed oxidation of sulfur(IV) oxides. Atmospheric-relevant processes and mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brandt, C.; Eldik, R. van

1995-01-01

The transition metal-catalyzed oxidation of sulfur(IV) oxides has been known for more than 100 years. There is a significant lack of information on the actual role of the transition metal-catalyzed reactions, and much of the earlier work was performed without a detailed knowledge of the chemical system. For this reason attention is focused on the role of transition metal ions in the oxidation of sulfur(IV) oxides in terms of the coordination chemistry involved, as well as the stability and chemical behavior of the various participating species. The oxidation process of sulfur(IV) oxides plays an important role in atmospheric chemistry (e.g.more » acid rain formation) as well as industrial processes (e.g. desulfurization of plume gases and ore). The present report deals with the mechanism of the transition metal-catalyzed oxidation of sulfur(IV) oxides with the aim to discuss this in terms of atmospheric and chemical processes. In addition, the authors would like to emphasize the key role of oxygen in these processes. 1,076 refs.« less

Sulfur, chlorine, and fluorine degassing and atmospheric loading by the 1783 1784 AD Laki (Skaftár Fires) eruption in Iceland

NASA Astrophysics Data System (ADS)

Thordarson, T.; Self, S.; Óskarsson, N.; Hulsebosch, T.

1996-09-01

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 ˜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 (˜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 ˜7.0 and 15.0 Mt, respectively. Furthermore, ˜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 confined to the lowest regions of the

Estimation of In-canopy Flux Distributions of Reactive Nitrogen and Sulfur within a Mixed Hardwood Forest in Southern Appalachia

NASA Astrophysics Data System (ADS)

Wu, Z.; Walker, J. T.; Chen, X.; Oishi, A. C.; Duman, T.

2017-12-01

Estimating the source/sink distribution and vertical fluxes of air pollutants within and above forested canopies is critical for understanding biological, physical, and chemical processes influencing the soil-vegetation-atmosphere exchange. The vertical source-sink profiles of reactive nitrogen and sulfur were examined using multiple inverse modeling methods in a mixed hardwood forest in the southern Appalachian Mountains where the ecosystem is highly sensitive to loads of pollutant from atmospheric depositions. Measurements of the vertical concentration profiles of ammonia (NH3), nitric acid (HNO3), sulfur dioxide (SO2), and ammonium (NH4+), nitrate (NO3-), and sulfate (SO42-) in PM2.5 were measured during five study periods between May 2015 and August 2016. The mean concentration of NH3 decreased with height in the upper canopy and increased below the understory toward the forest floor, indicating that the canopy was a sink for NH3 but the forest floor was a source. All other species exhibited patterns of monotonically decreasing concentration from above the canopy to the forest floor. Using the measured concentration profiles, we simulated the within-canopy flow fields and estimated the vertical source-sink flux profiles using three inverse approaches: a Eulerian high-order closure model (EUL), a Lagrangian localized near-field (LNF) model, and a new full Lagrangian stochastic model (LSM). The models were evaluated using the within- and above-canopy eddy covariance flux measurements of heat, CO2 and H2O. Differences between models were analyzed and the flux profiles were used to investigate the origin and fate of reactive nitrogen and sulfur compounds within the canopy. The knowledge gained in this study will benefit the development of soil-vegetation-atmosphere models capable of partitioning canopy-scale deposition of nitrogen and sulfur to specific ecosystem compartments.

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.

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...

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

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).

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

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

PubMed

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

2014-08-19

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 (Δ(33)S = +1.66‰ and Δ(36)S = +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 (Δ(36)S = -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.

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.

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.

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;…

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.

Probability model for atmospheric sulfur dioxide concentrations in the area of Venice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buttazzoni, C.; Lavagnini, I.; Marani, A.

1986-09-01

This paper deals with a comparative screening of existing air quality models based on their ability to simulate the distribution of sulfur dioxide data in the Venetian area. Investigations have been carried out on sulfur dioxide dispersion in the atmosphere of the Venetian area. The studies have been mainly focused on transport models (Gaussian, plume and K-models) aiming at meaningful correlations of sources and receptors. Among the results, a noteworthy disagreement of simulated and experimental data, due to the lack of thorough knowledge of source field conditions and of local meteorology of the sea-land transition area, has been shown. Investigationsmore » with receptor oriented models (based, e.g., on time series analysis, Fourier analysis, or statistical distributions) have also been performed.« less

Decoding mass-independent fractionation of sulfur isotopes in modern atmosphere using cosmogenic 35S: A five-isotope approach and possible implications for Archean sulfur isotope records

NASA Astrophysics Data System (ADS)

Lin, M.; Thiemens, M. H.; Shen, Y.; Zhang, X.; Huang, X.; Chen, K.; Zhang, Z.; Tao, J.

2017-12-01

The signature of sulfur isotopic mass-independent fractionation (S-MIF) observed in Archean sediments have been interpreted as a proxy of the origins and evolution of atmospheric oxygen and early life on Earth [1]. Photochemistry of SOx in the short (< 290 nm) wavelength region accounts for much of the Archean record, but the S-MIF widely observed in modern tropospheric sulfate aerosols remains unexplained, indicating embedded uncertainties in interpreting Archean S-MIF records [2]. Here we present combined measurements of cosmogenic 35S (a stratospheric tracer) [3] and all four stable sulfur isotopes in the same modern atmospheric sulfate samples to define the mechanisms. The five-sulfur-isotope approach reveals that an altitude-dependent process (probably SOx photochemistry) mainly contributes to a positive Δ33S and a combustion-related process mainly leads to a negative Δ36S. After eliminating combustion impacts, the obtained Δ36S/Δ33S slope of -4.0 in the modern atmosphere is close to the Δ36S/Δ33S slope (-3.6) in some records from Paleoarchean [4], an era probably with active volcanism [5]. The significant role of volcanic OCS in the Archean atmosphere has been called for in terms of its ability to provide a continual SO2 high altitude source for photolysis [2]. The strong but previously underappreciated stratospheric signature of S-MIF in tropospheric sulfates suggests that a more careful investigation of wavelength-dependent sulfur isotopic fractionation at different altitudes are required. The combustion-induced negative Δ36S may be linked to recombination reactions of elemental sulfur [6], and relevant experiments are being conducted to test the isotope effect. Although combustion is unlikely in Archean, recombination reactions may occur in other previously unappreciated processes such as volcanism and may contribute in part to the heavily depleted 36S in some Paleoarchean records [5,7]. The roles of both photochemical and non

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.

Biogenesis of Mercury-Sulfur Nanoparticles in Plant Leaves from Atmospheric Gaseous Mercury.

PubMed

Manceau, Alain; Wang, Jianxu; Rovezzi, Mauro; Glatzel, Pieter; Feng, Xinbin

2018-04-03

Plant leaves serve both as a sink for gaseous elemental mercury (Hg) from the atmosphere and a source of toxic mercury to terrestrial ecosystems. Litterfall is the primary deposition pathway of atmospheric Hg to vegetated soils, yet the chemical form of this major Hg input remains elusive. We report the first observation of in vivo formation of mercury sulfur nanoparticles in intact leaves of 22 native plants from six different species across two sampling areas from China. The plants grew naturally in soils from a mercury sulfide mining and retorting region at ambient-air gaseous-Hg concentrations ranging from 131 ± 19 to 636 ± 186 ng m -3 and had foliar Hg concentration between 1.9 and 31.1 ng Hg mg -1 dry weight (ppm). High energy resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy shows that up to 57% of the acquired Hg is nanoparticulate, and the remainder speciated as a bis-thiolate complex (Hg(SR) 2 ). The fractional amount of nanoparticulate Hg is not correlated with Hg concentration. Variation likely depends on leaf age, plant physiology, and natural variability. Nanoparticulate Hg atoms are bonded to four sulfide or thiolate sulfur atoms arranged in a metacinnabar-type (β-HgS) coordination environment. The nanometer dimension of the mercury-sulfur clusters outmatches the known binding capacity of plant metalloproteins. These findings give rise to challenging questions on their exact nature, how they form, and their biogeochemical reactivity and fate in litterfall, whether this mercury pool is recycled or stored in soils. This study provides new evidence that metacinnabar-type nanoparticles are widespread in oxygenated environments.

Photochemical Formation of Sulfur-Containing Aerosols

NASA Astrophysics Data System (ADS)

Kroll, Jay A.; Vaida, Veronica

2017-06-01

In order to understand planetary climate systems, modeling the properties of atmospheric aerosols is vital. Aerosol formation plays an important role in planetary climates and is tied to feedback loops that can either warm or cool a planet. Sulfur compounds are known to play an important role in new particle aerosol formation and have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere; however, several discrepancies arise when comparing observations of the Venusian atmosphere with model predictions. This suggests that there are still problems in our fundamental understanding of sulfur chemistry. This is concerning given recent renewed interest in sulfate injections in the stratosphere for solar radiation management geo-engineering schemes. We investigate the role of sunlight as a potential driver of the formation of sulfur-containing aerosols. I will present recent work investigating the generation of large quantities of aerosol from the irradiation of mixtures of SO_2 with water and organic species, using a solar simulator that mimics the light that is available in the Earth's troposphere and the Venusian middle atmosphere. I will present on recent work done in our lab suggesting the formation of sulfurous acid, H_2SO_3, and describe experimental work that supports this proposed mechanism. Additionally I will present on new work showing the highly reactive nature of electronically excited SO_2 with saturated alkane species. The implications of this photochemically induced sulfur aerosol formation in the atmosphere of Earth and other planetary atmospheres will be discussed.

Photochemistry of a Volcanically Driven Atmosphere on Io: Sulfur and Oxygen Species from a Pele-Type Eruption

NASA Astrophysics Data System (ADS)

Moses, Julianne I.; Zolotov, Mikhail Yu.; Fegley, Bruce

2002-03-01

To determine how active volcanism might affect the standard picture of sulfur dioxide photochemistry on Io, we have developed a one-dimensional atmospheric model in which a variety of sulfur-, oxygen-, sodium-, potassium-, and chlorine-bearing volatiles are volcanically outgassed at Io's surface and then evolve due to photolysis, chemical kinetics, and diffusion. Thermochemical equilibrium calculations in combination with recent observations of gases in the Pele plume are used to help constrain the composition and physical properties of the exsolved volcanic vapors. Both thermochemical equilibrium calculations (Zolotov and Fegley 1999, Icarus141, 40-52) and the Pele plume observations of Spencer et al. (2000; Science288, 1208-1210) suggest that S 2 may be a common gas emitted in volcanic eruptions on Io. If so, our photochemical models indicate that the composition of Io's atmosphere could differ significantly from the case of an atmosphere in equilibrium with SO 2 frost. The major differences as they relate to oxygen and sulfur species are an increased abundance of S, S 2, S 3, S 4, SO, and S 2O and a decreased abundance of O and O 2 in the Pele-type volcanic models as compared with frost sublimation models. The high observed SO/SO 2 ratio on Io might reflect the importance of a contribution from volcanic SO rather than indicate low eddy diffusion coefficients in Io's atmosphere or low SO "sticking" probabilities at Io's surface; in that case, the SO/SO 2 ratio could be temporally and/or spatially variable as volcanic activity fluctuates. Many of the interesting volcanic species (e.g., S 2, S 3, S 4, and S 2O) are short lived and will be rapidly destroyed once the volcanic plumes shut off; condensation of these species near the source vent is also likely. The diffuse red deposits associated with active volcanic centers on Io may be caused by S 4 radicals that are created and temporarily preserved when sulfur vapor (predominantly S 2) condenses around the volcanic

Biological cycling of atmospheric trace gases

NASA Technical Reports Server (NTRS)

Hitchcock, D. R.; Wechsler, A. E.

1972-01-01

A detailed critical review was conducted of present knowledge of the influence of biological processes on the cycling of selected atmospheric gas constituents--methane, carbon monoxide, and gaseous compounds of nitrogen (nitrous oxide, ammonia, nitric oxide, and nitrogen dioxide) and sulfur (hydrogen sulfide and sulfur dioxide). The identification was included of biological and other sources of each gas, a survey of abundance measurements reported in the literature, and a review of the atmospheric fate of each contituent. Information is provided on which to base conclusions regarding the importance of biological processes on the atmospheric distribution and surface-atmosphere exchange of each constituent, and a basis for estimating the adequacy of present knowledge of these factors. A preliminary analysis was conducted of the feasibility of monitoring the biologically influenced temporal and spatial variations in abundance of these gases in the atmosphere from satellites.

Dimethyl sulfide in the surface ocean and the marine atmosphere: a global view.

PubMed

Andreae, M O; Raemdonck, H

1983-08-19

Dimethyl sulfide (DMS) has been identified as the major volatile sulfur compound in 628 samples of surface seawater representing most of the major oceanic ecozones. In at least three respects, its vertical distribution, its local patchiness, and its distribution in oceanic ecozones, the concentration of DMS in the sea exhibits a pattern similar to that of primary production. The global weightedaverage concentration of DMS in surface seawater is 102 nanograms of sulfur (DMS) per liter, corresponding to a global sea-to-air flux of 39 x 10(12) grams of sulfur per year. When the biogenic sulfur contributions from the land surface are added, the biogenic sulfur gas flux is approximately equal to the anthropogenic flux of sulfur dioxide. The DMS concentration in air over the equatorial Pacific varies diurnally between 120 and 200 nanograms of sulfur (DMS) per cubic meter, in agreement with the predictions of photochemical models. The estimated source flux of DMS from the oceans to the marine atmosphere is in agreement with independently obtained estimates of the removal fluxes of DMS and its oxidation products from the atmosphere.

Dimethyl Sulfide in the Surface Ocean and the Marine Atmosphere: A Global View

NASA Astrophysics Data System (ADS)

Andreae, Meinrat O.; Raemdonck, Hans

1983-08-01

Dimethyl sulfide (DMS) has been identified as the major volatile sulfur compound in 628 samples of surface seawater representing most of the major oceanic ecozones. In at least three respects, its vertical distribution, its local patchiness, and its distribution in oceanic ecozones, the concentration of DMS in the sea exhibits a pattern similar to that of primary production. The global weighted-average concentration of DMS in surface seawater is 102 nanograms of sulfur (DMS) per liter, corresponding to a global sea-to-air flux of 39 × 1012 grams of sulfur per year. When the biogenic sulfur contributions from the land surface are added, the biogenic sulfur gas flux is approximately equal to the anthropogenic flux of sulfur dioxide. The DMS concentration in air over the equatorial Pacific varies diurnally between 120 and 200 nanograms of sulfur (DMS) per cubic meter, in agreement with the predictions of photochemical models. The estimated source flux of DMS from the oceans to the marine atmosphere is in agreement with independently obtained estimates of the removal fluxes of DMS and its oxidation products from the atmosphere.

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.

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...

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.

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

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

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.

Sulfur dioxide emissions and sectorial contributions to sulfur deposition in Asia

NASA Astrophysics Data System (ADS)

Arndt, Richard L.; Carmichael, Gregory R.; Streets, David G.; Bhatti, Neeloo

Anthropogenic and volcanic emissions of SO 2 in Asia for 1987-1988 are estimated on a 1° × 1° grid. Anthropogenic sources are estimated to be 31.6 Tg of SO 2 with the regions' volcanoes emitting an additional 3.8 Tg. For Southeast Asia and the Indian sub-continent, the emissions are further partitioned into biomass, industrial, utilities, and non-specific sources. In these regions emissions from biomass, utilities and industrial sources account for 16.7, 21.7, and 12.2%, respectively. In Bangladesh, ˜ 90% of the SO 2 emissions result from biomass burning and nearly 20% of India's 5 Tg of SO 2 emissions are due to biomass burning. Malaysia and Singapore's emissions are dominated by the utilities with 42 and 62% of their respective emissions coming from that sector. The spatial distribution of sulfur deposition resulting from these emissions is calculated using an atmospheric transport and deposition model. Sulfur deposition in excess of 2 g m -2 yr -1 is predicted in vast regions of east Asia, India, Thailand, Malaysia, Taiwan, and Indonesia with deposition in excess of 5 g m -2 yr -1 predicted in southern China. For the Indian sub-continent and Southeast Asia the contribution of biomass burning, industrial activities, and utilities to total sulfur emissions and deposition patterns are evaluated. Biomass burning is found to be a major source of sulfur deposition throughout southeast Asia. Deposition in Bangladesh and northern India is dominated by this emissions sector. Deposition in Thailand, the Malay Peninsula and the island of Sumatra is heavily influenced by emissions from utilities. The ecological impact of the deposition, in 1988 and in the year 2020, is also estimated using critical loads data developed in the RAINS-ASIA projects. Much of eastern China, the Korean Peninsula, Japan, Thailand, and large regions of India, Nepal, Bangladesh, Taiwan, the Philippines, Malaysia, Indonesia, and sections of Vietnam are at risk due to deposition in excess of their

The weathering of organic carbon and pyrite sulfur in Earth's crust and its importance for regulating atmospheric composition, seawater chemistry, and stable isotope records

NASA Astrophysics Data System (ADS)

Reinhard, C. T.; Planavsky, N.; Bolton, E. W.

2016-12-01

Earth's crust stores extremely large reservoirs of organic carbon and pyrite sulfur, and transient or secular changes in the sizes of these reservoirs have the capacity to dramatically alter atmospheric composition, climate, seawater acid-base chemistry, and the propagation of isotopic signals into the geologic record. This talk will present and discuss new quantitative approaches toward better understanding the factors that control organic carbon and pyrite sulfur weathering under a wide range of Earth surface conditions, as well as their downstream effects on seawater chemistry, stability of atmospheric pO2, and conventional interpretations of stable carbon isotope mass balance during pivotal events in Earth's biogeochemical evolution. In particular, we will focus on (1) development of a weathering-driven scaling between atmospheric pO2 and geologic carbon isotope signals that explains the relative stability of marine δ13C through time and provides a mechanism for protracted negative δ13C excursions during transient increases in atmospheric pO2; (2) experimental and theoretical approaches aimed at better understanding the role of pyrite sulfur weathering in stabilizing atmospheric pO2; and (3) the importance of redox balance in the sedimentary rock cycle for controlling the marine carbonate system and atmospheric pCO2.

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.

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.

Sputtering of sulfur by kiloelectronvolt ions - Application to the magnetospheric plasma interaction with Io

NASA Technical Reports Server (NTRS)

Chrisey, D. B.; Johnson, R. E.; Phipps, J. A.; Mcgrath, M. A.; Boring, J. W.

1987-01-01

Accurate measurements of the yields, mass spectra, and energy spectra of ejected sulfur are presented based on vapor deposits of sulfur at temperatures and ion energies relevant to the plasma interaction with the surface of Io. The measured sputtering yields are much lower than previous estimates for room temperature sulfur films, but are comparable to previous measurements of low-temperature keV ion sputtering of SO2. Results suggest that if ions reach the surface of Io its atmosphere will have a nonnegligible sulfur component which is primarily S2. Comparison of injection rates determined for sulfur with those for SO2 indicates that injection from sulfur deposits contributes 13 percent to the total mass injection rate of about 2-3 x 10 to the 29th amu/sec.

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.

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Heterogeneous chemistry of alkylamines with sulfuric acid: implications for atmospheric formation of alkylaminium sulfates.

PubMed

Wang, Lin; Lal, Vinita; Khalizov, Alexei F; Zhang, Renyi

2010-04-01

The heterogeneous interaction of alkylamines with sulfuric acid has been investigated to assess the role of amines in aerosol growth through the formation of alkylaminium sulfates. The kinetic experiments were conducted in a low-pressure fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS). The measurements of heterogeneous uptake of methylamine, dimethylamine, and trimethylamine were performed in the acidity range of 59-82 wt % H(2)SO(4) and between 243 and 283 K. Irreversible reactive uptakes were observed for all three alkylamines, with comparable uptake coefficients (gamma) in the range of 2.0 x 10(-2) to 4.4 x 10(-2). The measured gamma value was slightly higher in more concentrated sulfuric acid and at lower temperatures. The results imply that the heterogeneous reactions of alkylamines contribute effectively to the growth of atmospheric acidic particles and, hence, secondary organic aerosol formation.

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.

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

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.

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

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.

Online High Temporal Resolution Measurement of Atmospheric Sulfate and Sulfur Trioxide with a Light Emitting Diode and Liquid Core Waveguide-Based Sensor.

PubMed

Tian, Yong; Shen, Huiyan; Wang, Qiang; Liu, Aifeng; Gao, Wei; Chen, Xu-Wei; Chen, Ming-Li; Zhao, Zongshan

2018-06-13

High temporal resolution components analysis is still a great challenge for the frontier of atmospheric aerosol research. Here, an online high time resolution method for monitoring soluble sulfate and sulfur trioxide in atmospheric aerosols was developed by integrating a membrane-based parallel plate denuder, a particle collector, and a liquid waveguide capillary cell into a flow injection analysis system. The BaCl 2 solution (containing HCl, glycerin, and ethanol) was enabled to quantitatively transform sulfate into a well-distributed BaSO 4 solution for turbidimetric detection. The time resolution for monitoring the soluble sulfate and sulfur trioxide was 15 h -1 . The limits of detection were 86 and 7.3 μg L -1 ( S/ N = 3) with a 20 and 200 μL SO 4 2- solution injection, respectively. Both the interday and intraday precision values (relative standard deviation) were less than 6.0%. The analytical results of the certificated reference materials (GBW(E)08026 and GNM-M07117-2013) were identical to the certified values (no significant difference at a 95% confidence level). The validity and practicability of the developed device were also evaluated during a firecracker day and a routine day, obviously revealing the continuous variance in atmospheric sulfate and sulfur trioxide in both interday and intraday studies.

[Atmospheric parameter estimation for LAMOST/GUOSHOUJING spectra].

PubMed

Lu, Yu; Li, Xiang-Ru; Yang, Tan

2014-11-01

It is a key task to estimate the atmospheric parameters from the observed stellar spectra in exploring the nature of stars and universe. With our Large Sky Area Multi-Object Fiber Spectroscopy Telescope (LAMOST) which begun its formal Sky Survey in September 2012, we are obtaining a mass of stellar spectra in an unprecedented speed. It has brought a new opportunity and a challenge for the research of galaxies. Due to the complexity of the observing system, the noise in the spectrum is relatively large. At the same time, the preprocessing procedures of spectrum are also not ideal, such as the wavelength calibration and the flow calibration. Therefore, there is a slight distortion of the spectrum. They result in the high difficulty of estimating the atmospheric parameters for the measured stellar spectra. It is one of the important issues to estimate the atmospheric parameters for the massive stellar spectra of LAMOST. The key of this study is how to eliminate noise and improve the accuracy and robustness of estimating the atmospheric parameters for the measured stellar spectra. We propose a regression model for estimating the atmospheric parameters of LAMOST stellar(SVM(lasso)). The basic idea of this model is: First, we use the Haar wavelet to filter spectrum, suppress the adverse effects of the spectral noise and retain the most discrimination information of spectrum. Secondly, We use the lasso algorithm for feature selection and extract the features of strongly correlating with the atmospheric parameters. Finally, the features are input to the support vector regression model for estimating the parameters. Because the model has better tolerance to the slight distortion and the noise of the spectrum, the accuracy of the measurement is improved. To evaluate the feasibility of the above scheme, we conduct experiments extensively on the 33 963 pilot surveys spectrums by LAMOST. The accuracy of three atmospheric parameters is log Teff: 0.006 8 dex, log g: 0.155 1 dex

An evaluation of possible mechanisms for conversion of sulfur dioxide to sulfuric acid and sulfate aerosols in the troposphere

Treesearch

Jack G. Calvert

1976-01-01

The mechanisms and rates of conversion of sulfur dioxide to sulfur trioxide, sulfuric acid, and other "sulfate" aerosol precursors are considered in view of current knowledge related to atmospheric reactions and chemical kinetics. Several heterogeneous pathways exist for SO2 oxidation promoted on solid catalyst particles and in aqueous...

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...

Sulfuric acid in the Venus clouds.

NASA Technical Reports Server (NTRS)

Sill, G. T.

1972-01-01

The extremely dry nature of the Venus upper atmosphere appears to demand the presence of an efficient desiccating agent as the chief constituent of the clouds of Venus. On the basis of polarization measures it is to be expected that this substance is present as spherical droplets, 1 to 2 microns in diameter, with a refractive index n of 1.46 plus or minus 0.02 at 3500A in the observed region of the atmosphere, with T about equal to 235 K. This substance must have ultraviolet, visible, and infrared reflection properties not inconsistent with the observed spectrum of Venus. Sulfuric acid, of about 86% by weight composition, roughly fulfills the first of these properties. The visible and ultraviolet transmission features of a thin layer of elemental bromine and hydrobromic acid dissolved in sulfuric acid somewhat resemble the Venus spectrum, up to 14 microns. The chemical process postulated for forming sulfuric acid involves the oxidation of sulfur and its compounds to sulfuric acid through the agency of elemental bromine produced by the photolytic decomposition of hydrogen bromide.

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.

Preliminary Analysis of Pyrite Reactivity Under Venusian Temperature and Atmosphere

NASA Technical Reports Server (NTRS)

Radoman-Shaw, B. G.; Harvey, R. P.; Jacobson, N. S.; Costa, G. C. C.

2015-01-01

Measurements of Venus surface chemistry suggest a basaltic composition with a predominantly CO2 atmosphere. In order to understand the reactivity of certain possible mineral species on the surface, previous simulation chambers conduct experiments at 1 atmosphere with a simplified CO2 atmosphere. Following this procedure, pyrite (FeS2) samples are used to estimate the reactivity of sulfide minerals under a Venusian atmosphere and climate. Sulfurous gas species have been identified and quantified in the Venusian atmosphere, and sulfurous gas and mineral species are known to be created through volcanism, which is suggested to still occur on the surface of Venus. This experimentation is necessary to constrain reactions that could occur between the surface and atmosphere of Venus to understand terrestrial geology in a thick and hot greenhouse atmosphere. Quantifying this reaction can lead to approximations necessary for further experimentation in more complex environments such as those in the GEER chamber at Glenn Research Center that can simulate pressure along with temperature and a more inclusive and representative Venusian atmosphere.

Parameter Estimation in Atmospheric Data Sets

NASA Technical Reports Server (NTRS)

Wenig, Mark; Colarco, Peter

2004-01-01

In this study the structure tensor technique is used to estimate dynamical parameters in atmospheric data sets. The structure tensor is a common tool for estimating motion in image sequences. This technique can be extended to estimate other dynamical parameters such as diffusion constants or exponential decay rates. A general mathematical framework was developed for the direct estimation of the physical parameters that govern the underlying processes from image sequences. This estimation technique can be adapted to the specific physical problem under investigation, so it can be used in a variety of applications in trace gas, aerosol, and cloud remote sensing. As a test scenario this technique will be applied to modeled dust data. In this case vertically integrated dust concentrations were used to derive wind information. Those results can be compared to the wind vector fields which served as input to the model. Based on this analysis, a method to compute atmospheric data parameter fields will be presented. .

SURFACE REACTIONS OF OXIDES OF SULFUR

EPA Science Inventory

Surface reactions of several sulfur-containing molecules have been studied in order to understand the mechanism by which sulfate ions are formed on atmospheric aerosols. At 25C the heterogeneous oxidation of SO2 by NO2 to sulfuric acid and sulfate ions occurred on hydrated silica...

Sulfur, ultraviolet radiation, and the early evolution of life

NASA Technical Reports Server (NTRS)

Kasting, J. F.; Zahnle, K. J.; Pinto, J. P.; Young, A. T.

1989-01-01

The present biosphere is shielded from harmful solar near ultraviolet (UV) radiation by atmospheric ozone. It is suggested that elemental sulfur vapor could have played a similar role in an anoxic, ozone-free, primitive atmosphere. Sulfur vapor would have been produced photochemically from volcanogenic SO2 and H2S. It is composed of ring molecules, primarily S8, that absorb strongly throughout the near UV, yet are expected to be relatively stable against photolysis and chemical attack. It is also insoluble in water and would thus have been immune to rainout or surface deposition over the oceans. Since the concentration of S8 in the primitive atmosphere would have been limited by its saturation vapor pressure, surface temperatures of 45 C or higher, corresponding to carbon dioxide partial pressures exceeding 2 bars, are required to sustain an effective UV screen. A warm, sulfur-rich, primitive atmosphere is consistent with inferences drawn from molecular phylogeny, which suggest that some of the earliest organisms were thermophilic bacteria that metabolized elemental sulfur.

Decoupling of Neoarchean sulfur sources recorded in Algoma-type banded iron formation

NASA Astrophysics Data System (ADS)

Diekrup, David; Hannington, Mark D.; Strauss, Harald; Ginley, Stephen J.

2018-05-01

Neoarchean Algoma-type banded iron formations (BIFs) are widely viewed as direct chemical precipitates from proximal volcanic-hydrothermal vents. However, a systematic multiple sulfur isotope study of oxide-facies BIF from a type locality in the ca. 2.74 Ga Temagami greenstone belt reveals mainly bacterial turnover of atmospheric elemental sulfur in the host basin rather than deposition of hydrothermally cycled seawater sulfate or sulfur from direct volcanic input. Trace amounts of chromium reducible sulfur that were extracted for quadruple sulfur isotope (32S-33S-34S-36S) analysis record the previously known mass-independent fractionation of volcanic SO2 in the Archean atmosphere (S-MIF) and biological sulfur cycling but only minor contributions from juvenile sulfur, despite the proximity of volcanic sources. We show that the dominant bacterial metabolisms were iron reduction and sulfur disproportionation, and not sulfate reduction, consistent with limited availability of organic matter and the abundant ferric iron deposited as Fe(OH)3. That sulfur contained in the BIF was not a direct volcanic-hydrothermal input, as expected, changes the view of an important archive of the Neoarchean sulfur cycle in which the available sulfur pools were strongly decoupled and only species produced photochemically under anoxic atmospheric conditions were deposited in the BIF-forming environment.

Abatement of sulfur hexafluoride emissions from the semiconductor manufacturing process by atmospheric-pressure plasmas.

PubMed

Lee, How Ming; Chang, Moo Been; Wu, Kuan Yu

2004-08-01

Sulfur hexafluoride (SF6) is an important gas for plasma etching processes in the semiconductor industry. SF6 intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF6 abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes--dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)--were employed and evaluated. Experimental results indicated that as much as 91% of SF6 was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF6, 12% oxygen (O2), and 40% argon (Ar), with nitrogen (N2) as the carrier gas. Four additives, including Ar, O2, ethylene (C2H4), and H2O(g), are effective in enhancing SF6 abatement in the range of conditions studied. DBD achieves a higher SF6 removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF6 is mainly converted to SOF2, SO2F4, sulfur dioxide (SO2), oxygen difluoride (OF2), and fluoride (F2). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF6 emissions.

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.

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems.

PubMed

Bern, Carleton R; Chadwick, Oliver A; Kendall, Carol; Pribil, Michael J

2015-05-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ(34)S VCDT) of -0.8‰. Bulk deposition on the island of Maui had a δ(34)S VCDT that varied temporally, spanned a range from +8.2 to +19.7‰, and reflected isotopic mixing from three sources: sea-salt (+21.1‰), marine biogenic emissions (+15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to +2.7‰) to relatively high (+17.8 to +19.3‰) soil δ(34)S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from +8.1 to +20.3‰ and generally decreased with increasing elevation (0-2000 m), distance from the coast (0-12 km), and annual rainfall (180-5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over ecosystem sulfur

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

The growing contribution of sulfur emissions from ships in Asian waters, 1988-1995.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Streets, D. G.; Guttikunda, S. K.; Carmichael, G. R.

2000-01-01

International shipping is a major source of sulfur emissions in Asia. Because the fuel oil used by ships is high in sulfur, the resulting emissions of SO{sub 2}2 are large and contribute as much as 20% to the atmospheric loading in the vicinity of ports and heavily traveled waterways. Because of the rapid growth of Asian economies in the 1980s and early 1990s, it is estimated that shipping trade grew by an average of 5.4% per year between 1988 and 1995; in particular, crude oil shipments to Asian countries other than Japan grew by an average of 11.4% per year.more » The emissions of SO{sub 2} from shipping are estimated to have grown by 5.9% per year between 1988 and 1995, rising from 545 Gg in 1988 to 817 Gg in 1995. This study uses the ATMOS atmospheric transport and deposition model to study the effects of these emissions, both in absolute terms and relative to land-based emissions, on wet and dry deposition of sulfur. Southeast Asia is most heavily affected by emissions from ships, particularly Sumatra, peninsular Malaysia, and Singapore, which routinely receive in excess of 10% of their deposition from ships. A strong seasonal component is also observed, with large areas of Southeast Asia and coastal Japan receiving sulfur deposition that exceeds 10 mg S m{sup -2} season{sup -1}. Deposition is at least 25% higher in summer and fall than in winter and spring. Peak values of 25-50 mg S m{sup -2} season{sup -1} are calculated for winter in the Strait of Malacca. This work suggests a need to introduce policies to reduce the sulfur content of marine fuels or otherwise reduce emissions of SO{sub 2} from ships in Asian waters.« less

The growing contribution of sulfur emissions from ships in Asian waters, 1988-1995

NASA Astrophysics Data System (ADS)

Streets, David G.; Guttikunda, Sarath K.; Carmichael, Gregory R.

International shipping is a major source of sulfur emissions in Asia. Because the fuel oil used by ships is high in sulfur, the resulting emissions of SO 2 are large and contribute as much as 20% to the atmospheric loading in the vicinity of ports and heavily traveled waterways. Because of the rapid growth of Asian economies in the 1980s and early 1990s, it is estimated that shipping trade grew by an average of 5.4% per year between 1988 and 1995; in particular, crude oil shipments to Asian countries other than Japan grew by an average of 11.4% per year. The emissions of SO 2 from shipping are estimated to have grown by 5.9% per year between 1988 and 1995, rising from 545 Gg in 1988 to 817 Gg in 1995. This study uses the ATMOS atmospheric transport and deposition model to study the effects of these emissions, both in absolute terms and relative to land-based emissions , on wet and dry deposition of sulfur. Southeast Asia is most heavily affected by emissions from ships, particularly Sumatra, peninsular Malaysia, and Singapore, which routinely receive in excess of 10% of their deposition from ships. A strong seasonal component is also observed, with large areas of Southeast Asia and coastal Japan receiving sulfur deposition that exceeds 10 mg S m -2 season -1. Deposition is at least 25% higher in summer and fall than in winter and spring. Peak values of 25-50 mg S m -2 season -1 are calculated for winter in the Strait of Malacca. This work suggests a need to introduce policies to reduce the sulfur content of marine fuels or otherwise reduce emissions of SO 2 from ships in Asian waters.

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

PubMed

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

2009-09-01

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 Delta33S 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 lambda >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.

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

40 CFR 60.104 - Standards for sulfur oxides.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 7 2013-07-01 2013-07-01 false Standards for sulfur oxides. 60.104... Refineries § 60.104 Standards for sulfur oxides. Each owner or operator that is subject to the requirements... atmosphere from any Claus sulfur recovery plant containing in excess of: (i) For an oxidation control system...

40 CFR 60.104 - Standards for sulfur oxides.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 7 2014-07-01 2014-07-01 false Standards for sulfur oxides. 60.104... Refineries § 60.104 Standards for sulfur oxides. Each owner or operator that is subject to the requirements... atmosphere from any Claus sulfur recovery plant containing in excess of: (i) For an oxidation control system...

40 CFR 60.104 - Standards for sulfur oxides.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standards for sulfur oxides. 60.104... Refineries § 60.104 Standards for sulfur oxides. Each owner or operator that is subject to the requirements... atmosphere from any Claus sulfur recovery plant containing in excess of: (i) For an oxidation control system...

40 CFR 60.104 - Standards for sulfur oxides.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 6 2010-07-01 2010-07-01 false Standards for sulfur oxides. 60.104... Refineries § 60.104 Standards for sulfur oxides. Each owner or operator that is subject to the requirements... atmosphere from any Claus sulfur recovery plant containing in excess of: (i) For an oxidation control system...

40 CFR 60.104 - Standards for sulfur oxides.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 7 2012-07-01 2012-07-01 false Standards for sulfur oxides. 60.104... Refineries § 60.104 Standards for sulfur oxides. Each owner or operator that is subject to the requirements... atmosphere from any Claus sulfur recovery plant containing in excess of: (i) For an oxidation control system...

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

40 CFR 60.173 - Standard for sulfur dioxide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 7 2013-07-01 2013-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain sulfur...

40 CFR 60.173 - Standard for sulfur dioxide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 7 2012-07-01 2012-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain sulfur...

40 CFR 60.173 - Standard for sulfur dioxide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 7 2014-07-01 2014-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain sulfur...

40 CFR 60.173 - Standard for sulfur dioxide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 6 2011-07-01 2011-07-01 false Standard for sulfur dioxide. 60.173... Smelters § 60.173 Standard for sulfur dioxide. (a) On and after the date on which the performance test... subpart shall cause to be discharged into the atmosphere from any roaster any gases which contain sulfur...

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

Claus sulfur recovery unit startups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parnell, D.C.

1973-08-01

Because of the recent emphasis on reducing sulfur emissions to the atmosphere, Claus-type sulfur recovery units are becoming more prevalent throughout the industry. Many plants, including refinery, chemical, and natural gasoline units, are being required to install Claus sulfur recovery facilities to meet pollution requirements. Although Claus units in some cases cannot alone meet the most rigid air pollution codes currently being enforced, they are still the most economical and practical method for recovering about 94 to 97% of the sulfur from hydrogen sulfide rich gases. For best operation and longer service life, proper startup and shutdown procedures for thesemore » sulfur recovery units should be followed. On all startups and shutdowns, these units require considerable operator attention; improper operation during these critical phases can affect overall plant efficiency.« less

Estimation of the vertical profile of sulfur dioxide injection into the atmosphere by a volcanic eruption using satellite column measurements and inverse transport modeling

NASA Astrophysics Data System (ADS)

Eckhardt, S.; Prata, A. J.; Seibert, P.; Stebel, K.; Stohl, A.

2008-07-01

An analytical inversion method has been developed to estimate the vertical profile of SO2 emissions from volcanic eruptions. The method uses satellite-observed total SO2 columns and an atmospheric transport model (FLEXPART) to exploit the fact that winds change with altitude thus, the position and shape of the volcanic plume bear information on its emission altitude. The method finds the vertical emission distribution which minimizes the total difference between simulated and observed SO2 columns while also considering a priori information. We have tested the method with the eruption of Jebel at Tair, Yemen, on 30 September 2007 for which a comprehensive observational data set from various satellite instruments (AIRS, OMI, SEVIRI, CALIPSO) is available. Using satellite data from the first 24 h after the eruption for the inversion, we found an emission maximum near 16 km above sea level (a.s.l.), and secondary maxima near 5, 9, 12 and 14 km a.s.l. 60% of the emission occurred above the tropopause. The emission profile obtained in the inversion was then used to simulate the transport of the plume over the following week. The modeled plume agrees very well with SO2 total columns observed by OMI, and its altitude agrees with CALIPSO aerosol observations to within 1 2 km. The inversion result is robust against various changes in both the a priori and the observations. Even when using only SEVIRI data from the first 15 h after the eruption, the emission profile was reasonably well estimated. The method is computationally very fast. It is therefore suitable for implementation within an operational environment, such as the Volcanic Ash Advisory Centers, to predict the threat posed by volcanic ash for air traffic. It could also be helpful for assessing the sulfur input into the stratosphere, be it in the context of volcanic processes or also for proposed geo-engineering techniques to counteract global warming.

Estimation of the vertical profile of sulfur dioxide injection into the atmosphere by a volcanic eruption using satellite column measurements and inverse transport modeling

NASA Astrophysics Data System (ADS)

Eckhardt, S.; Prata, A. J.; Seibert, P.; Stebel, K.; Stohl, A.

2008-02-01

An analytical inversion method has been developed to estimate the vertical profile of SO2 emissions from volcanic eruptions. The method uses satellite-observed total SO2 columns and an atmospheric transport model (FLEXPART) to exploit the fact that winds change with altitude - thus, the position and shape of the volcanic plume bear information on its emission altitude. The method finds the vertical emission distribution which minimizes the total difference between simulated and observed SO2 columns while also considering a priori information. We have tested the method with the eruption of Jebel at Tair on 30 September 2007 for which a comprehensive observational data set from various satellite instruments (AIRS, OMI, SEVIRI, CALIPSO) is available. Using satellite data from the first 24 h after the eruption for the inversion, we found an emission maximum near 16 km above sea level (asl), and secondary maxima near 5, 9, 12 and 14 km a.s.l. 60% of the emission occurred above the tropopause. The emission profile obtained in the inversion was then used to simulate the transport of the plume over the following week. The modeled plume agrees very well with SO2 total columns observed by OMI, and its altitude and width agree mostly within 1-2 km with CALIPSO observations of stratospheric aerosol produced from the SO2. The inversion result is robust against various changes in both the a priori and the observations. Even when using only SEVIRI data from the first 15 h after the eruption, the emission profile was reasonably well estimated. The method is computationally very fast. It is therefore suitable for implementation within an operational environment, such as the Volcanic Ash Advisory Centers, to predict the threat posed by volcanic ash for air traffic. It could also be helpful for assessing the sulfur input into the stratosphere, be it in the context of volcanic processes or also for proposed geo-engineering techniques to counteract global warming.

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.

Microwave absorptivity by sulfuric acid in the Venus atmosphere derived from the Venus Express Radio Science Experiment VeRa

NASA Astrophysics Data System (ADS)

Oschlisniok, J.; Pätzold, M.; Häusler, B.; Tellmann, S.; Bird, M.; Andert, T.; Remus, S.; Krüger, C.; Mattei, R.

2011-10-01

Earth's nearest planetary neighbour Venus is shrouded within a roughly 22 km thick three-layered cloud deck, which is located approximately 48 km above the surface and extends to an altitude of about 70 km. The clouds are mostly composed of sulfuric acid. The latter is responsible for a strong absorption of radio signals at microwaves, which is observed in radio occultation experiments. The absorption of the radio signal intensity is used to determine the abundance of H2SO4. This way a detailed study of the H2SO4 height distribution within the cloud deck is possible. The Venus Express spacecraft is orbiting Venus since 2006. The Radio Science Experiment VeRa onboard probes the atmosphere with radio signals at 3.4 cm (X-Band) and 13 cm (S-Band). Absorptivity profiles of the 3.4 cm radio wave and the resulting vertical sulfuric acid profiles in the cloud region of Venus' atmosphere are presented. The three-layered structure and a distinct latitudinal variation of H2SO4 are observed. Convective atmospheric motions within the equatorial latitudes, which transport absorbing material from lower to higher altitudes, are clearly visible. Results of the Venus Monitoring Camera (VMC) and the Visible and Infrared Thermal Imaging Spectrometer (VIRTIS) are compared with the VeRa results.

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

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

USGS Publications Warehouse

Bern, Carleton R.; Chadwick, Oliver A.; Kendall, Carol; Pribil, Michael J.

2015-01-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ34S VCDT) of − 0.8‰. Bulk deposition on the island of Maui had a δ34S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7‰, and reflected isotopic mixing from three sources: sea-salt (+ 21.1‰), marine biogenic emissions (+ 15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7‰) to relatively high (+ 17.8 to + 19.3‰) soil δ34S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3‰ and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls

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

Sulfate burial constraints on the Phanerozoic sulfur cycle.

PubMed

Halevy, Itay; Peters, Shanan E; Fischer, Woodward W

2012-07-20

The sulfur cycle influences the respiration of sedimentary organic matter, the oxidation state of the atmosphere and oceans, and the composition of seawater. However, the factors governing the major sulfur fluxes between seawater and sedimentary reservoirs remain incompletely understood. Using macrostratigraphic data, we quantified sulfate evaporite burial fluxes through Phanerozoic time. Approximately half of the modern riverine sulfate flux comes from weathering of recently deposited evaporites. Rates of sulfate burial are unsteady and linked to changes in the area of marine environments suitable for evaporite formation and preservation. By contrast, rates of pyrite burial and weathering are higher, less variable, and largely balanced, highlighting a greater role of the sulfur cycle in regulating atmospheric oxygen.

The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions

DOE PAGES

Perraud, Véronique; Horne, Jeremy R.; Martinez, Andrew S.; ...

2015-10-19

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present paper, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine–California Institute ofmore » Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. Finally, this could be particularly important in agricultural areas where there are significant sources of OSCs.« less

The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions.

PubMed

Perraud, Véronique; Horne, Jeremy R; Martinez, Andrew S; Kalinowski, Jaroslaw; Meinardi, Simone; Dawson, Matthew L; Wingen, Lisa M; Dabdub, Donald; Blake, Donald R; Gerber, R Benny; Finlayson-Pitts, Barbara J

2015-11-03

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine-California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs.

The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions

PubMed Central

Perraud, Véronique; Horne, Jeremy R.; Martinez, Andrew S.; Kalinowski, Jaroslaw; Meinardi, Simone; Dawson, Matthew L.; Wingen, Lisa M.; Dabdub, Donald; Blake, Donald R.; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

2015-01-01

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine–California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs. PMID:26483454

The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perraud, Véronique; Horne, Jeremy R.; Martinez, Andrew S.

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present paper, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine–California Institute ofmore » Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. Finally, this could be particularly important in agricultural areas where there are significant sources of OSCs.« less

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.

Sulfur compound concentrations at swine and poultry facilities

USDA-ARS?s Scientific Manuscript database

Reduced sulfur compounds are emitted from waste handling at animal agriculture operations. These sulfur compounds are responsible for odor production as well as participating in atmospheric chemistry. We have adapted a chromatographic method for providing 10 minute online monitoring capability of re...

The Provenance of Sulfur that Becomes Non-Seasalt Sulfate (NSS)

NASA Astrophysics Data System (ADS)

Huebert, B. J.; Simpson, R. M.; Howell, S. G.

2012-12-01

As a part of the Pacific Atmospheric Sulfur Experiment (PASE), we measured sulfur gases and aerosol chemistry (vs size) from the NCAR C-130 near Christmas Island. Monthly (project) average concentrations in the Marine Boundary Layer (MBL, the lowest mixed layer) and Buffer Layer (BuL, a more stable layer atop the MBL, with clouds) are used to evaluate the formation, loss, and exchange rates for DMS, SO2, and NSS in each layer. We evaluate entrainment, divergence, vertical mixing, chemical formation and loss for each to make a self-consistent budget of oxidized sulfur in the remote marine atmosphere. We find that long-range transport of sulfur from continental sources can be larger than the sulfur source from biogenic dimethyl sulfide, DMS. DMS does not appear to control either the number of NSS particles or NSS mass.

Iron and sulfur in the pre-biologic ocean

NASA Technical Reports Server (NTRS)

Walker, J. C.; Brimblecombe, P.

1985-01-01

Tentative geochemical cycles for the pre-biologic Earth are developed by comparing the relative fluxes of oxygen, dissolved iron, and sulfide to the atmosphere and ocean. The flux of iron is found to exceed both the oxygen and the sulfide fluxes. Because of the insolubility of iron oxides and sulfides the implication is that dissolved iron was fairly abundant and that oxygen and sulfide were rare in the atmosphere and ocean. Sulfate, produced by the oxidation of volcanogenic sulfur gases, was the most abundant sulfur species in the ocean, but its concentration was low by modern standards because of the absence of the river-borne flux of dissolved sulfate produced by oxidative weathering of the continents. These findings are consistent with the geologic record of the isotopic composition of sedimentary sulfates and sulfides. Except in restricted environments, the sulfur metabolism of the earliest organisms probably involved oxidized sulfur species not sulfide.

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 for the same period. Emissions from smelters in the region 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 of sulfate. No relation between regional stream chemistry and smelter or regional sulfur dioxide emissions is detected for the watersheds. Local emissions trends, however, do appear to affect sulfate concentrations in the streams. Year-to-year variability in stream sulfate concentration is much greater than any long-term trends that might be inferred.

Catalyst for elemental sulfur recovery process

DOEpatents

Flytzani-Stephanopoulos, M.; Liu, W.

1995-01-24

A catalytic reduction process is described for the direct recovery of elemental sulfur from various SO[sub 2]-containing industrial gas streams. The catalytic process provides high activity and selectivity, as well as stability in the reaction atmosphere, for the reduction of SO[sub 2] to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over a metal oxide composite catalyst having one of the following empirical formulas: [(FO[sub 2])[sub 1[minus]n](RO)[sub n

Using biogenic sulfur gases as remotely detectable biosignatures on anoxic planets.

PubMed

Domagal-Goldman, Shawn D; Meadows, Victoria S; Claire, Mark W; Kasting, James F

2011-06-01

We used one-dimensional photochemical and radiative transfer models to study the potential of organic sulfur compounds (CS(2), OCS, CH(3)SH, CH(3)SCH(3), and CH(3)S(2)CH(3)) to act as remotely detectable biosignatures in anoxic exoplanetary atmospheres. Concentrations of organic sulfur gases were predicted for various biogenic sulfur fluxes into anoxic atmospheres and were found to increase with decreasing UV fluxes. Dimethyl sulfide (CH(3)SCH(3), or DMS) and dimethyl disulfide (CH(3)S(2)CH(3), or DMDS) concentrations could increase to remotely detectable levels, but only in cases of extremely low UV fluxes, which may occur in the habitable zone of an inactive M dwarf. The most detectable feature of organic sulfur gases is an indirect one that results from an increase in ethane (C(2)H(6)) over that which would be predicted based on the planet's methane (CH(4)) concentration. Thus, a characterization mission could detect these organic sulfur gases-and therefore the life that produces them-if it could sufficiently quantify the ethane and methane in the exoplanet's atmosphere.

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.

Heterogeneous atmospheric chemistry

NASA Technical Reports Server (NTRS)

Schryer, D. R.

1982-01-01

The present conference on heterogeneous atmospheric chemistry considers such topics concerning clusters, particles and microparticles as common problems in nucleation and growth, chemical kinetics, and catalysis, chemical reactions with aerosols, electron beam studies of natural and anthropogenic microparticles, and structural studies employing molecular beam techniques, as well as such gas-solid interaction topics as photoassisted reactions, catalyzed photolysis, and heterogeneous catalysis. Also discussed are sulfur dioxide absorption, oxidation, and oxidation inhibition in falling drops, sulfur dioxide/water equilibria, the evidence for heterogeneous catalysis in the atmosphere, the importance of heterogeneous processes to tropospheric chemistry, soot-catalyzed atmospheric reactions, and the concentrations and mechanisms of formation of sulfate in the atmospheric boundary layer.

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

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...

Metal emissions from Kilauea, and a suggested revision of the estimated worldwide metal output by quiescent degassing of volcanoes

USGS Publications Warehouse

Hinkley, T.K.; Lamothe, P.J.; Wilson, S.A.; Finnegan, David L.; Gerlach, T.M.

1999-01-01

Measurements of a large suite of metals (Pb, Cd, Cu, Zn and several others) and sulfur at Kilauea volcano over an extended period of time has yielded a detailed record of the atmospheric injection of ordinarily-rare metals from this quiescently degassing volcano, representative of an important type. We have combined the Kilauea data with data of recent studies by others (emissions from volcanoes in the Indonesian arc; the large Laki eruption of two centuries ago; Etna: estimates of total volcanic emissions of sulfur) to form the basis for a new working estimate of the rate of worldwide injection of metals to the atmosphere by volcanoes. The new estimate is that volcanoes inject a substantially smaller mass of ordinarily-rare metals into the atmosphere than was stated in a widely cited previous estimate [J.O. Nriagu, A global assessment of natural sources of atmospheric trace metals, Nature 338 (1989) 47-49]. Our estimate, which is an upper limit, is an annual injection mass of about 10,000 tons of the metals considered, versus the earlier estimate of about 23,000 tons. Also, the proportions of the metals are substantially different in our new estimate.

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.

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.

Transition metal-catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

NASA Astrophysics Data System (ADS)

Alexander, Becky; Park, Rokjin J.; Jacob, Daniel J.; Gong, Sunling

2009-01-01

We use observations of the oxygen-17 excess (Δ17O) of sulfate in the Arctic to quantify the sulfate source from aqueous SO2 (S(IV)) oxidation by O2 catalyzed by transition metals. Due to the lack of photochemically produced OH and H2O2 in high latitudes during winter, combined with high anthropogenic SO2 emissions in the Northern Hemisphere, oxidation by O3 is predicted to dominate sulfate formation during winter in this region. However, Δ17O measurements of sulfate aerosol collected in Alert, Canada, are not consistent with O3 as the dominant oxidant and indicate that a S(IV) oxidant with near-zero Δ17O values (O2) is important during winter. We use a global chemical transport model to interpret quantitatively the Alert observations and assess the global importance of sulfate production by Fe(III)- and Mn(II)-catalyzed oxidation of S(IV) by O2. We scale anthropogenic and natural atmospheric metal concentrations to primary anthropogenic sulfate and dust concentrations, respectively. The solubility and oxidation state of these metals is determined by cloud liquid water content, source, and sunlight. By including metal-catalyzed S(IV) oxidation, the model is consistent with the Δ17O magnitudes in the Alert data during winter. Globally, we find that this mechanism contributes 9-17% to sulfate production. The inclusion of metal-catalyzed oxidation does not resolve model discrepancies with surface SO2 and sulfate observations in Europe. Oxygen isotope measurements of sulfate aerosols collected near anthropogenic and dust sources of metals would help to verify the importance of this sulfur oxidation pathway.

Sulfurized carbohydrates: an important sedimentary sink for organic carbon?

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Kok, Marika D.; Köster, Jürgen; Schouten, Stefan

1998-12-01

In contrast to the general belief that carbohydrate carbon (C CHO) is preferentially degraded and is not extensively preserved in the sedimentary record, it is shown here that C CHO forms a large fraction of the organic matter (OM) of the total organic carbon (TOC)-rich upper Jurassic Kimmeridge Clay Formation as a result of early diagenetic sulfurization, a previously unrecognized pathway of OM preservation. This is evident from both changes in the molecular composition of the insoluble OM and from δ 13C TOC shifts of 6‰ with varying C CHO contents. Furthermore, experiments simulating the natural sulfurization of the C CHO-rich alga Phaeocystis spp. demonstrated that sulfurization can indeed lead to a substantial preservation of C CHO with a molecular fingerprint identical to that of the Kimmeridge Clay and many other Recent and ancient marine OM-rich sediments. These results imply that preservation of C CHO can exert a fundamental control on δ 13C TOC in OM-rich sediments, complicating the interpretation of δ 13C TOC records with regard to estimating terrestrial versus aquatic OM fractions, reconstruction of past atmospheric CO 2 levels and global carbon budget models.

Tracing Archean sulfur across stitched lithospheric blocks

NASA Astrophysics Data System (ADS)

LaFlamme, Crystal; Fiorentini, Marco; Lindsay, Mark; Wing, Boswell; Selvaraja, Vikraman; Occhipinti, Sandra; Johnson, Simon; Bui, Hao Thi

2017-04-01

Craton margins are loci for volatile exchange among lithospheric geochemical reservoirs during crust formation processes. Here, we seek to revolutionise the current understanding of the planetary flux and lithospheric transfer of volatiles during supercontinent formation by tracing sulfur from the atmosphere-hydrosphere through to the lithosphere during crust formation. To do so, we trace the transfer of sulfur by following mass independently fractionated sulfur at ancient tectonic boundaries has the potential to. Mass independent fractionation of sulfur (MIF-S) is a signature (quantified as Δ33S and Δ36S) that is unique to the Archean sedimentary rock record and imparted to sulfur reservoirs that interacted with the oxygen-poor atmosphere before the Great Oxidation Event (GOE) at ca. 2.4 Ga. Here we present multiple sulfur isotopes from across a Proterozoic post-GOE orogenic belt, formed when Archean cratons were stitched together during supercontinent amalgamation. For the first time, multiple sulfur isotope data are presented spatially to elucidate volatile pathways across lithospheric blocks. Across the orogenic belt, the Proterozoic granitoid and hydrothermal rock records proximal to Archean cratons preserve values of Δ33S up to +0.8\\permil and a Δ33S-Δ36S array of -1.2, whereas magmatic and hydrothermal systems located more distally from the margin do not display any evidence of MIF-S. This is the first study to identify MIF-S in a Proterozoic orogen indicates that tectonic processes controlling lithospheric evolution and crust formation at tectonic boundaries are able to transfer sulfur from Archean supracrustal rock reservoirs to newly formed Proterozoic granitoid crust. The observation of MIF-S in the Proterozoic granitoid rock record has the potential to revolutionise our understanding of secular changes in the evolution of crust formation mechanisms through time.

Formation rates, stability and reactivity of sulfuric acid - amine clusters predicted by computational chemistry

NASA Astrophysics Data System (ADS)

Kurtén, Theo; Ortega, Ismael; Kupiainen, Oona; Olenius, Tinja; Loukonen, Ville; Reiman, Heidi; McGrath, Matthew; Vehkamäki, Hanna

2013-04-01

Despite the importance of atmospheric particle formation for both climate and air quality, both experiments and non-empirical models using e.g. sulfuric acid, ammonia and water as condensing vapors have so far been unable to reproduce atmospheric observations using realistic trace gas concentrations. Recent experimental and theoretical evidence has shown that this mystery is likely resolved by amines. Combining first-principles evaporation rates for sulfuric acid - dimethylamine clusters with cluster kinetic modeling, we show that even sub-ppt concentrations of amines, together with atmospherically realistic concentrations of sulfuric acid, result in formation rates close to those observed in the atmosphere. Our simulated cluster formation rates are also close to, though somewhat larger than, those measured at the CLOUD experiment in CERN for both sulfuric acid - ammonia and sulfuric acid - dimethylamine systems. A sensitivity analysis indicates that the remaining discrepancy for the sulfuric acid - amine particle formation rates is likely caused by steric hindrances to cluster formation (due to alkyl groups of the amine molecules) rather than by significant errors in the evaporation rates. First-principles molecular dynamic and reaction kinetic modeling shed further light on the microscopic physics and chemistry of sulfuric acid - amine clusters. For example, while the number and type of hydrogen bonds in the clusters typically reach their equilibrium values on a picosecond timescale, and the overall bonding patterns predicted by traditional "static" quantum chemical calculations seem to be stable, the individual atoms participating in the hydrogen bonds continuously change at atmospherically realistic temperatures. From a chemical reactivity perspective, we have also discovered a surprising phenomenon: clustering with sulfuric acid molecules slightly increases the activation energy required for the abstraction of alkyl hydrogens from amine molecules. This implies

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.

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.

Anoxic atmospheres on Mars driven by volcanism: Implications for past environments and life

NASA Astrophysics Data System (ADS)

Sholes, Steven F.; Smith, Megan L.; Claire, Mark W.; Zahnle, Kevin J.; Catling, David C.

2017-07-01

Mars today has no active volcanism and its atmosphere is oxidizing, dominated by the photochemistry of CO2 and H2O. Mars experienced widespread volcanism in the past and volcanic emissions should have included reducing gases, such as H2 and CO, as well as sulfur-bearing gases. Using a one-dimensional photochemical model, we consider whether plausible volcanic gas fluxes could have switched the redox-state of the past martian atmosphere to reducing conditions. In our model, the total quantity and proportions of volcanic gases depend on the water content, outgassing pressure, and oxygen fugacity of the source melt. We find that, with reasonable melt parameters, the past martian atmosphere (∼3.5 Gyr to present) could have easily reached reducing and anoxic conditions with modest levels of volcanism, >0.14 km3 yr-1, which are well within the range of estimates from thermal evolution models or photogeological studies. Counter-intuitively we also find that more reducing melts with lower oxygen fugacity require greater amounts of volcanism to switch a paleo-atmosphere from oxidizing to reducing. The reason is that sulfur is more stable in such melts and lower absolute fluxes of sulfur-bearing gases more than compensate for increases in the proportions of H2 and CO. These results imply that ancient Mars should have experienced periods with anoxic and reducing atmospheres even through the mid-Amazonian whenever volcanic outgassing was sustained at sufficient levels. Reducing anoxic conditions are potentially conducive to the synthesis of prebiotic organic compounds, such as amino acids, and are therefore relevant to the possibility of life on Mars. Also, anoxic reducing conditions should have influenced the type of minerals that were formed on the surface or deposited from the atmosphere. We suggest looking for elemental polysulfur (S8) as a signature of past reducing atmospheres. Finally, our models allow us to estimate the amount of volcanically sourced atmospheric

Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria (Final)

EPA Science Inventory

The SOx ISA reviews information on atmospheric science, exposure, dosimetry, mode of action, and health effects related to sulfur oxides and sulfur dioxide (SO2), including evidence from controlled human exposure, epidemiologic, and toxicological studies.

Total sulfur dioxide emissions and pre-eruption vapor-saturated magma at Mount St. Helens, 1980-88

NASA Astrophysics Data System (ADS)

Gerlach, T. M.; McGee, K. A.

1994-12-01

SO2 from explosive volcanism can cause significant climatic and atmospheric impacts, but the source of the sulfur is controversial. Total ozone mapping spectrometer (TOMS), correlation spectrometer (COSPEC), and ash leachate data for Mount St. Helens from the time of the climactic eruption on 18 May 1980 to the final stages of non-explosive degassing in 1988 give a total SO2 emission of 2 Mt. COSPEC data show a sharp drop in emission rate that was apparently controlled by a decreasing rate of magma supply. A total SO2 emission of only 0.08 Mt is estimated from melt inclusion data and the conventional assumption that the main sulfur source was pre-eruption melt; commonly invoked sources of 'excess sulfur' (anhydrite decomposition, basaltic magma, and degassing of non-erupted magma) are unlikely in this case. Thus melt inclusions may significantly underestimate SO2 emissions and impacts of explosive volcanism on climate and the atmosphere. Measured CO2 emissions, together with the H2O content of melt inclusions and experimental solubility data, indicate the Mount St. Helens dacite was vapor-saturated at depth prior to ascent and suggest that a vapor phase was the main source of sulfur for the 2-Mt of SO2. A vapor source is consistent with experimental studies on the Mount St. Helens dacite and removes the need for a much debated shallow magma body.

Using Biogenic Sulfur Gases as Remotely Detectable Biosignatures on Anoxic Planets

PubMed Central

Meadows, Victoria S.; Claire, Mark W.; Kasting, James F.

2011-01-01

Abstract We used one-dimensional photochemical and radiative transfer models to study the potential of organic sulfur compounds (CS2, OCS, CH3SH, CH3SCH3, and CH3S2CH3) to act as remotely detectable biosignatures in anoxic exoplanetary atmospheres. Concentrations of organic sulfur gases were predicted for various biogenic sulfur fluxes into anoxic atmospheres and were found to increase with decreasing UV fluxes. Dimethyl sulfide (CH3SCH3, or DMS) and dimethyl disulfide (CH3S2CH3, or DMDS) concentrations could increase to remotely detectable levels, but only in cases of extremely low UV fluxes, which may occur in the habitable zone of an inactive M dwarf. The most detectable feature of organic sulfur gases is an indirect one that results from an increase in ethane (C2H6) over that which would be predicted based on the planet's methane (CH4) concentration. Thus, a characterization mission could detect these organic sulfur gases—and therefore the life that produces them—if it could sufficiently quantify the ethane and methane in the exoplanet's atmosphere. Key Words: Exoplanets—Biosignatures—Anoxic atmospheres—Planetary atmospheres—Remote life detection—Photochemistry. Astrobiology 11, 419–441. PMID:21663401

Multiple sulfur isotopes of sulfides from sediments in the aftermath of Paleoproterozoic glaciations

NASA Astrophysics Data System (ADS)

Papineau, D.; Mojzsis, S. J.; Coath, C. D.; Karhu, J. A.; McKeegan, K. D.

2005-11-01

Geochemical evidence reported from Paleoproterozoic sediments has long been used to evaluate the transition from the anoxic Archean atmosphere to an oxygenated atmosphere. Sulfur isotopes ( 32S, 33S, 34S and 36S) in sedimentary sulfides and sulfates are an especially sensitive means to monitor this transition, such that the timing of the Paleoproterozoic "Great Oxidation Event" can be investigated using mass-independently fractionated (MIF) sulfur isotope systematics expressed as Δ 33S. Here we report data from 83 individual analyses of pyrite, pyrrhotite and chalcopyrite on a new suite of 30 different samples from Finland, South Africa, Wyoming and Ontario that span ˜600 My and follow one or several "Snowball Earth" events in the Paleoproterozoic. The samples were measured using a high-resolution secondary ion mass spectrometry technique in multicollection mode that investigates multiple sulfur isotopes in microdomains (<30 μm) within individual sulfide grains while preserving petrographic context. We focused on sediments deposited in the aftermath of the Paleoproterozoic glaciations (between 1.9 and 2.2 Ga) to trace fluctuations in atmospheric O 2 concentrations that were likely affected by an interplay of O 2 sinks in the atmosphere and the upper ocean and continental crust, and by the emergence and diversification of aerobic organisms. Our results demonstrate that MIF sulfur isotopes are absent in sediments deposited after the period of protracted global cooling in the Paleoproterozoic and independently confirm observations that MIF ceased during this time. We interpret our results by integrating Δ 33S and δ 34S data in sulfides, δ 13C data in carbonates and the estimated timing of glaciation events in the Paleoproterozoic. Data strongly hint at the presence of microbial sulfate reduction and fluctuations in the concentration of dissolved seawater sulfate and/or in δ 34S sulfate in the aftermath of glaciations and likely were affected by changing erosion

A Hybrid Approach for Estimating Total Deposition in the ...

EPA Pesticide Factsheets

Atmospheric deposition of nitrogen and sulfur causes many deleterious effects on ecosystems including acidification and excess eutrophication. Assessments to support development of strategies to mitigate these effects require spatially and temporally continuous values of nitrogen and sulfur deposition. In the U.S., national monitoring networks exist that provide values of wet and dry deposition at discrete locations. While wet deposition can be interpolated between the monitoring locations, dry deposition cannot. Additionally, monitoring networks do not measure the complete suite of chemicals that contribute to total sulfur and nitrogen deposition. Regional air quality models provide spatially continuous values of deposition of monitored species as well as important unmeasured species. However, air quality modeling values are not generally available for an extended continuous time period. Air quality modeling results may also be biased for some chemical species. We developed a novel approach for estimating dry deposition using data from monitoring networks such as the Clean Air Status and Trends Network (CASTNET), the National Atmospheric Deposition Program (NADP) Ammonia Monitoring Network (AMoN), and the Southeastern Aerosol Research and Characterization (SEARCH) network and modeled data from the Community Multiscale Air Quality (CMAQ) model. These dry deposition values estimates are then combined with wet deposition values from the NADP National Trends Networ

A Novel Hybrid Approach for Estimating Total Deposition in ...

EPA Pesticide Factsheets

Atmospheric deposition of nitrogen and sulfur causes many deleterious effects on ecosystems including acidification and excess eutrophication. Assessments to support development of strategies to mitigate these effects require spatially and temporally continuous values of nitrogen and sulfur deposition. In the U.S., national monitoring networks exist that provide values of wet and dry deposition at discrete locations. While wet deposition can be interpolated between the monitoring locations, dry deposition cannot. Additionally, monitoring networks do not measure the complete suite of chemicals that contribute to total sulfur and nitrogen deposition. Regional air quality models provide spatially continuous values of deposition of monitored species as well as important unmeasured species. However, air quality modeling values are not generally available for an extended continuous time period. Air quality modeling results may also be biased for some chemical species. We developed a novel approach for estimating dry deposition using data from monitoring networks such as the Clean Air Status and Trends Network (CASTNET), the National Atmospheric Deposition Program (NADP) Ammonia Monitoring Network (AMoN), and the Southeastern Aerosol Research and Characterization (SEARCH) network and modeled data from the Community Multiscale Air Quality (CMAQ) model. These dry deposition values estimates are then combined with wet deposition values from the NADP National Trends Networ

Terpolymerization of ethylene, sulfur dioxide and carbon monoxide

DOEpatents

Johnson, Richard; Steinberg, Meyer

1981-01-01

This invention relates to a high molecular weight terpolymer of ethylene, sulfur dioxide and carbon monoxide stable to 280.degree. C. and containing as little as 36 mol % ethylene and about 41-51 mol % sulfur dioxide; and to the method of producing said terpolymer by irradiation of a liquid and gaseous mixture of ethylene, sulfur dioxide and carbon monoxide by means of Co-60 gamma rays or an electron beam, at a temperature of about 10.degree.-50.degree. C., and at a pressure of about 140 to 680 atmospheres, to initiate polymerization.

Binding of dinitrogen to an iron-sulfur-carbon site

NASA Astrophysics Data System (ADS)

Čorić, Ilija; Mercado, Brandon Q.; Bill, Eckhard; Vinyard, David J.; Holland, Patrick L.

2015-10-01

Nitrogenases are the enzymes by which certain microorganisms convert atmospheric dinitrogen (N2) to ammonia, thereby providing essential nitrogen atoms for higher organisms. The most common nitrogenases reduce atmospheric N2 at the FeMo cofactor, a sulfur-rich iron-molybdenum cluster (FeMoco). The central iron sites that are coordinated to sulfur and carbon atoms in FeMoco have been proposed to be the substrate binding sites, on the basis of kinetic and spectroscopic studies. In the resting state, the central iron sites each have bonds to three sulfur atoms and one carbon atom. Addition of electrons to the resting state causes the FeMoco to react with N2, but the geometry and bonding environment of N2-bound species remain unknown. Here we describe a synthetic complex with a sulfur-rich coordination sphere that, upon reduction, breaks an Fe-S bond and binds N2. The product is the first synthetic Fe-N2 complex in which iron has bonds to sulfur and carbon atoms, providing a model for N2 coordination in the FeMoco. Our results demonstrate that breaking an Fe-S bond is a chemically reasonable route to N2 binding in the FeMoco, and show structural and spectroscopic details for weakened N2 on a sulfur-rich iron site.

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.

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.

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.

Large sulfur isotope fractionations in Martian sediments at Gale crater

NASA Astrophysics Data System (ADS)

Franz, H. B.; McAdam, A. C.; Ming, D. W.; Freissinet, C.; Mahaffy, P. R.; Eldridge, D. L.; Fischer, W. W.; Grotzinger, J. P.; House, C. H.; Hurowitz, J. A.; McLennan, S. M.; Schwenzer, S. P.; Vaniman, D. T.; Archer, P. D., Jr.; Atreya, S. K.; Conrad, P. G.; Dottin, J. W., III; Eigenbrode, J. L.; Farley, K. A.; Glavin, D. P.; Johnson, S. S.; Knudson, C. A.; Morris, R. V.; Navarro-González, R.; Pavlov, A. A.; Plummer, R.; Rampe, E. B.; Stern, J. C.; Steele, A.; Summons, R. E.; Sutter, B.

2017-09-01

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA’s Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in 34S. Measured values of δ34S range from -47 +/- 14‰ to 28 +/- 7‰, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

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.

Theoretical and modeling studies of the atmospheric chemistry of sulfur oxide and hydroxyl radical systems

NASA Astrophysics Data System (ADS)

El-Zanan, Hazem S.

Models are the tools that integrate our understanding of the atmospheric processes. Box models are utilized frequently and used to simulate the fates and transformation of atmospheric pollutants. The results from models are usually used to produce one integrated system and further help the policy makers to develop control strategies. We have investigated the atmospheric chemistry of the SOx and HOx systems. The results of 15 laboratory experiments that involved the studies of the HO-SO2, reaction have been analyzed. Mixtures of HONO, NO, NO2, H2O, SO2 and CO were photolyzed in synthetic air or in nitrogen containing approximately 50 ppm oxygen. Upon analyzing the data we have found that a very large amount of the observed SO2 oxidation (70.0 +/- 9.1%) can not be explained through the gas phase reaction of HO + SO2 reaction alone. The Regional Atmospheric Chemistry Mechanism, Version 2 (RACM2) was used to investigate additional chemical pathways for the oxidation of SO2. The results indicate that a mechanism(s) involving photochemical heterogeneous reactions could account for the observed additional sulfur dioxide oxidation not accounted for by gas phase oxidation alone. We have also investigated the distribution of the hydroxyl radical in different urban and rural areas. Photolysis of ozone and its reactions with nitrogen oxides and organic compounds, including both anthropogenic and biogenic volatile organic compounds (VOCs), control the mixing ratios of the hydroxyl radical (HO). Measurements of ozone, nitrogen oxides and volatile hydrocarbons from a deciduous forest in July 1999 and six sites located in the San Joaquin Valley obtained during the Central California Ozone Study (CCOS) measured in July 2000 and September 2000 were used to estimate the hydroxyl radical concentrations. Two methods were employed to determine the concentrations: (1) box model simulations and (2) steady state approximation of the species concentrations (Production-Loss Method). The

An Aerosol Condensation Model for Sulfur Trioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grant, K E

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,more » 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

Sulfur "Concrete" for Lunar Applications - Sublimation Concerns

NASA Technical Reports Server (NTRS)

Grugel, Richard N.; Toutanji, Houssam

2006-01-01

Melting sulfur and mixing it with an aggregate to form "concrete" is commercially well established and constitutes a material that is particularly well-suited for use in corrosive environments. Discovery of the mineral troilite (FeS) on the moon poses the question of extracting the sulfur for use as a lunar construction material. This would be an attractive alternative to conventional concrete as it does not require water. However, the viability of sulfur concrete in a lunar environment, which is characterized by lack of an atmosphere and extreme temperatures, is not well understood. Here it is assumed that the lunar ore can be mined, refined, and the raw sulfur melded with appropriate lunar regolith to form, for example, bricks. This study evaluates pure sulfur and two sets of small sulfur concrete samples that have been prepared using JSC-1 lunar stimulant and SiO2 powder as aggregate additions. Each set was subjected to extended periods in a vacuum environment to evaluate sublimation issues. Results from these experiments are presented and discussed within the context of the lunar environment.

A novel hybrid approach for estimating total deposition in the United States

NASA Astrophysics Data System (ADS)

Schwede, Donna B.; Lear, Gary G.

2014-08-01

Atmospheric deposition of nitrogen and sulfur causes many deleterious effects on ecosystems including acidification and excess eutrophication. Assessments to support development of strategies to mitigate these effects require spatially and temporally continuous values of nitrogen and sulfur deposition. In the U.S., national monitoring networks exist that provide values of wet and dry deposition at discrete locations. While wet deposition can be interpolated between the monitoring locations, dry deposition cannot. Additionally, monitoring networks do not measure the complete suite of chemicals that contribute to total sulfur and nitrogen deposition. Regional air quality models provide spatially continuous values of deposition of monitored species as well as important unmeasured species. However, air quality modeling values are not generally available for an extended continuous time period. Air quality modeling results may also be biased for some chemical species. We developed a novel approach for estimating dry deposition using data from monitoring networks such as the Clean Air Status and Trends Network (CASTNET), the National Atmospheric Deposition Program (NADP) Ammonia Monitoring Network (AMoN), and the Southeastern Aerosol Research and Characterization (SEARCH) network and modeled data from the Community Multiscale Air Quality (CMAQ) model. These dry deposition values estimates are then combined with wet deposition values from the NADP National Trends Network (NTN) to develop values of total deposition of sulfur and nitrogen. Data developed using this method are made available via the CASTNET website.

Acid-base chemical reaction model for nucleation rates in the polluted atmospheric boundary layer.

PubMed

Chen, Modi; Titcombe, Mari; Jiang, Jingkun; Jen, Coty; Kuang, Chongai; Fischer, Marc L; Eisele, Fred L; Siepmann, J Ilja; Hanson, David R; Zhao, Jun; McMurry, Peter H

2012-11-13

Climate models show that particles formed by nucleation can affect cloud cover and, therefore, the earth's radiation budget. Measurements worldwide show that nucleation rates in the atmospheric boundary layer are positively correlated with concentrations of sulfuric acid vapor. However, current nucleation theories do not correctly predict either the observed nucleation rates or their functional dependence on sulfuric acid concentrations. This paper develops an alternative approach for modeling nucleation rates, based on a sequence of acid-base reactions. The model uses empirical estimates of sulfuric acid evaporation rates obtained from new measurements of neutral molecular clusters. The model predicts that nucleation rates equal the sulfuric acid vapor collision rate times a prefactor that is less than unity and that depends on the concentrations of basic gaseous compounds and preexisting particles. Predicted nucleation rates and their dependence on sulfuric acid vapor concentrations are in reasonable agreement with measurements from Mexico City and Atlanta.

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.

The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth.

PubMed

DeWitt, H Langley; Hasenkopf, Christa A; Trainer, Melissa G; Farmer, Delphine K; Jimenez, Jose L; McKay, Christopher P; Toon, Owen B; Tolbert, Margaret A

2010-10-01

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 × 10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S(8)) and sulfuric acid (H(2)SO(4)) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO(2) either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H(2)) or methane (CH(4)), increased the formation of S(8). With UV photolysis, formation of S(8) aerosols is highly dependent on the initial SO(2) pressure; and S(8) is only formed at a 2% SO(2) mixing ratio and greater in the absence of a reductant, and at a 0.2% SO(2) mixing ratio and greater in the presence of 1000 ppmv CH(4). We also found that organosulfur compounds are formed from the photolysis of CH(4) and moderate amounts of SO(2). The implications for sulfur aerosols on early Earth are discussed. Key Words: S-MIF-Archean atmosphere-Early Earth-Sulfur aerosols.

Volcanoes and atmospheres; catastrophic influences on the planets

USGS Publications Warehouse

Kieffer, S.W.

1986-01-01

For a rare and brief instant in geologic time, we can imagine that the sulfurous, chromatic surface of Io (one of the satellites of Jupiter) lies quiet. Perhaps stars glisten brilliantly through the tenuous nigh sky. Here and there, thick icy fogs enshroud fumaroles where sulfur dioxide leaks from the underworld. Suddenly, a fissure splits the surface and billowing clouds of sulfurous gases and ice hurl orange and black ash into the atmosphere. Minute by minute, the intensity of the eruption builds; stars begin disappearing from the night sky. The rising plume inhales the nearby atmosphere, mixing it with the exhalations from the volcano. Particles of sulfur, sulfur dioxide snow and ash rise to 300 kilometers, later raining down across the planet a thousand kilometers away. 

TRENDS IN RURAL SULFUR CONCENTRATIONS

EPA Science Inventory

This paper presents an analysis of regional trends in atmospheric concentrations in sulfur dioxide (502) and particulate sulfate (50~- ) at rural monitoring sites in the Clean Air Act Status and Trends Monitoring Network (CAsTNet) from 1990 to 1999. A two-stage approach is used t...

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

Terpolymerization of ethylene, sulfur dioxide and carbon monoxide

DOEpatents

Johnson, R.; Steinberg, M.

This invention relates to high molecular weight terpolymer of ethylene, sulfur dioxide and carbon monoxide stable to 280/sup 0/C and containing as little as 36 mo1% ethylene and about 41 to 51 mo1% sulfur dioxide, and to the method of producing said terpolymer by irradiation of a liquid and gaseous mixture of ethylene, sulfur dioxide and carbon monoxide by means of Co-60 gamma rays or an electron beam, at a temperature of about 10 to 50/sup 0/C, and at a pressure of about 140 to 680 atmospheres, to initiate polymerization.

Future Sulfur Dioxide Emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Steven J.; Pitcher, Hugh M.; Wigley, Tom M.

2005-12-01

The importance of sulfur dioxide emissions for climate change is now established, although substantial uncertainties remain. This paper presents projections for future sulfur dioxide emissions using the MiniCAM integrated assessment model. A new income-based parameterization for future sulfur dioxide emissions controls is developed based on purchasing power parity (PPP) income estimates and historical trends related to the implementation of sulfur emissions limitations. This parameterization is then used to produce sulfur dioxide emissions trajectories for the set of scenarios developed for the Special Report on Emission Scenarios (SRES). We use the SRES methodology to produce harmonized SRES scenarios using the latestmore » version of the MiniCAM model. The implications, and requirements, for IA modeling of sulfur dioxide emissions are discussed. We find that sulfur emissions eventually decline over the next century under a wide set of assumptions. These emission reductions result from a combination of emission controls, the adoption of advanced electric technologies, and a shift away from the direct end use of coal with increasing income levels. Only under a scenario where incomes in developing regions increase slowly do global emission levels remain at close to present levels over the next century. Under a climate policy that limits emissions of carbon dioxide, sulfur dioxide emissions fall in a relatively narrow range. In all cases, the relative climatic effect of sulfur dioxide emissions decreases dramatically to a point where sulfur dioxide is only a minor component of climate forcing by the end of the century. Ecological effects of sulfur dioxide, however, could be significant in some developing regions for many decades to come.« less

Sulfur Dioxide Plume from Mt. Etna Eruption 2002 as Detected with AIRS Data

NASA Technical Reports Server (NTRS)

2007-01-01

Mt. Etna, a volcano on the island of Sicily, erupted on October 26, 2002. Preliminary analysis of data taken by the Atmospheric Infrared Sounder (AIRS) on NASA's Aqua satellite on October 28 shows the instrument can provide an excellent means to study the evolution and structure of the sulfur dioxide plume emitted from volcanoes. These data also demonstrate that AIRS can be used to obtain the total mass of sulfur dioxide injected into the atmosphere during a volcanic event, information that may help us to better understand these dangerous natural occurrences in the future.

The image clearly shows the sulfur dioxide plume. This image was created by comparing data taken at two different frequencies, or channels, and creating one image that highlights the differences between these two channels. Both channels are sensitive to water vapor, but one of the channels is also sensitive to sulfur dioxide. By subtracting out the common water vapor signal in both channels, the sulfur dioxide feature remains and shows up as an enhancement in the difference image.

The Atmospheric Infrared Sounder Experiment, with its visible, infrared, and microwave detectors, provides a three-dimensional look at Earth's weather. Working in tandem, the three instruments can make simultaneous observations all the way down to the Earth's surface, even in the presence of heavy clouds. With more than 2,000 channels sensing different regions of the atmosphere, the system creates a global, 3-D map of atmospheric temperature and humidity and provides information on clouds, greenhouse gases, and many other atmospheric phenomena. The AIRS Infrared Sounder Experiment flies onboard NASA's Aqua spacecraft and is managed by NASA's Jet Propulsion Laboratory, Pasadena, Calif., under contract to NASA. JPL is a division of the California Institute of Technology in Pasadena.

Sulfur isotopes in coal constrain the evolution of the Phanerozoic sulfur cycle

PubMed Central

Canfield, Donald E.

2013-01-01

Sulfate is the second most abundant anion (behind chloride) in modern seawater, and its cycling is intimately coupled to the cycling of organic matter and oxygen at the Earth’s surface. For example, the reduction of sulfide by microbes oxidizes vast amounts of organic carbon and the subsequent reaction of sulfide with iron produces pyrite whose burial in sediments is an important oxygen source to the atmosphere. The concentrations of seawater sulfate and the operation of sulfur cycle have experienced dynamic changes through Earth’s history, and our understanding of this history is based mainly on interpretations of the isotope record of seawater sulfates and sedimentary pyrites. The isotope record, however, does not give a complete picture of the ancient sulfur cycle. This is because, in standard isotope mass balance models, there are more variables than constraints. Typically, in interpretations of the isotope record and in the absence of better information, one assumes that the isotopic composition of the input sulfate to the oceans has remained constant through time. It is argued here that this assumption has a constraint over the last 390 Ma from the isotopic composition of sulfur in coal. Indeed, these compositions do not deviate substantially from the modern surface-water input to the oceans. When applied to mass balance models, these results support previous interpretations of sulfur cycle operation and counter recent suggestions that sulfate has been a minor player in sulfur cycling through the Phanerozoic Eon. PMID:23650346

Atmospheric corrections for TIMS estimated emittance

NASA Technical Reports Server (NTRS)

Warner, T. A.; Levandowski, D. W.

1992-01-01

The estimated temperature of the average of 500 lines of Thermal Infrared Multispectral Scanner (TIMS) data of the Pacific Ocean, from flight line 94, collected on 30 Sep. 1988, at 1931 GMT is shown. With no atmospheric corrections, estimated temperature decreases away from nadir (the center of the scan line). A LOWTRAN modeled correction, using local radiosonde data and instrument scan angle information, results in reversed limb darkening effects for most bands, and does not adequately correct all bands to the same temperature. The atmosphere tends to re-radiate energy at the wavelengths at which it most absorbs, and thus the overall difference between corrected and uncorrected temperatures is approximately 40 C, despite the average LOWTRAN calculated transmittance of only 60 percent between 8.1 and 11.6 microns. An alternative approach to atmospheric correction is a black body normalization. This is done by calculating a normalization factor for each pixel position and wavelength, which when applied results in a single calculated temperature, as would be expected for a gray body with near uniform emittance. The black body adjustment is based on the atmospheric conditions over the sea. The ground elevation profile along the remaining 3520 scan lines (approximately 10 km) of flight line 94, up the slopes of Kilauea, determined from aircraft pressure and laser altimeter data is shown. This flight line includes a large amount of vegetation that is clearly discernible on the radiance image, being much cooler than the surrounding rocks. For each of the 3520 scan lines, pixels were classified as vegetation or 'other'. A moving average of 51 lines was applied to the composite vegetation emittance for each scan line, to reduce noise. Assuming vegetation to be like water, and to act as gray body with an emittance of 0.986 across the spectrum, it is shown that that the LOWTRAN induced artifacts are severe, and other than for the 0.9.9 micron channel, not significantly

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

The millimeter-wavelength sulfur dioxide absorption spectra measured under simulated Venus conditions

NASA Astrophysics Data System (ADS)

Bellotti, Amadeo; Steffes, Paul G.

2015-07-01

Over 130 laboratory measurements of the 2-4 mm wavelength opacity of sulfur dioxide in a carbon dioxide atmosphere under simulated conditions for the upper Venus troposphere (temperatures between 308 and 343 K and pressures between 0.03 and 2 bar) have been made. These measurements along with the centimeter wavelength measurements by Steffes et al. (Steffes, P.G. et al. [2015]. Icarus 245, 153-161) have been used to empirically assess existing formalisms for sulfur dioxide opacity in a carbon dioxide atmosphere (Fahd, A.K., Steffes, P.G. [1992]. Icarus 97(2), 200-210; Suleiman, S.H. et al. [1996]. J. Geophys. Res.: Planets 101(E2), 4623-4635). The Van Vleck and Weisskopf Model (VVW) used by Fahd and Steffes with the JPL rotational line catalog (Pickett, H. et al. [1998]. J. Quant. Spectrosc. Radiat. Transfer 60(5), 499-890) was found to fit 85.88% of all 500 measurements within the 2-sigma uncertainty. This work will improve the confidence in retrievals of the atmospheric abundance of sulfur dioxide from millimeter-wavelength observations of the Venus atmosphere.

Bacterial sulfur disproportionation constrains timing of neoproterozoic oxygenation

USGS Publications Warehouse

Kunzmann, Marcus; Bui, Thi Hao; Crockford, Peter W.; Halverson, Galen P.; Scott, Clinton T.; Lyons, Timothy W.; Wing, Boswell A.

2017-01-01

Various geochemical records suggest that atmospheric O2 increased in the Ediacaran (635–541 Ma), broadly coincident with the emergence and diversification of large animals and increasing marine ecosystem complexity. Furthermore, geochemical proxies indicate that seawater sulfate levels rose at this time too, which has been hypothesized to reflect increased sulfide oxidation in marine sediments caused by sediment mixing of the newly evolved macrofauna. However, the exact timing of oxygenation is not yet understood, and there are claims for significant oxygenation prior to the Ediacaran. Furthermore, recent evidence suggests that physical mixing of sediments did not become important until the late Silurian. Here we report a multiple sulfur isotope record from a ca. 835–630 Ma succession from Svalbard, further supported by data from Proterozoic strata in Canada, Australia, Russia, and the United States, in order to investigate the timing of oxygenation. We present isotopic evidence for onset of globally significant bacterial sulfur disproportionation and reoxidative sulfur cycling following the 635 Ma Marinoan glaciation. Widespread sulfide oxidation helps to explain the observed first-order increase in seawater sulfate concentration from the earliest Ediacaran to the Precambrian-Cambrian boundary by reducing the amount of sulfur buried as pyrite. Expansion of reoxidative sulfur cycling to a global scale also indicates increasing environmental O2 levels. Thus, our data suggest that increasing atmospheric O2 levels may have played a role in the emergence of the Ediacaran macrofauna and increasing marine ecosystem complexity.

Atmosphere-Ocean Coupling through Trace Gases

NASA Astrophysics Data System (ADS)

Tegtmeier, S.; Atlas, E. L.; Krüger, K.; Lennartz, S. T.; Marandino, C. A.; Patra, P. K.; Quack, B.; Schlundt, C.

2017-12-01

Halogen- and sulfur-containing trace gases, as well as other volatile organic compounds (VOCs, such as isoprene) from biogeochemical marine sources are important constituents of the ocean and the atmosphere. These compounds exert wide-ranging influence on atmospheric chemical processes and climate interactions, as well as on human health in coastal regions. In their reactive form, they can affect the oxidizing capacity of the air and lead to the formation of new particles or the growth of existing ones. In this contribution, marine derived halogen-, sulfur-, and oxygen-containing compounds will be discussed. Their net flux into the atmosphere and their impact on atmospheric processes is analyzed based on observations and model simulations.

Acid–base chemical reaction model for nucleation rates in the polluted atmospheric boundary layer

PubMed Central

Chen, Modi; Titcombe, Mari; Jiang, Jingkun; Jen, Coty; Kuang, Chongai; Fischer, Marc L.; Eisele, Fred L.; Siepmann, J. Ilja; Hanson, David R.; Zhao, Jun; McMurry, Peter H.

2012-01-01

Climate models show that particles formed by nucleation can affect cloud cover and, therefore, the earth's radiation budget. Measurements worldwide show that nucleation rates in the atmospheric boundary layer are positively correlated with concentrations of sulfuric acid vapor. However, current nucleation theories do not correctly predict either the observed nucleation rates or their functional dependence on sulfuric acid concentrations. This paper develops an alternative approach for modeling nucleation rates, based on a sequence of acid–base reactions. The model uses empirical estimates of sulfuric acid evaporation rates obtained from new measurements of neutral molecular clusters. The model predicts that nucleation rates equal the sulfuric acid vapor collision rate times a prefactor that is less than unity and that depends on the concentrations of basic gaseous compounds and preexisting particles. Predicted nucleation rates and their dependence on sulfuric acid vapor concentrations are in reasonable agreement with measurements from Mexico City and Atlanta. PMID:23091030

Elemental sulfur aerosol-forming mechanism

NASA Astrophysics Data System (ADS)

Kumar, Manoj; Francisco, Joseph S.

2017-01-01

Elemental sulfur aerosols are ubiquitous in the atmospheres of Venus, ancient Earth, and Mars. There is now an evolving body of evidence suggesting that these aerosols have also played a role in the evolution of early life on Earth. However, the exact details of their formation mechanism remain an open question. The present theoretical calculations suggest a chemical mechanism that takes advantage of the interaction between sulfur oxides, SOn (n = 1, 2, 3) and hydrogen sulfide (nH2S), resulting in the efficient formation of a Sn+1 particle. Interestingly, the SOn + nH2S → Sn+1 + nH2O reactions occur via low-energy pathways under water or sulfuric acid catalysis. Once the Sn+1 particles are formed, they may further nucleate to form larger polysulfur aerosols, thus providing a chemical framework for understanding the formation mechanism of S0 aerosols in different environments.

Emissions of sulfur gases from wetlands

NASA Technical Reports Server (NTRS)

Hines, Mark E.

1992-01-01

Data on the emissions of sulfur gases from marine and freshwater wetlands are summarized with respect to wetland vegetation type and possible formation mechanisms. The current data base is largest for salt marshes inhabited by Spartina alterniflora. Both dimethyl sulfide (DMS) and hydrogen sulfide (H2S) dominate emissions from salt marshes, with lesser quantities of methyl mercaptan (MeSH), carbonyl sulfide (COS), carbon disulfide (CS2) and dimethyl disulfide (DMDS) being emitted. High emission rates of DMS are associated with vegetation that produces the DMS precursor dimethylsulfonionpropionate (DMSP). Although large quantities of H2S are produced in marshes, only a small percentage escapes to the atmosphere. High latitude marshes emit less sulfur gases than temperate ones, but DMS still dominates. Mangrove-inhabited wetlands also emit less sulfur than temperate S. alterniflora marshes. Few data are available on sulfur gas emissions from freshwater wetlands. In most instances, sulfur emissions from temperate freshwater sites are low. However, some temperate and subtropical freshwater sites are similar in magnitude to those from marine wetlands which do not contain vegetation that produces DMSP. Emissions are low in Alaskan tundra but may be considerably higher in some bogs and fens.

Non-steady state diagenesis of organic and inorganic sulfur in lake sediments

NASA Astrophysics Data System (ADS)

Couture, Raoul-Marie; Fischer, Rachele; Van Cappellen, Philippe; Gobeil, Charles

2016-12-01

Sulfur controls the fate of many geochemical elements in lake sediments, including iron, phosphorus and environmentally important trace elements. We measured the speciation of pore-water and sediment-bound sulfur (aqueous sulfate and sulfides, elemental sulfur, iron monosulfide, pyrite, organic sulfur) and supporting geochemical variables (carbon, oxygen, iron) in the sediments of a perennially oxygenated and a seasonally anoxic basin of an oligotrophic lake in Québec, using a combination of pore-water analyses, sequential extractions and X-ray absorption near edge structure. A non-steady state early diagenetic model was developed and calibrated against this extensive dataset to help unravel the pathways and quantify the rates of S transformations. Results suggest that the main source of S to the sediments is the settling of organic ester-sulfate (R-O-SO3-H). Hydrolysis of these compounds provides an additional source of sulfate for anaerobic microbial oxidation of sedimentary organic matter, releasing sulfide to the pore-water. Reduced solid-bound S species accumulate as thiols (R-SH) and iron sulfides in the perennially oxygenated and seasonally anoxic basin, respectively. The model-estimated rate constant for R-SH formation is lower than previously estimated for this particular lacustrine site, but similar to that proposed for marine shelf sediments. The solid sediment S profiles, however, carry the imprint of the time-dependent sulfate input to the lake. Iron sulfide enrichments formed during past decades of elevated atmospheric SO4 deposition are presently dissolving. In the sediments of the perennially oxygenated basin this reaction hampers the build-up of Fe(III) (oxy)hydroxide near the sediment-water interface.

Photo-oxidative doping in π-conjugated zig-zag chain of carbon atoms with sulfur-functional group

NASA Astrophysics Data System (ADS)

Ikeura-Sekiguchi, Hiromi; Sekiguchi, Tetsuhiro

2017-12-01

Photo-oxidative doping processes were studied for the trans-polyacetylene backbone with the -SCH3 side group as a chemically representative of the precisely controlled S-functionalized zig-zag graphene nanoribbon edge. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy indicates that photochemical reaction of S-CH3 with atmospheric O2 forms selectively oxidized products such as -S(O)CH3 and -SO3- bound to the polyacetylene (PA) backbone. Using the correlation between the oxidation states of sulfur and the XANES peak positions, the partial charge distribution of CH3Sδ+-PAδ- has been estimated. Such positively charged sulfur atoms can attract higher electronegative oxygen atoms and expect to enhance the photooxidization capabilities. The formation of the -SO3- side group is evidently responsible for hole doping into the PA backbone. The results can provide some strategy for area-selective and controllable doping processes of atomic-scale molecular systems with the assistance of UV light.

Some thoughts on GAIA and the sulfur cycle

NASA Technical Reports Server (NTRS)

Lovelock, J. E.

1985-01-01

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

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

Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs

PubMed Central

2014-01-01

Background The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. Results Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 μmol L-1) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ34S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ34S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur–polysulfide – hydrogen sulfide system. Triple sulfur isotope (32S, 33S, 34S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆33S among

Photochemical Formation of Aerosol in Planetary Atmospheres: Photon and Water Mediated Chemistry of SO_2

NASA Astrophysics Data System (ADS)

Kroll, Jay A.; Donaldson, D. J.; Vaida, Veronica

2016-06-01

Sulfur compounds have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere. However, several discrepancies between modeling and observations of the Venusian atmosphere show there are still problems in our fundamental understanding of sulfur chemistry. This is of particular concern due to the important role sulfur compounds play in the formation of aerosols, which have a direct impact on planetary climates, including Earth's. We investigate the role of water complexes in the hydration of sulfur oxides and dehydration of sulfur acids and will present spectroscopic studies to document such effects. I will present recent work investigating mixtures of SO_2 and water that generate large quantities of aerosol when irradiated with solar UV light, even in the absence of traditional OH chemistry. I will discuss a proposed mechanism for the formation of sulfurous acid (H_2SO_3) and present recent experimental work that supports this proposed mechanism. Additionally, the implications that photon-induced hydration of SO_2 has for aerosol formation in the atmosphere of earth as well as other planetary atmospheres will be discussed.

Maxine: A spreadsheet for estimating dose from chronic atmospheric radioactive releases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jannik, Tim; Bell, Evaleigh; Dixon, Kenneth

MAXINE is an EXCEL© spreadsheet, which is used to estimate dose to individuals for routine and accidental atmospheric releases of radioactive materials. MAXINE does not contain an atmospheric dispersion model, but rather doses are estimated using air and ground concentrations as input. Minimal input is required to run the program and site specific parameters are used when possible. Complete code description, verification of models, and user’s manual have been included.

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

Sulfuric acid-sulfur heat storage cycle

DOEpatents

Norman, John H.

1983-12-20

A method of storing heat is provided utilizing a chemical cycle which interconverts sulfuric acid and sulfur. The method can be used to levelize the energy obtained from intermittent heat sources, such as solar collectors. Dilute sulfuric acid is concentrated by evaporation of water, and the concentrated sulfuric acid is boiled and decomposed using intense heat from the heat source, forming sulfur dioxide and oxygen. The sulfur dioxide is reacted with water in a disproportionation reaction yielding dilute sulfuric acid, which is recycled, and elemental sulfur. The sulfur has substantial potential chemical energy and represents the storage of a significant portion of the energy obtained from the heat source. The sulfur is burned whenever required to release the stored energy. A particularly advantageous use of the heat storage method is in conjunction with a solar-powered facility which uses the Bunsen reaction in a water-splitting process. The energy storage method is used to levelize the availability of solar energy while some of the sulfur dioxide produced in the heat storage reactions is converted to sulfuric acid in the Bunsen reaction.

Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions.

PubMed

Baroni, Mélanie; Thiemens, Mark H; Delmas, Robert J; Savarino, Joël

2007-01-05

The observed mass-independent sulfur isotopic composition (Delta33S) of volcanic sulfate from the Agung (March 1963) and Pinatubo (June 1991) eruptions recorded in the Antarctic snow provides a mechanism for documenting stratospheric events. The sign of Delta33S changes over time from an initial positive component to a negative value. Delta33S is created during photochemical oxidation of sulfur dioxide to sulfuric acid on a monthly time scale, which indicates a fast process. The reproducibility of the results reveals that Delta33S is a reliable tracer to chemically identify atmospheric processes involved during stratospheric volcanism.

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.

REGIONAL TRENDS IN RURAL SULFUR CONCENTRATIONS

EPA Science Inventory

This paper presents an analysis of trends in atmospheric concentrations of sulfur dioxide (SO,) and particulate sulfate (SO42-) at rural monitoring sites in the Clean Air Act Status and Trends Monitoring Network (CASTNet) from 1990 to 1999. A two-stage approach is used to estimat...

Oxidized sulfur-rich mafic magma at Mount Pinatubo, Philippines

USGS Publications Warehouse

de Hoog, J.C.M.; Hattori, K.H.; Hoblitt, R.P.

2004-01-01

Basaltic fragments enclosed in andesitic dome lavas and pyroclastic flows erupted during the early stages of the 1991 eruption of Mount Pinatubo, Philippines, contain amphiboles that crystallized during the injection of mafic magma into a dacitic magma body. The amphiboles contain abundant melt inclusions, which recorded the mixing of andesitic melt in the mafic magma and rhyolitic melt in the dacitic magma. The least evolved melt inclusions have high sulfur contents (up to 1,700 ppm) mostly as SO42, which suggests an oxidized state of the magma (NNO + 1.4). The intrinsically oxidized nature of the mafic magma is confirmed by spinel-olivine oxygen barometry. The value is comparable to that of the dacitic magma (NNO + 1.6). Hence, models invoking mixing as a means of releasing sulfur from the melt are not applicable to Pinatubo. Instead, the oxidized state of the dacitic magma likely reflects that of parental mafic magma and the source region in the sub-arc mantle. Our results fit a model in which long-lived SO2 discharge from underplated mafic magma accumulated in the overlying dacitic magma and immiscible aqueous fluids. The fluids were the most likely source of sulfur that was released into the atmosphere during the cataclysmic eruption. The concurrence of highly oxidized basaltic magma and disproportionate sulfur output during the 1991 Mt. Pinatubo eruption suggests that oxidized mafic melt is an efficient medium for transferring sulfur from the mantle to shallow crustal levels and the atmosphere. As it can carry large amounts of sulfur, effectively scavenge sulfides from the source mantle and discharge SO2 during ascent, oxidized mafic magma forms arc volcanoes with high sulfur fluxes, and potentially contributes to the formation of metallic sulfide deposits. ?? Springer-Verlag 2003.

Hydrogen sulfide emission in sewer networks: a two-phase modeling approach to the sulfur cycle.

PubMed

Yongsiri, C; Vollertsen, J; Hvitved-Jacobsen, T

2004-01-01

Wherever transport of anaerobic wastewater occurs, potential problems associated with hydrogen sulfide in relation to odor nuisance, health risk and corrosion exist. Improved understanding of prediction of hydrogen sulfide emission into the sewer atmosphere is needed for better evaluation of such problems in sewer networks. A two-phase model for emission of hydrogen sulfide along stretches of gravity sewers is presented to estimate the occurrence of both sulfide in the water phase and hydrogen sulfide in the sewer atmosphere. The model takes into account air-water mass transfer of hydrogen sulfide and interactions with other processes in the sulfur cycle. Various emission scenarios are simulated to illustrate the release characteristics of hydrogen sulfide.

Quantitative determination of sulfur content in concrete with laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Weritz, F.; Ryahi, S.; Schaurich, D.; Taffe, A.; Wilsch, G.

2005-08-01

Laser-induced breakdown spectroscopy has been employed for the investigation of the sulfur content of concrete. Sulfur compounds are a natural but minor component in building materials. The ingress of sulfates or sulfuric acid constitutes a major risk of chemical aggression for concrete. There is a need for a fast method, which can be used on-site and is able to investigate a wide range of different measuring points, so that damages can be characterized. For quantitative determination the sulfur spectral line at 921.3 nm is used. The optimum ambient atmosphere has been determined by comparison of measurements accomplished under air, argon and helium atmosphere. Reference samples have been produced and calibration curves have been determined, the results of LIBS measurements are compared with results from chemical analysis. Defining a limit for the intensity ratio of a calcium and a oxygen spectral line can reduce the influence of the heterogeneity of the material, so that only spectra with a high amount of cementitious material are evaluated. Depth profiles and spatial resolved sulfur distributions are presented measured on concrete cores originating from a highly sulfate contaminated clarifier.

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

DOEpatents

Clay, David T.; Lynn, Scott

1976-10-19

A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

The Formation of Sulfate and Elemental Sulfur Aerosols Under Varying Laboratory Conditions: Implications for Early Earth

NASA Technical Reports Server (NTRS)

DeWitt, H. Langley; Hasenkopf, Christa A.; Trainer, Melissa G.; Farmer, Delphine K.; Jimenez, Jose L.; McKay, Christopher P.; Toon, Owen B.; Tolbert, Margaret A.

2010-01-01

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 x 10(exp 9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO2) by UV light with lambda < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S8) and sulfuric acid (H2S04) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO2 either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H2) or methane (CH4), increased the formation of S8. With UV photolysis, formation of S8 aerosols is highly dependent on the initial SO2 pressure; and S8 is only formed at a 2% SO2 mixing ratio and greater in the absence of a reductant, and at a 0.2% SO2 mixing ratio and greater in the presence of 1000 ppmv CH4. We also found that organosulfur compounds are formed from the photolysis of CH4 and moderate amounts of SO2, The implications for sulfur aerosols on early Earth are discussed.

Development of {110}<001> annealing texture in Al-free and 0.1 %Mn-added 3 %Si-Fe alloy strips containing 95 ppm sulfur

NASA Astrophysics Data System (ADS)

Heo, N. H.; Yoon, G. G.

2010-04-01

The solubility of sulfur is calculated in 0.1 %Mn-added 3 %Si-Fe alloys. The segregation kinetics of sulfur is compared in the alloy containing 95 ppm sulfur, depending on the annealing atmosphere. The effects of pre-annealing and annealing atmosphere on final annealing texture are investigated. Segregation behaviors of sulfur at free surfaces and grain boundaries are compared and, during the selective growth, the importance of the grain boundary concentration of sulfur is emphasized. Finally, a correlation between the development of the annealing texture and segregation kinetics of sulfur in the alloy strip is discussed.

Atmospheric sulfur cycling in the southeastern Pacific - longitudinal distribution, vertical profile, and diel variability observed during VOCALS-REx

NASA Astrophysics Data System (ADS)

Yang, M.; Huebert, B. J.; Blomquist, B. W.; Howell, S. G.; Shank, L. M.; McNaughton, C. S.; Clarke, A. D.; Hawkins, L. N.; Russell, L. M.; Covert, D. S.; Coffman, D. J.; Bates, T. S.; Quinn, P. K.; Zagorac, N.; Bandy, A. R.; de Szoeke, S. P.; Zuidema, P. D.; Tucker, S. C.; Brewer, W. A.; Benedict, K. B.; Collett, J. L.

2011-05-01

Dimethylsulfide (DMS) emitted from the ocean is a biogenic precursor gas for sulfur dioxide (SO2) and non-sea-salt sulfate aerosols (SO42-). During the VAMOS-Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) in 2008, multiple instrumented platforms were deployed in the Southeastern Pacific (SEP) off the coast of Chile and Peru to study the linkage between aerosols and stratocumulus clouds. We present here observations from the NOAA Ship Ronald H. Brown and the NSF/NCAR C-130 aircraft along ~20° S from the coast (70° W) to a remote marine atmosphere (85° W). While SO42- and SO2 concentrations were distinctly elevated above background levels in the coastal marine boundary layer (MBL) due to anthropogenic influence (~800 and 80 pptv, respectively), their concentrations rapidly decreased west of 78° W (~100 and 25 pptv). In the remote region, entrainment from the free troposphere (FT) increased MBL SO2 burden at a rate of 0.05 ± 0.02 μmoles m-2 day-1 and diluted MBL SO42 burden at a rate of 0.5 ± 0.3 μmoles m-2 day-1, while the sea-to-air DMS flux (3.8 ± 0.4 μmoles m-2 day-1) remained the predominant source of sulfur mass to the MBL. In-cloud oxidation was found to be the most important mechanism for SO2 removal and in situ SO42- production. Surface SO42- concentration in the remote MBL displayed pronounced diel variability, increasing rapidly in the first few hours after sunset and decaying for the rest of the day. We theorize that the increase in SO42- was due to nighttime recoupling of the MBL that mixed down cloud-processed air, while decoupling and sporadic precipitation scavenging were responsible for the daytime decline in SO42-.

Sulfur and Methylmercury in the Florida Everglades - the Biogeochemical Connection

NASA Astrophysics Data System (ADS)

Orem, W. H.; Gilmour, C. C.; Krabbenhoft, D. P.; Aiken, G.

2011-12-01

Methylmercury (MeHg) is a serious environmental problem in aquatic ecosystems worldwide because of its toxicity and tendency to bioaccumulate. The Everglades receives some of the highest levels of atmospheric mercury deposition and has some of the highest levels of MeHg in fish in the USA, posing a threat to pisciverous wildlife and people through fish consumption. USGS studies show that a combination of biogeochemical factors make the Everglades especially susceptible to MeHg production and bioaccumulation: (1) vast wetland area with anoxic soils supporting anaerobic microbial activity, (2) high rates of atmospheric mercury deposition, (3) high levels of dissolved organic carbon (DOC) that complexes and stabilizes mercury in solution for transport to sites of methylation, and (4) high sulfate loading in surface water that drives microbial sulfate reduction and mercury methylation. The high levels of sulfate in the Everglades represent an unnatural condition. Background sulfate levels are estimated to be <1 mg/L, but about 60% of the Everglades has surface water sulfate concentrations exceeding background. Highly sulfate-enriched marshes in the northern Everglades have average sulfate levels of 60 mg/L. Sulfate loading to the Everglades is principally a result of land and water management in south Florida. The highest concentrations of sulfate, averaging 60-70 mg/L, are in canal water in the Everglades Agricultural Area (EAA). Geochemical data and a preliminary sulfur mass balance for the EAA are consistent with sulfur currently used in agriculture, and sulfur released by oxidation of organic EAA soils (including legacy agricultural applications and natural sulfur) as the primary sources of sulfate enrichment to the canals and ecosystem. Sulfate loading increases microbial sulfate reduction and MeHg production in soils. The relationship between sulfate loading and MeHg production, however, is complex. Sulfate levels up to about 20-30 mg/L increase mercury

Sulfur 'Concrete' for Lunar Applications - Environmental Considerations

NASA Technical Reports Server (NTRS)

Grugel, R. N.

2008-01-01

Commercial use of sulfur concrete on Earth is well established, particularly in corrosive, e.g., acid and salt, environments. Having found troilite (FeS) on the Moon raises the question of using extracted sulfur as a lunar construction material, an attractive alternative to conventional concrete as it does not require water. For the purpose of this Technical Memorandum, it is assumed that lunar ore is mined, refined, and the raw sulfur processed with appropriate lunar regolith to form, for example, bricks. With this stipulation, it is then noted that the viability of sulfur concrete in a lunar environment, which is characterized by lack of an atmosphere and extreme temperatures, is not well understood. The work presented here evaluates two sets of small sulfur concrete samples that have been prepared using JSC-1 lunar simulant as an aggregate addition. One set was subjected to extended periods in high vacuum to evaluate sublimation issues, and the other was cycled between room and liquid nitrogen temperatures to investigate their subsequent mechanical integrity. Results are presented from both investigations, discussed, and put into the context of the lunar environment.

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

Estimating atmospheric visibility using synergy of MODIS data and ground-based observations

NASA Astrophysics Data System (ADS)

Komeilian, H.; Mohyeddin Bateni, S.; Xu, T.; Nielson, J.

2015-05-01

Dust events are intricate climatic processes, which can have adverse effects on human health, safety, and the environment. In this study, two data mining approaches, namely, back-propagation artificial neural network (BP ANN) and supporting vector regression (SVR), were used to estimate atmospheric visibility through the synergistic use of Moderate Resolution Imaging Spectroradiometer (MODIS) Level 1B (L1B) data and ground-based observations at fourteen stations in the province of Khuzestan (southwestern Iran), during 2009-2010. Reflectance and brightness temperature in different bands (from MODIS) along with in situ meteorological data were input to the models to estimate atmospheric visibility. The results show that both models can accurately estimate atmospheric visibility. The visibility estimates from the BP ANN network had a root-mean-square error (RMSE) and Pearson's correlation coefficient (R) of 0.67 and 0.69, respectively. The corresponding RMSE and R from the SVR model were 0.59 and 0.71, implying that the SVR approach outperforms the BP ANN.

Bidirectional Interaction of Alanine with Sulfuric Acid in the Presence of Water and the Atmospheric Implication.

PubMed

Wang, Chun-Yu; Ma, Yan; Chen, Jiao; Jiang, Shuai; Liu, Yi-Rong; Wen, Hui; Feng, Ya-Juan; Hong, Yu; Huang, Teng; Huang, Wei

2016-04-21

Amino acids are recognized as important components of atmospheric aerosols, which impact on the Earth's climate directly and indirectly. However, much remains unknown about the initial events of nucleation. In this work, the interaction of alanine [NH2CH(CH3)COOH or Ala], one of the most abundant amino acids in the atmosphere, with sulfuric acid (SA) and water (W) has been investigated at the M06-2X/6-311++G(3df, 3pd) level of theory. We have studied thermodynamics of the hydrated (Ala)(SA) core system with up to four water molecules. We found that Ala, with one amino group and one carboxyl group, can interact with H2SO4 and H2O in two directions and that it has a high cluster stabilizing effect similar to that of ammonia, which is one of the key nucleation precursor. The corresponding Gibbs free energies of the (Ala)(SA)(W)n (n = 0-4) clusters formation at 298.15 K predicted that Ala can contribute to the stabilization of small binary clusters. Our results showed that the hydrate distribution is temperature-dependent and that a higher humidity and temperature can contribute to the formation of hydrated clusters.

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

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].

Review of sulfur dioxide to sulfate aerosol chemistry at Kīlauea Volcano, Hawai'i

NASA Astrophysics Data System (ADS)

Pattantyus, Andre K.; Businger, Steven; Howell, Steven G.

2018-07-01

Sulfur dioxide emissions from the Kīlauea Volcano on the island of Hawai'i and the subsequent formation of sulfate aerosols have caused a public health hazard across the state of Hawai'i since the volcano began erupting continuously in 1983. The University of Hawai'i at Mānoa began to forecast the trajectory and dispersion of emissions in 2010 to help mitigate the hazards to public health. In this paper a comprehensive review of potential conversion reactions is presented with the goal of more accurately representing the sulfur dioxide chemistry in the dispersion model. Atmospheric sulfur dioxide chemistry and major process responsible for sulfate formation are well documented in urban and industrial settings. The atmosphere in the vicinity of Kīlauea Volcano on the island of Hawai'i differs from that in previous investigations by virtue of being far removed from both urban and industrial settings in a remote, tropical marine atmosphere. Additionally, the combination of the high rate of sulfur dioxide emissions and trace gases and metals from Kīlauea Volcano creates a unique circumstance that requires a new look at potential conversion pathways to determine the dominant reactions. The theoretical analysis suggests that the dominant reaction in clear air will be between sulfur dioxide and the hydroxyl radical (0.01-5% h-1) and the dominant reaction in cloudy air involves hydrogen peroxide (3-50% s-1). Moreover, given the high SO2 emissions from the Halema'uma'u Crater vent, the oxidation of sulfur dioxide by these reactants is limited by their rate of production.

Integrated Science Assessment (ISA) for Sulfur Oxides ...

EPA Pesticide Factsheets

This draft document provides EPA’s evaluation and synthesis of the most policy-relevant science related to the health effects of sulfur oxides. When final, it will provide a critical part of the scientific foundation for EPA’s decision regarding the adequacy of the current primary (health-based) National Ambient Air Quality Standard (NAAQS) for sulfur dioxide. The references considered for inclusion in or cited in the external review draft ISA are available at https://hero.epa.gov/hero/sulfur-oxides. The intent of the ISA, according to the CAA, is to “accurately reflect the latest scientific knowledge expected from the presence of [a] pollutant in ambient air” (U.S. Code, 1970a, 1970b). It includes an assessment of scientific research from atmospheric sciences, exposure sciences, dosimetry, mode of action, animal and human toxicology, and epidemiology. Key information and judgments formerly found in the Air Quality Criteria Documents (AQCDs) for sulfur oxides (SOx) are included; Annexes provide additional details supporting the ISA. Together, the ISA and Annexes serve to update and revise the last SOx ISA which was published in 2008.

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.

Improved atmospheric effect elimination method for the roughness estimation of painted surfaces.

PubMed

Zhang, Ying; Xuan, Jiabin; Zhao, Huijie; Song, Ping; Zhang, Yi; Xu, Wujian

2018-03-01

We propose a method for eliminating the atmospheric effect in polarimetric imaging remote sensing by using polarimetric imagers to simultaneously detect ground targets and skylight, which does not need calibrated targets. In addition, calculation efficiencies are improved by the skylight division method without losing estimation accuracy. Outdoor experiments are performed to obtain the polarimetric bidirectional reflectance distribution functions of painted surfaces and skylight under different weather conditions. Finally, the roughness of the painted surfaces is estimated. We find that the estimation accuracy with the proposed method is 6% on cloudy weather, while it is 30.72% without atmospheric effect elimination.

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

USGS Publications Warehouse

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

2016-01-01

tree-ring δ15N values at these sites. Other factors, such as decreased sulfur deposition, disturbance, long-term successional trends, and/or increasing atmospheric CO2concentrations, 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.

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.

The simulations of sulfuric acid concentration and new particle formation in an urban atmosphere in China

NASA Astrophysics Data System (ADS)

Wang, Z. B.; Hu, M.; Mogensen, D.; Yue, D. L.; Zheng, J.; Zhang, R. Y.; Liu, Y.; Yuan, B.; Li, X.; Shao, M.; Zhou, L.; Wu, Z. J.; Wiedensohler, A.; Boy, M.

2013-11-01

Simulations of sulfuric acid concentration and new particle formation are performed by using the zero-dimensional version of the model MALTE (Model to predict new Aerosol formation in the Lower TropospherE) and measurements from the Campaign of Air Quality Research in Beijing and Surrounding areas (CAREBeijing) in 2008. Chemical reactions from the Master Chemical Mechanism version 3.2 (MCM v3.2) are used in the model. High correlation (slope = 0.72, R = 0.74) between the modelled and observed sulfuric acid concentrations is found during daytime (06:00-18:00). The aerosol dynamics are simulated by the University of Helsinki Multicomponent Aerosol (UHMA) model including several nucleation mechanisms. The results indicate that the model is able to predict the on- and offset of new particle formation in an urban atmosphere in China. In addition, the number concentrations of newly formed particles in kinetic-type nucleation including homogenous homomolecular (J=K[H2SO4]2) and homogenous heteromolecular nucleation involving organic vapours (J=Khet[H2SO4][Org]) are in satisfactory agreement with the observations. However, the specific organic compounds that possibly participate in the nucleation process should be investigated in further studies. For the particle growth, only a small fraction of the oxidized total organics condense onto the particles in polluted environments. Meanwhile, the OH and O3 oxidation mechanism contribute 5.5% and 94.5% to the volume concentration of small particles, indicating the particle growth is more controlled by the precursor gases and their oxidation by O3.

Sulfur in zircons: A new window into melt chemistry

NASA Astrophysics Data System (ADS)

Tang, H.; Bell, E. A.; Boehnke, P.; Barboni, M.; Harrison, T. M.

2017-12-01

The abundance and isotopic composition of sulfur are important tools for exploring the photochemistry of the atmosphere, the thermal history of mantle and igneous rocks, and ancient metabolic processes on the early Earth. Because the oldest terrestrial samples are zircons, we developed a new in-situ procedure to analyze the sulfur content of zircons using the CAMECA ims 1290 at UCLA. We analyzed zircons from three metaluminous/I-type granites (reduced and oxidized Peninsular range and Elba), which exhibit low sulfur abundance with the average of 0.5ppm, and one peraluminous/S-type zircon (Strathbogie Range), which shows an elevated sulfur level with the average of 1.5ppm. Additionally, we found that sulfur content ranges between 0.4 and 2.3 ppm in young volcanic zircons (St. Lucia). Our analyses of zircons from the Jack Hills, Western Australia, whose ages range between 3.4 and 4.1 Ga, show a variety of sulfur contents. Three out of the ten zircons are consistent with the sulfur contents of S-type zircons; the rest have low sulfur contents, which are similar to those of I-type zircons. The high sulfur content in some of these Jack Hills zircons can be interpreted as indicating their origin in either a S-type granite or a volcanic reservoir. We favor the former interpretation since the Ti-in-zircon temperatures of our Jack Hills zircons is lower than those of volcanic zircons. Future work will be undertaken to develop a systematic understanding of the relationship between melt volatile content, melt chemistry, and zircon sulfur content.

Changes in atmospheric sulfur burdens and concentrations and resulting radiative forcings under IPCC SRES emission scenarios for 1990-2100

NASA Astrophysics Data System (ADS)

Pham, M.; Boucher, O.; Hauglustaine, D.

2005-03-01

Simulations of the global sulfur cycle under the IPCC SRES scenarios have been performed. Sulfur dioxide and sulfate burdens, as well as the direct and first indirect radiative forcing (RF) by sulfate aerosols only, are presented for the period 1990 to 2100. By 2100, global sulfur emission rates decline everywhere in all scenarios. At that time, the anthropogenic sulfate burden ranges from 0.34 to 1.03 times the 1990 value of 0.47 Tg S. Direct and indirect global and annually mean RFs relative to the year 1990 are near 0 or positive (range of -0.07 to 0.28 Wm-2 and 0.01 to 0.38 Wm-2 for the direct and indirect effects, respectively). For reference these forcings amount respectively to -0.42 and -0.79 Wm-2 in 1990 relative to preindustrial conditions (around 1750). Sulfur aerosols will therefore induce a smaller cooling effect in 2100 than in 1990 relative to preindustrial conditions. For the period 1990 to 2100, the forcing efficiencies (computed relatively to 1990) are fairly constant for the direct effect (around -160 W (g sulfate)-1). The forcing efficiencies for the indirect effect are around -200 and -100 W (g sulfate)-1 for negative and positive burden differences, respectively. This is due to a shift in regional patterns of emissions and a saturation in the indirect effect. The simulated annually averaged SO2 concentrations for A1B scenario in 2020 are close to air quality objectives for public health in some parts of Africa and exceed these objectives in some parts of China and Korea. Moreover, sulfate deposition rates are estimated to increase by 200% from the present level in East and Southeast Asia. This shows that Asia may experience in the future sulfur-related environmental and human health problems as important as Europe and the United States did in the 1970s.

MIPAS ESA v7 carbon tetrachloride data: distribution, trend and atmospheric lifetime estimation

NASA Astrophysics Data System (ADS)

Valeri, M.; Barbara, F.; Boone, C. D.; Ceccherini, S.; Gai, M.; Maucher, G.; Raspollini, P.; Ridolfi, M.; Sgheri, L.; Wetzel, G.; Zoppetti, N.

2017-12-01

Carbon tetrachloride (CCl4) is a strong ozone-depleting atmospheric gas regulated by the Montreal protocol. Recently it received increasing interest due to the so called "mystery of CCl4": it was found that its atmospheric concentration at the surface declines with a rate significantly smaller than its lifetime-limited rate. Indeed there is a discrepancy between atmospheric observations and the estimated distribution based on the reported production and consumption. Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) measurements are used to estimate CCl4 distributions, its trend, and atmospheric lifetime in the upper troposphere / lower stratosphere (UTLS) region. In particular, here we use MIPAS product generated with Version 7 of the Level 2 algorithm operated by the European Space Agency. The CCl4 distribution shows features typical of long-lived species of anthropogenic origin: higher concentrations in the troposphere, decreasing with altitude due to the photolysis. We compare MIPAS CCl4 data with independent observations from Atmospheric Chemistry Experiment - Fourier Transform Spectrometer (ACE - FTS) and stratospheric balloon version of MIPAS (MIPAS-B). The comparison shows a general good agreement between the different datasets. CCl4 trends are evaluated as a function of both latitude and altitude: negative trends (-10/ -15 pptv/decade, -10/ -30 %/decade) are found at all latitudes in the UTLS, apart from a region in the Southern mid-latitudes between 50 and 10 hPa where the trend is slightly positive (5/10 pptv/decade, 15/20 %/decade). At the lowest altitudes sounded by the MIPAS scan we find trend values consistent with those determined on the basis of the Advanced Global Atmospheric Gases Experiment (AGAGE) and the National Oceanic and Atmospheric Administration / Earth System Research Laboratory / Halocarbons and other Atmospheric Trace Species (NOAA / ESRL / HATS) networks. CCl4 global average lifetime of 47(39 - 61) years has been

Sulfuric acid on Europa and the radiolytic sulfur cycle.

PubMed

Carlson, R W; Johnson, R E; Anderson, M S

1999-10-01

A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

Model Simulations of the Global Carbon and Sulfur Cycles: Implications for the Paleocene-Eocene Thermal Maximum

NASA Astrophysics Data System (ADS)

Higgins, J. A.; Schrag, D. P.

2004-12-01

Extreme global warmth and an abrupt negative carbon isotope excursion during the Paleocene-Eocene Thermal Maximum (PETM) have been attributed to a rapid addition of isotopically depleted carbon to the ocean-atmosphere system. Potential carbon sources include the abrupt release of 1000-2000 Gt C as methane hydrate (\\delta13C ~-60\\permil) from sediments on the continental slope (Dickens et al., 1995) and the oxidation of 8000-9000 Gt of organic carbon (\\delta13C ~-25\\permil) in rampant global wildfires (Kurtz et al., 2003). Using a simple geochemical model of the global carbon and sulfur cycles, we investigate whether these hypotheses are consistent with estimates of climate warming during the PETM by considering the effects of atmospheric composition and climate in the Paleocene and feedbacks driven by changes in sulfur cycling and seawater chemistry. Modest increases in atmospheric CO2 (70-150 ppm) associated with methane hydrate release cannot, without additional feedbacks in the climate system, account for a 5-6° C increase in global sea surface temperature during the PETM. In contrast, a significant increase in atmospheric CO2 (600-700 ppm) is observed following the oxidation of 8000-9000 Gt of organic carbon. However, constraints on the size and extent of the Paleocene terrestrial carbon pool and the absence of geologic evidence indicative of vast wildfires argue against a global conflagration as an important source of depleted carbon. Instead, we interpret the PETM and its associated negative carbon isotope excursion as representing the oxidation of 8000-9000 Gt C as organic matter in shallow marine and near shore terrestrial sediments following the retreat of major epicontinental seaways in the Paleocene. This hypothesis is also consistent with large changes in the sulfur cycle in the early Eocene inferred from the \\delta34S of seawater sulfate. References: Dickens G.R., et al., (1995) Paleoceanography, 10, 965-971. Kurtz, A.C., et al., (2003

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

Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

NASA Technical Reports Server (NTRS)

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

2001-01-01

To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

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.

Extraction of mercury(II) with sulfurized jojoba oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wisniak, J.; Schorr, G.; Zacovsky, D.

1990-09-01

Sulfurized jojoba oil containing 12% by weight S has been tested as an extractant for Hg(II) from aqueous solutions. This paper reports on experiments performed with the extractant dissolved in a solvent (liquid--liquid extraction) or adsorbed in an appropriate resin matrix (solid--liquid extraction). The extraction characteristics of both systems have been measured and show that sulfurized jojoba oil exhibits very good possibilities as an extractant. The performance of several resins treated with sulfurized jojoba oil for adsorbing mercury(II) was studied. The morphology of the different resins was examined by using scanning electron microscopy. The sulfurized oil is attached to themore » resin sites through the sulfur atoms; it is estimated that there are about 2 mol of S active sites per kilogram of resin.« less

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.

Estimation of Atmospheric Corrosion of High-Strength, Low-Alloy Steels

DOT National Transportation Integrated Search

1997-05-01

This data analysis was undertaken to investigate the weatherability of steels whose compositions do not fall in the range of ASTM Standard G101, Estimating the Atmospheric Corrosion Resistance of Low-Alloy Steels.

The removal of sulfur dioxide from flue gases

PubMed Central

Kettner, Helmut

1965-01-01

The growth of industrialization makes it imperative to reduce the amounts of sulfur dioxide emitted into the atmosphere. This article describes various processes for cleaning flue gases, and gives details of new methods being investigated. Wet scrubbing with water, though widely practised, has many disadvantages. Scrubbing with zinc oxide, feasible in zinc works, is more satisfactory. Dry methods use a solid absorbent; they have the advantage of a high emission temperature. Other methods are based on the addition to the fuel or the flue gases of substances such as activated metal oxides, which react with the sulfur to form compounds less harmful than sulfur dioxide. Also being investigated are a two-stage combustion system, in which the sulfur dioxide is removed in the first stage, and the injection of activated powdered dolomite into burning fuel; the resulting sulfates being removed by electrostatic precipitation. A wet catalysis process has recently been developed. Most of the cleaning processes are not yet technically mature, but first results show good efficiency and relatively low cost. PMID:14315714

Emissions of biogenic sulfur gases from Alaskan tundra

NASA Technical Reports Server (NTRS)

Hines, Mark E.; Morrison, Michael C.

1992-01-01

Results of sulfur emission measurements made in freshwater and marine wetlands in Alaskan tundra during the Arctic Boundary Layer Expedition 2A (ABLE 3A) in July 1988 are presented. The data indicate that this type of tundra emits very small amounts of gaseous sulfur and, when extrapolated globally, accounts for a very small percentage of the global flux of biogenic sulfur to the atmosphere. Sulfur emissions from marine sites are up to 20-fold greater than fluxes from freshwater habitats and are dominated by dimethyl sulfide (DMS). Highest emissions, with a mean of 6.0 nmol/sq m/h, occurred in water-saturated wet meadow areas. In drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/sq m/h and lowest fluxes were from lichen-dominated areas at 0.9 nmol/sq m/h. DMS was the dominant gas emitted from all these sites. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea.

Space-based detection of missing sulfur dioxide sources of global air pollution

NASA Astrophysics Data System (ADS)

McLinden, Chris A.; Fioletov, Vitali; Shephard, Mark W.; Krotkov, Nick; Li, Can; Martin, Randall V.; Moran, Michael D.; Joiner, Joanna

2016-07-01

Sulfur dioxide is designated a criteria air contaminant (or equivalent) by virtually all developed nations. When released into the atmosphere, sulfur dioxide forms sulfuric acid and fine particulate matter, secondary pollutants that have significant adverse effects on human health, the environment and the economy. The conventional, bottom-up emissions inventories used to assess impacts, however, are often incomplete or outdated, particularly for developing nations that lack comprehensive emission reporting requirements and infrastructure. Here we present a satellite-based, global emission inventory for SO2 that is derived through a simultaneous detection, mapping and emission-quantifying procedure, and thereby independent of conventional information sources. We find that of the 500 or so large sources in our inventory, nearly 40 are not captured in leading conventional inventories. These missing sources are scattered throughout the developing world--over a third are clustered around the Persian Gulf--and add up to 7 to 14 Tg of SO2 yr-1, or roughly 6-12% of the global anthropogenic source. Our estimates of national total emissions are generally in line with conventional numbers, but for some regions, and for SO2 emissions from volcanoes, discrepancies can be as large as a factor of three or more. We anticipate that our inventory will help eliminate gaps in bottom-up inventories, independent of geopolitical borders and source types.

Space-Based Detection of Missing Sulfur Dioxide Sources of Global Air Pollution

NASA Technical Reports Server (NTRS)

McLinden, Chris A.; Fioletov, Vitali; Shephard, Mark W.; Krotkov, Nick; Li, Can; Martin, Randall V.; Moran, Michael D.; Joiner, Joanna

2016-01-01

Sulfur dioxide is designated a criteria air contaminant (or equivalent) by virtually all developed nations. When released into the atmosphere, sulfur dioxide forms sulfuric acid and fine particulate matter, secondary pollutants that have significant adverse effects on human health, the environment and the economy. The conventional, bottom-up emissions inventories used to assess impacts, however, are often incomplete or outdated, particularly for developing nations that lack comprehensive emission reporting requirements and infrastructure. Here we present a satellite-based, global emission inventory for SO2 that is derived through a simultaneous detection, mapping and emission-quantifying procedure, and thereby independent of conventional information sources. We find that of the 500 or so large sources in our inventory, nearly 40 are not captured in leading conventional inventories. These missing sources are scattered throughout the developing world-over a third are clustered around the Persian Gulf-and add up to 7 to 14 Tg of SO2 yr(exp -1), or roughly 6-12% of the global anthropogenic source. Our estimates of national total emissions are generally in line with conventional numbers, but for some regions, and for SO2 emissions from volcanoes, discrepancies can be as large as a factor of three or more. We anticipate that our inventory will help eliminate gaps in bottom-up inventories, independent of geopolitical borders and source types.

Fabrication and Characterization of CZTS Thin Films Prepared by the Sulfurization of RF-Sputtered Stacked Metal Precursors

NASA Astrophysics Data System (ADS)

Abusnina, Mohamed; Moutinho, Helio; Al-Jassim, Mowafak; DeHart, Clay; Matin, Mohammed

2014-09-01

In this work, Cu2ZnSnS4 (CZTS) thin films were prepared by the sulfurization of metal precursors deposited sequentially via radio frequency magnetron sputtering on Mo-coated soda-lime glass. The stack order of the precursors was Mo/Zn/Sn/Cu. Sputtered precursors were annealed in sulfur atmosphere with nine different conditions to study the impact of sulfurization time and substrate temperature on the structural, morphological, and optical properties of the final CZTS films. X-ray fluorescence was used to determine the elemental composition ratio of the metal precursors. Final CZTS films were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). XRD and EDS were combined to investigate the films' structure and to identify the presence of secondary phases. XRD analysis indicated an improvement in film crystallinity with an increase of the substrate temperature and annealing times. Also indicated was the minimization and/or elimination of secondary phases when the films experienced longer annealing time. EDS revealed slight Sn loss in films sulfurized at 550°C; however, an increase of the sulfurization temperature to 600°C did not confirm these results. SEM study showed that films treated with higher temperatures exhibited dense morphology, indicating the completion of the sulfurization process. The estimated absorption coefficient was on the order of 104 cm-1 for all CZTS films, and the values obtained for the optical bandgap energy of the films were between 1.33 eV and 1.52 eV.

Uncertainties associated with parameter estimation in atmospheric infrasound arrays.

PubMed

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.

Seasonal trends of atmospheric nitrogen dioxide and sulfur dioxide over North Santa Clara, Cuba.

PubMed

Alejo, Daniellys; Morales, Mayra C; de la Torre, Jorge B; Grau, Ricardo; Bencs, László; Van Grieken, René; Van Espen, Piet; Sosa, Dismey; Nuñez, Vladimir

2013-07-01

Atmospheric nitrogen dioxide (NO2) and sulfur dioxide (SO2) levels were monitored simultaneously by means of Radiello passive samplers at six sites of Santa Clara city, Cuba, in the cold and the warm seasons in 2010. The dissolved ionic forms of NO2 and SO2 as nitrate and sulfite plus sulfate, respectively, were determined by means of ion chromatography. Analysis of NO2 as nitrite was also performed by UV-Vis spectrophotometry. For NO2, significant t tests show good agreement between the results of IC and UV-Vis methods. The NO2 and SO2 concentrations peaked in the cold season, while their minimum levels were experienced in the warm season. The pollutant levels do not exceed the maximum allowable limit of the Cuban Standard 39:1999, i.e., 40 μg/m(3) and 50 μg/m(3) for NO2 and SO2, respectively. The lowest pollutant concentrations obtained in the warm season can be attributed to an increase in their removal via precipitation (scavenging) while to the decreased traffic density and industrial emission during the summer holidays (e.g., July and August).

Gas-phase hydration of glyoxylic acid: Kinetics and atmospheric implications.

PubMed

Liu, Ling; Zhang, Xiuhui; Li, Zesheng; Zhang, Yunhong; Ge, Maofa

2017-11-01

Oxocarboxylic acids are one of the most important organic species found in secondary organic aerosols and can be detected in diverse environments. But the hydration of oxocarboxylic acids in the atmosphere has still not been fully understood. Neglecting the hydration of oxocarboxylic acids in atmospheric models may be one of the most important reasons for the significant discrepancies between field measurements and abundance predictions of atmospheric models for oxocarboxylic acids. In the present paper, glyoxylic acid, as the most abundant oxocarboxylic acids in the atmosphere, has been selected as an example to study whether the hydration process can occur in the atmosphere and what the kinetic process of hydration is. The gas-phase hydration of glyoxylic acid to form the corresponding geminal diol and those catalyzed by atmospheric common substances (water, sulfuric acid and ammonia) have been investigated at the CCSD(T)-F12/cc-pVDZ-F12//M06-2X/6-311++G(3df,3pd) level of theory. The contour map of electron density difference of transition states have been further analyzed. It is indicated that these atmospheric common substances can all catalyze on the hydration to some extent and sulfuric acid is the most effective reducing the Gibbs free energy of activation to 9.48 kcal/mol. The effective rate constants combining the overall rate constants and concentrations of the corresponding catalysts have shown that water and sulfuric acid are both important catalysts and the catalysis of sulfuric acid is the most effective for the gas-phase hydration of glyoxylic acid. This catalyzed processes are potentially effective in coastal regions and polluted regions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Laboratory Measurements and Modeling of Molecular Photoabsorption Cross Sections in the Ultraviolet: Diatomic Sulfur (S2) and Sulfur Monoxide (SO)

NASA Astrophysics Data System (ADS)

Stark, Glenn; Lyons, James; Herde, Hannah; Nave, Gillian; de Oliveira, Nelson

2015-11-01

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 (S2) and sulfur monoxide (SO) are in progress.S2: Interpretations of atmospheric (Io, Jupiter, cometary comae) S2 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 S2 from 240 to 300 nm based on laboratory measurements and theoretical calculations. We have constructed an experimental apparatus to produce a stable column of S2 vapor at a temperature of 800 K. High-resolution measurements of the absorption spectrum of the strong B - X system of S2 were completed using the NIST VUV-FTS at Gaithersburg, MD. These measurements are being incorporated into a coupled-channel model of the absorption spectrum of S2 to quantify the contributions from individual bands 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 SO radicals in the UV and VUV regions, where the molecule strongly predissociates, for modeling the atmospheres of Io and Venus, and for understanding sulfur isotope effects in the ancient (pre-O2) atmosphere of Earth. We have produced a measurable column of SO in a continuous-flow DC discharge cell, using SO2 as a parent molecule. Photoabsorption measurements were recently recorded with the high-resolution VUV-FTS on the DESIRS beamline of the SOLEIL synchrotron. A number of strong, predissociated SO bands were measured in the 140 to 200 nm region. Weaker features associated with the SO B - X system were simultaneously

Using box models to quantify zonal distributions and emissions of halocarbons in the background atmosphere.

NASA Astrophysics Data System (ADS)

Elkins, J. W.; Nance, J. D.; Dutton, G. S.; Montzka, S. A.; Hall, B. D.; Miller, B.; Butler, J. H.; Mondeel, D. J.; Siso, C.; Moore, F. L.; Hintsa, E. J.; Wofsy, S. C.; Rigby, M. L.

2015-12-01

The Halocarbons and other Atmospheric Trace Species (HATS) of NOAA's Global Monitoring Division started measurements of the major chlorofluorocarbons and nitrous oxide in 1977 from flask samples collected at five remote sites around the world. Our program has expanded to over 40 compounds at twelve sites, which includes six in situ instruments and twelve flask sites. The Montreal Protocol for Substances that Deplete the Ozone Layer and its subsequent amendments has helped to decrease the concentrations of many of the ozone depleting compounds in the atmosphere. Our goal is to provide zonal emission estimates for these trace gases from multi-box models and their estimated atmospheric lifetimes in this presentation and make the emission values available on our web site. We plan to use our airborne measurements to calibrate the exchange times between the boxes for 5-box and 12-box models using sulfur hexafluoride where emissions are better understood.

SHRIMP-SI Multiple Sulfur Isotope Analysis of Sulfides from Brazilian Deposits: Analytical Capability to Resolve Single Grain Textural Complexities and Distinct Sulfur Sources

NASA Astrophysics Data System (ADS)

Ireland, T. R.; Teles, G. D. S.; Chemale, F., Jr.; Avila, J.

2016-12-01

The Archean atmosphere is thought to be several times more reducing than the present day atmosphere, and the occurrence of Mass Independent Fractionation of Sulfur isotopes (MIF-S) in sulfides of sedimentary and volcanogenic rocks older than 2.45 Ga reinforces it. The most accepted mechanism to generate MIF-S requires photochemical reactions with volcanogenic SO2 in an anoxic atmosphere (O2 levels <10-5 PAL). The identification of MIF-S, noted as Δ33S and Δ36S, requires precise measurements of less abundant 33S and 36S isotopes, which were first attained by bulk isotope analyses. However, in-situ analysis has become essential, as many of ancient sulfide samples have suffered post-depositional processes, and their primary isotopic signature from the atmosphere are now overprinted by mass-dependent fractionation processes. High-precision and resolution in situ measurements of 32S, 33S, 34S and 36S in sulfides can be achieved by SHRIMP-SI, which allows isotopic determinations with internal errors better than 0.05‰ for Δ33S and 0.2‰ for Δ36S (2SE), and reproducibility about 0.1‰ for Δ33S and better than 0.5‰ for Δ36S (2SD). Examples of the SHRIMP-SI capability are provided by multiple sulfur isotope analysis of samples from Brazil, the Au-(U) and pyrite deposits of Jacobina Basin and the massive sulfide deposits of the 3.3 Ga Mundo Novo Greenstone Belt. The level of precision and spatial resolution achievable with SHRIMP-SI allowed the isotopic distinction between sedimentary and post-depositional pyrites in Jacobina Basin, as well as the identification of different sulfur sources in the Mundo Novo Greenstone Belt VMS deposits.

[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.

SEM-EDX and isotope characterization of the organic sulfur in macerals and chars in Illinois Basin coals

USGS Publications Warehouse

Demir, I.; Harvey, R.D.; Hackley, Keith C.

1993-01-01

Two samples of the Herrin (Illinois No. 6) Coal and one sample of the Colchester (Illinois No. 2) Coal from the Illinois Basin were studied to evaluate the spatial distribution of organic sulfur within macerals occurring next to pyrite grains, both in the raw coal and their chars. The chars were produced by pyrolysing the coal at 250-550??C in a nitrogen atmosphere. Representative splits of the coals and their chars were mounted in epoxy and polished for optical microscopy and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX). Determinations of organic sulfur concentrations were made at 996 locations within macerals, mostly vitrinite, around 115 grains of pyrite and at 50 locations around 5 pores in chars. The pyrite considered here is restricted to the disseminated type within macerals. On the average, the organic sulfur content increased near pyrite grains after the coals were charred at 550??C, indicating that some of the pyritic sulfur released during charring was retained within the organic matrix rather than being emitted to the atmosphere. One of the coal samples and its chars were isotopically characterized by chemically separating the pyritic and organic sulfur fractions, followed by analyzing the isotopes of the sulfur forms with a Nuclide 6-60 ratio mass spectrometer. The sulfur isotope (??34S) data confirmed the movement of pyritic sulfur into the macerals after charring to 550??C. About 18% of the organic sulfur that remained in the 550??C char had originally been pyritic sulfur in the untreated coal. ?? 1993.

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.

Global sulfur emissions from 1850 to 2000.

PubMed

Stern, David I

2005-01-01

The ASL database provides continuous time-series of sulfur emissions for most countries in the World from 1850 to 1990, but academic and official estimates for the 1990s either do not cover all years or countries. This paper develops continuous time series of sulfur emissions by country for the period 1850-2000 with a particular focus on developments in the 1990s. Global estimates for 1996-2000 are the first that are based on actual observed data. Raw estimates are obtained in two ways. For countries and years with existing published data I compile and integrate that data. Previously published data covers the majority of emissions and almost all countries have published emissions for at least 1995. For the remaining countries and for missing years for countries with some published data, I interpolate or extrapolate estimates using either an econometric emissions frontier model, an environmental Kuznets curve model, or a simple extrapolation, depending on the availability of data. Finally, I discuss the main movements in global and regional emissions in the 1990s and earlier decades and compare the results to other studies. Global emissions peaked in 1989 and declined rapidly thereafter. The locus of emissions shifted towards East and South Asia, but even this region peaked in 1996. My estimates for the 1990s show a much more rapid decline than other global studies, reflecting the view that technological progress in reducing sulfur based pollution has been rapid and is beginning to diffuse worldwide.

SIMULTANEOUS CAPTURE OF METAL, SULFUR AND CHLORINE BY SORBENTS DURING FLUIDIZED BED INCINERATION. (R826694C697)

EPA Science Inventory

Metal capture experiments were carried out in an atmospheric fluidized bed incinerator to investigate the effect of sulfur and chlorine on metal capture efficiency and the potential for simultaneous capture of metal, sulfur and chlorine by sorbents. In addition to experimental...

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.

Evaluation of Sulfur 'Concrete' for Use as a Construction Material on the Lunar Surface

NASA Technical Reports Server (NTRS)

Grugel, R. N.

2008-01-01

Combining molten sulfur with any number of aggregate materials forms, when solid, a mixture having attributes similar, if not better, to conventional water-based concrete. As a result the use of sulfur "concrete" on Earth is well established, particularly in corrosive environments. Consequently, discovery of troilite (FeS) on the lunar surface prompted numerous scenarios about its reduction to elemental sulfur for use, in combination with lunar regolith, as a potential construction material; not requiring water, a precious resource, for its manufacture is an obvious advantage. However, little is known about the viability of sulfur concrete in an environment typified by extreme temperatures and essentially no atmosphere. The experimental work presented here evaluates the response of pure sulfur and sulfur concrete subjected to laboratory conditions that approach those expected on the lunar surface, the results suggesting a narrow window of application.

Graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

DOEpatents

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuiliang; Li, Xiaolin

2014-06-17

Rechargeable lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter less than 50 nm..

Advanced Sulfur Control Processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gangwal, S.K.; Portzer, J.W.; Turk, B.S.

1996-12-31

The primary objective of this project is to determine the feasibility of an alternate concept for the regeneration of high temperature desulfurization sorbents in which elemental sulfur, instead of SO{sub 2}, is produced. If successful, this concept will eliminate or alleviate problems caused by the highly exothermic nature of the regeneration reaction, the tendency for metal sulfate formation, and the need to treat the regeneration off-gas to prevent atmospheric SO{sub 2}, emissions. Iron and cerium-based sorbents were chosen on the basis of thermodynamic analysis to determine the feasibility of elemental sulfur production. The ability of both to remove H{sub 2}Smore » during the sulfidation phase is less than that of zinc-based sorbents, and a two-stage desulfurization process will likely be required. Preliminary experimental work used electrobalance reactors to compare the relative rates of reaction of O{sub 2} and H{sub 2}O with FeS. More detailed studies of the regeneration of FeS as well as the sulfidation of CeO{sub 2} and regeneration of Ce{sub 2}O{sub 2}S are being carried out in a laboratory-scale fixed-bed reactor equipped with a unique analytical system which permits semi-continuous analysis of the distribution of elemental sulfur, H{sub 2}S, and SO{sub 2} in the reaction product gas.« less

The shadow price of substitutable sulfur in the US electric power plant: a distance function approach.

PubMed

Lee, Myunghun

2005-10-01

Given restrictions on sulfur dioxide emissions, a feasible long-run response could involve either an investment in improving boiler fuel-efficiency or a shift to a production process that is effective in removing sulfur dioxide. To allow for the possibility of substitution between sulfur and productive capital, we measure the shadow price of sulfur dioxide as the opportunity cost of lowering sulfur emissions in terms of forgone capital. The input distance function is estimated with data from 51 coal-fired US power units operating between 1977 and 1986. The indirect Morishima elasticities of substitution indicate that the substitutability of capital for sulfur is relatively high. The overall weighted average estimate of the shadow price of sulfur is -0.076 dollars per pound in constant 1976 dollars.

Metabolic Reactions among Organic Sulfur Compounds

NASA Technical Reports Server (NTRS)

Schulte, M.; Rogers, K.

2005-01-01

Sulfur is central to the metabolisms of many organisms that inhabit extreme environments. Numerous authors have addressed the energy available from a variety of inorganic sulfur redox pairs. Less attention has been paid, however, to the energy required or gained from metabolic reactions among organic sulfur compounds. Work in this area has focused on the oxidation of alkyl sulfide or disulfide to thiol and formaldehyde, e.g. (CH3)2S + H2O yields CH3SH + HCHO + H2, eventually resulting in the formation of CO2 and SO4(-2). It is also found that reactions among thiols and disulfides may help control redox disequilibria between the cytoplasm and the periplasm. Building on our earlier efforts for thiols, we have compiled and estimated thermodynamic properties for alkyl sulfides. We are investigating metabolic reactions among various sulfur compounds in a variety of extreme environments, ranging from sea floor hydrothermal systems to organic-rich sludge. Using thermodynamic data and the revised HKF equation of state, along with constraints imposed by the geochemical environments sulfur-metabolizing organisms inhabit, we are able to calculate the amount of energy available to these organisms.

Electron-induced chemistry in microhydrated sulfuric acid clusters

NASA Astrophysics Data System (ADS)

Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

2017-11-01

We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H2SO4)m(H2O)n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4)m(H2O)nHSO4- and (H2O)nH2SO4-. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4- ṡ ṡ ṡ H3O+) formation in the neutral H2SO4(H2O)n clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO4)2(H2O)n this process starts as early as n ≥ 2 water molecules. The (H2SO4)m(H2O)nHSO4- clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4- ṡ ṡ ṡ H3O+) ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2O)nH2SO4- cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

Above-ground sulfur cycling in adjacent coniferous and deciduous forest and watershed sulfur retention in the Georgia Piedmont, U.S.A.

USGS Publications Warehouse

Cappellato, R.; Peters, N.E.; Meyers, T.P.

1998-01-01

Atmospheric deposition and above-ground cycling of sulfur (S) were evaluated in adjacent deciduous and coniferous forests at the Panola Mountain Research Watershed (PMRW), Georgia U.S.A. Total atmospheric S deposition (wet plus dry) was 12.9 and 12.7 kg ha-1 yr-1 for the deciduous and coniferous forests, respectively, from October 1987 through November 1989. Dry deposition contributes more than 40% to the total atmospheric S deposition, and SO2 is the major source (~55%) of total dry S deposition. Dry deposition to these canopies is similar to regional estimates suggesting that 60-km proximity to emission sources does not noticeably impact dry deposition at PMRW. Below-canopy S fluxes (throughfall plus stemflow) in each forest are 37% higher annually in the deciduous forest than in the coniferous forest. An excess in below-canopy S flux in the deciduous forest is attributed to leaching and higher dry deposition than in the coniferous forest. Total S deposition to the forest floor by throughfall, stemflow and litterfall was 2.4 and 2.8 times higher in the deciduous and coniferous forests, respectively, than annual S growth requirement for foliage and wood. Although A deposition exceeds growth requirement, more than 95% of the total atmospheric S deposition was retained by the watershed in 1988 and 1989. The S retention at PMRW is primarily due to SO2+4 adsorption by iron oxides and hydroxides in watershed soils. The S content in while oak and loblolly pine boles have increased more than 200% in the last 20 yr, possibly reflecting increases in emissions.

Comparisons of Watershed Sulfur Budgets in Southeast Canada and Northeast US: New Approaches and Implications

EPA Science Inventory

Most of eastern North America receives elevated levels of atmospheric deposition of sulfur (S) that result from anthropogenic SO₂ emissions from fossil fuel combustion. Atmospheric S deposition has acidified sensitive terrestrial and aquatic ecosystems in this region; ...

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

SOA FORMATION FROM THE IRRADIATION OF A-PINENE-NOX IN THE ABSENCE AND PRESENCE OF SULFUR DIOXIDE

EPA Science Inventory

Sulfur dioxide (SO2) is an important constituent in the polluted atmosphere. It is emitted from combustion sources using fuels that contain sulfur. Emissions of SO2 in the United States were reportedly 17 Tg in 1996 with most coming from coal and petroleum combustion. The pr...

A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries

PubMed Central

Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E. C.; Matic, Aleksandar

2016-01-01

Societies’ increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3–5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of “no battery without binder” and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications. PMID:28008981

A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries.

PubMed

Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E C; Matic, Aleksandar

2016-12-23

Societies' increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3-5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of "no battery without binder" and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm 2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications.

A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries

NASA Astrophysics Data System (ADS)

Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E. C.; Matic, Aleksandar

2016-12-01

Societies’ increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3-5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of “no battery without binder” and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications.

Global atmospheric particle formation from CERN CLOUD measurements.

PubMed

Dunne, Eimear M; Gordon, Hamish; Kürten, Andreas; Almeida, João; Duplissy, Jonathan; Williamson, Christina; Ortega, Ismael K; Pringle, Kirsty J; Adamov, Alexey; Baltensperger, Urs; Barmet, Peter; Benduhn, Francois; Bianchi, Federico; Breitenlechner, Martin; Clarke, Antony; Curtius, Joachim; Dommen, Josef; Donahue, Neil M; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Guida, Roberto; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Jokinen, Tuija; Kangasluoma, Juha; Kirkby, Jasper; Kulmala, Markku; Kupc, Agnieszka; Lawler, Michael J; Lehtipalo, Katrianne; Makhmutov, Vladimir; Mann, Graham; Mathot, Serge; Merikanto, Joonas; Miettinen, Pasi; Nenes, Athanasios; Onnela, Antti; Rap, Alexandru; Reddington, Carly L S; Riccobono, Francesco; Richards, Nigel A D; Rissanen, Matti P; Rondo, Linda; Sarnela, Nina; Schobesberger, Siegfried; Sengupta, Kamalika; Simon, Mario; Sipilä, Mikko; Smith, James N; Stozkhov, Yuri; Tomé, Antonio; Tröstl, Jasmin; Wagner, Paul E; Wimmer, Daniela; Winkler, Paul M; Worsnop, Douglas R; Carslaw, Kenneth S

2016-12-02

Fundamental questions remain about the origin of newly formed atmospheric aerosol particles because data from laboratory measurements have been insufficient to build global models. In contrast, gas-phase chemistry models have been based on laboratory kinetics measurements for decades. We built a global model of aerosol formation by using extensive laboratory measurements of rates of nucleation involving sulfuric acid, ammonia, ions, and organic compounds conducted in the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber. The simulations and a comparison with atmospheric observations show that nearly all nucleation throughout the present-day atmosphere involves ammonia or biogenic organic compounds, in addition to sulfuric acid. A considerable fraction of nucleation involves ions, but the relatively weak dependence on ion concentrations indicates that for the processes studied, variations in cosmic ray intensity do not appreciably affect climate through nucleation in the present-day atmosphere. Copyright © 2016, American Association for the Advancement of Science.

Iron-Sulfur-Carbonyl and -Nitrosyl Complexes: A Laboratory Experiment.

ERIC Educational Resources Information Center

Glidewell, Christopher; And Others

1985-01-01

Background information, materials needed, procedures used, and typical results obtained, are provided for an experiment on iron-sulfur-carbonyl and -nitrosyl complexes. The experiment involved (1) use of inert atmospheric techniques and thin-layer and flexible-column chromatography and (2) interpretation of infrared, hydrogen and carbon-13 nuclear…

Estimation of Dynamical Parameters in Atmospheric Data Sets

NASA Technical Reports Server (NTRS)

Wenig, Mark O.

2004-01-01

In this study a new technique is used to derive dynamical parameters out of atmospheric data sets. This technique, called the structure tensor technique, can be used to estimate dynamical parameters such as motion, source strengths, diffusion constants or exponential decay rates. A general mathematical framework was developed for the direct estimation of the physical parameters that govern the underlying processes from image sequences. This estimation technique can be adapted to the specific physical problem under investigation, so it can be used in a variety of applications in trace gas, aerosol, and cloud remote sensing. The fundamental algorithm will be extended to the analysis of multi- channel (e.g. multi trace gas) image sequences and to provide solutions to the extended aperture problem. In this study sensitivity studies have been performed to determine the usability of this technique for data sets with different resolution in time and space and different dimensions.

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.

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

Gridded anthropogenic emissions inventory and atmospheric transport of carbonyl sulfide in the U.S.

NASA Astrophysics Data System (ADS)

Zumkehr, Andrew; Hilton, Timothy W.; Whelan, Mary; Smith, Steve; Campbell, J. Elliott

2017-02-01

Carbonyl sulfide (COS or OCS), the most abundant sulfur-containing gas in the troposphere, has recently emerged as a potentially important atmospheric tracer for the carbon cycle. Atmospheric inverse modeling studies may be able to use existing tower, airborne, and satellite observations of COS to infer information about photosynthesis. However, such analysis relies on gridded anthropogenic COS source estimates that are largely based on industry activity data from over three decades ago. Here we use updated emission factor data and industry activity data to develop a gridded inventory with a 0.1° resolution for the U.S. domain. The inventory includes the primary anthropogenic COS sources including direct emissions from the coal and aluminum industries as well as indirect sources from industrial carbon disulfide emissions. Compared to the previously published inventory, we found that the total anthropogenic source (direct and indirect) is 47% smaller. Using this new gridded inventory to drive the Sulfur Transport and Deposition Model/Weather Research and Forecasting atmospheric transport model, we found that the anthropogenic contribution to COS variation in the troposphere is small relative to the biosphere influence, which is encouraging for carbon cycle applications in this region. Additional anthropogenic sectors with highly uncertain emission factors require further field measurements.

Cat cracking technology with reduced discharge of harmful substances to the atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elshin, A.I.; Aliev, R.R.; Solyar, B.Z.

1995-11-01

The operation of cat crackers creates a number of ecological problems involving pollution of the atmosphere. In the regeneration of coked catalyst, up to 10 tonnes/day of sulfur oxides are discharged to the atmosphere, along with catalyst dust in amounts up to 2 tonnes/day and carbon monoxide up to 120 tonnes/day. With increasingly severe requirements for environmental protection, the problem of reducing harmful discharges to the atmosphere has become more acute, necessitating either preliminary hydrotreating of the feed or scrubber cleanup of the stack gas to remove sulfur oxides. The high cost of these processes has provided the impetus formore » proposing various types of bifunctional cracking catalysts and effective catalyst additives to bind sulfur oxides directly in the regenerator. Basic oxides (of aluminum, magnesium, calcium, etc.) react with sulfur oxides to form stable sulfates that are then reduced to hydrogen sulfide in the reactor, while re-forming the basic oxide. Binding sulfur oxides in the regenerator is favored by the presence of an oxidizing agent or by the introduction of a promoter for afterburning carbon monoxide to dioxide. Compositions consisting mainly of aluminum oxide ({>=}90% by weight) have been patented as catalyst additives for binding sulfur oxides; other compositions that have been patented consist of Group II metal oxides and other oxides that have oxidizing properties. The additives are introduced into the catalyst charge in amounts of 5-10% by weight. On the basis of research, an aluminium oxide additive, PS-17, has been developed for binding sulfur oxides in the course of cracking.« less

Wet Chemistry Synthesis of Multidimensional Nanocarbon-Sulfur Hybrid Materials with Ultrahigh Sulfur Loading for Lithium-Sulfur Batteries.

PubMed

Du, Wen-Cheng; Yin, Ya-Xia; Zeng, Xian-Xiang; Shi, Ji-Lei; Zhang, Shuai-Feng; Wan, Li-Jun; Guo, Yu-Guo

2016-02-17

An optimized nanocarbon-sulfur cathode material with ultrahigh sulfur loading of up to 90 wt % is realized in the form of sulfur nanolayer-coated three-dimensional (3D) conducting network. This 3D nanocarbon-sulfur network combines three different nanocarbons, as follows: zero-dimensional carbon nanoparticle, one-dimensional carbon nanotube, and two-dimensional graphene. This 3D nanocarbon-sulfur network is synthesized by using a method based on soluble chemistry of elemental sulfur and three types of nanocarbons in well-chosen solvents. The resultant sulfur-carbon material shows a high specific capacity of 1115 mA h g(-1) at 0.02C and good rate performance of 551 mA h g(-1) at 1C based on the mass of sulfur-carbon composite. Good battery performance can be attributed to the homogeneous compositing of sulfur with the 3D hierarchical hybrid nanocarbon networks at nanometer scale, which provides efficient multidimensional transport pathways for electrons and ions. Wet chemical method developed here provides an easy and cost-effective way to prepare sulfur-carbon cathode materials with high sulfur loading for application in high-energy Li-S batteries.

Does nitrogen and sulfur deposition affect forest productivity?

Treesearch

Brittany A. Johnson; Kathryn B. Piatek; Mary Beth Adams; John R. Brooks

2010-01-01

We studied the effects of atmospheric nitrogen and sulfur deposition on forest productivity in a 10-year-old, aggrading forest stand at the Fernow Experimental Forest in Tucker County, WV. Forest productivity was expressed as total aboveground wood biomass, which included stem and branch weight of standing live trees. Ten years after stand regeneration and treatment...

Impact of Sulfur Hazes on the Reflected Light Spectra of Giant Exoplanets

NASA Astrophysics Data System (ADS)

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

2017-01-01

Recent work has shown that photochemical hazes composed of elemental sulfur and its allotropes may arise in the atmospheres of warm and temperate giant exoplanets due to the photolysis of H2S. We investigate the impact such a haze would have on an exoplanet's geometric albedo spectrum using a suite of established radiative-convective, cloud, and albedo models, and how this may impact future direct imaging missions, such as WFIRST. For Jupiter-massed planets, photochemical destruction of H2S results in the production of ~1 ppmv of S8 between 100 and 0.1 mbar. The S8 mixing ratio is largely independent of the stellar UV flux, vertical mixing rates, and atmospheric temperature for expected ranges of those values, such that the S8 haze mass is dependent only on the S8 supersaturation, controlled by the local temperature. 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 its purely scattering nature. Strong absorption by the haze shortward of 0.4 μm results in albedos <0.1, contrasting the high albedos produced by Rayleigh scattering in a clear atmosphere. These dramatic alteration in the geometric albedo spectra will lead to substantial color changes for hazy planets away from that expected for more Jupiter-like planets. For this reason colors are unlikely to provide definitive identification of warm Jupiter-like planets. The albedo change due to a sulfur haze is largely independent of the location of the haze in the atmosphere, but is a strong function of the haze optical depth as controlled by its column number density and mean particle size, though the absorption feature at short wavelengths remains robust. Detection of such a haze by future direct imaging missions like WFIRST is possible, though discriminating between a sulfur haze and any other reflective

Optimal Estimation of the Carbonyl Sulfide Surface Flux Through Inverse Modeling of TES Observations

NASA Astrophysics Data System (ADS)

Kuai, L.; Worden, J.; Lee, M.; Campbell, J. E.; Kulawik, S. S.; Weidner, R. J.

2014-12-01

Carbonyl sulfide (OCS) is the most abundant sulfur gas in the troposphere with a global averaging mixing ratio of about 500 part per trillion (ppt). The ocean is the primary source of OCS, emitting OCS directly or its precursors, carbon disulfide and dimethyl sulfide. The most important atmospheric sink of OCS is uptake by terrestrial plants via photosynthesis. Although the global budget of atmospheric OCS has been studied, the global integrated OCS fluxes have large uncertainties, e.g. the uncertainties of the ocean fluxes are as large as 100% or more and a large missing ocean sources required to balance the global budgets. A first tropical ocean map of the free tropospheric OCS has been developed using retrieval data from radiance measurements from the AURA Tropospheric Emission Spectrometer (TES). The monthly mean ocean data has been evaluated to estimate the biases and uncertainties in the TES OCS against aircraft profiles from the HIPPO campaign and ground data from the NOAA Mauna Loa site. We found the TES OCS data to be consistent (within the calculated uncertainties) with NOAA ground observations and HIPPO aircraft measurements and it captured the seasonal and latitudinal variations observed by these in situ data within the estimated uncertainties. In this study, we first update bottom-up estimate of global source and sinks of atmospheric OCS. The global forward simulations of atmospheric OCS using updated bottom-up fluxes with GEOS-Chem show improvement of the seasonal variation over multiple NOAA ground stations in both north and south hemispheres. Inverse analysis of surface fluxes from TES OCS data will provide further constraints to estimate the missing ocean source and understand the enhanced OCS over eastern Asia and west Pacific, which could be driven by wind, Asian outflow, a mystery process, or a combination of all of the above. The investigation will provide the fundamental measurements and analysis needed to estimate the missing source in the

Clustering of amines and hydrazines in atmospheric nucleation

NASA Astrophysics Data System (ADS)

Li, Siyang; Qu, Kun; Zhao, Hailiang; Ding, Lei; Du, Lin

2016-06-01

It has been proved that the presence of amines in the atmosphere can enhance aerosol formation. Hydrazine (HD) and its substituted derivatives, monomethylhydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH), which are organic derivatives of amine and ammonia, are common trace atmospheric species that may contribute to the growth of nucleation clusters. The structures of the hydrazine and amine clusters containing one or two common nucleation molecules (ammonia, water, methanol and sulfuric acid) have been optimized using density functional theory (DFT) methods. The clusters growth mechanism has been explored from the thermochemistry by calculating the Gibbs free energies of adding an ammonia, water, methanol or sulfuric acid molecule step by step at room temperature, respectively. The results show that hydrazine and its derivatives could enhance heteromolecular homogeneous nucleation in the earth's atmosphere.

Sulfur and Nitrogen Deposition on Ecosystems in the United States

EPA Science Inventory

The ecological impacts of atmospheric sulfur and nitrogen deposition first gained attention in the United States in the early 1970s with reports of "acid rain" falling to earth, causing lakes and streams to become acidic and resulting in conditions that were unsuitable for repro...

Improved Atmospheric Correction Over the Indian Subcontinent Using Fast Radiative Transfer and Optimal Estimation

NASA Astrophysics Data System (ADS)

Natraj, V.; Thompson, D. R.; Mathur, A. K.; Babu, K. N.; Kindel, B. C.; Massie, S. T.; Green, R. O.; Bhattacharya, B. K.

2017-12-01

Remote Visible / ShortWave InfraRed (VSWIR) spectroscopy, typified by the Next-Generation Airborne Visible/Infrared Imaging Spectrometer (AVIRIS-NG), is a powerful tool to map the composition, health, and biodiversity of Earth's terrestrial and aquatic ecosystems. These studies must first estimate surface reflectance, removing the atmospheric effects of absorption and scattering by water vapor and aerosols. Since atmospheric state varies spatiotemporally, and is insufficiently constrained by climatological models, it is important to estimate it directly from the VSWIR data. However, water vapor and aerosol estimation is a significant ongoing challenge for existing atmospheric correction models. Conventional VSWIR atmospheric correction methods evolved from multi-band approaches and do not fully utilize the rich spectroscopic data available. We use spectrally resolved (line-by-line) radiative transfer calculations, coupled with optimal estimation theory, to demonstrate improved accuracy of surface retrievals. These spectroscopic techniques are already pervasive in atmospheric remote sounding disciplines but have not yet been applied to imaging spectroscopy. Our analysis employs a variety of scenes from the recent AVIRIS-NG India campaign, which spans various climes, elevation changes, a wide range of biomes and diverse aerosol scenarios. A key aspect of our approach is joint estimation of surface and aerosol parameters, which allows assessment of aerosol distortion effects using spectral shapes across the entire measured interval from 380-2500 nm. We expect that this method would outperform band ratio approaches, and enable evaluation of subtle aerosol parameters where in situ reference data is not available, or for extreme aerosol loadings, as is observed in the India scenarios. The results are validated using existing in-situ reference spectra, reflectance measurements from assigned partners in India, and objective spectral quality metrics for scenes without any

New particle formation from sulfuric acid and amines: Similarities and differences between mono-, di-, and trimethylamines

NASA Astrophysics Data System (ADS)

Olenius, Tinja; Halonen, Roope; Kurtén, Theo; Henschel, Henning; Kupiainen-Määttä, Oona; Ortega, Ismael K.; Vehkamäki, Hanna; Riipinen, Ilona

2017-04-01

Amines are organic base species that are emitted to the atmosphere from both anthropogenic and natural sources. Both theoretical and laboratory studies suggest that mono-, di-, and trimethylamines (MMA, DMA, and TMA, respectively) are capable of enhancing the initial steps of sulfuric acid-driven aerosol particle formation much more strongly than ammonia (Kurtén et al., 2008; Jen et al., 2014). Despite the potential importance for atmospheric new particle formation, quantitative estimates on the emissions and thermochemical properties of amines remain relatively uncertain. Because of this and also due to computational reasons, recent large-scale modeling studies have treated sulfuric acid-amine nucleation by introducing a single surrogate amine species, the total emissions of which combine together MMA, DMA and TMA but which resembles DMA or TMA in its various properties (e.g. Bergman et al., 2015). On the other hand, there are likely to be differences in the potentials of the three amines to enhance particle formation, causing uncertainties to the lumping approach. Systematic comparisons are needed to evaluate how to treat these species in atmospheric models and to assess what level of simplification is justifiable. In this work, we study the differences and similarities of MMA, DMA and TMA by modeling nanoparticle formation from sulfuric acid, water, and each of the three amines. We simulate molecular cluster concentrations and formation rates at boundary layer conditions with a dynamic cluster population model using quantum chemistry-based cluster evaporation rates, and study the dependence of particle formation rate on precursor vapor concentrations, temperature and relative humidity. The results suggest that for the three amines, there are differences in the nucleation mechanism and hygroscopicity of molecular clusters. However, for DMA and TMA, formation of nanometer-sized particles and its dependence on ambient conditions is roughly similar: both

Measurements of Nucleation-Mode Particle Size Distributions in Aircraft Plumes during SULFUR 6

NASA Technical Reports Server (NTRS)

Brock, Charles A.; Bradford, Deborah G.

1999-01-01

This report summarizes the participation of the University of Denver in an airborne measurement program, SULFUR 6, which was undertaken in late September and early October of 1998 by the Deutsches Zentrum fur Luft und Raumfahrt (DLR). Scientific findings from two papers that have been published or accepted and from one manuscript that is in preparation are presented. The SULFUR 6 experiment was designed to investigate the emissions from subsonic aircraft to constrain calculations of possible atmospheric chemical and climatic effects. The University of Denver effort contributed toward the following SULFUR 6 goals: (1) To investigate the relationship between fuel sulfur content (FSC--mass of sulfur per mass of fuel) and particle number and mass emission index (El--quantity emitted per kg of fuel burned); (2) To provide upper and lower limits for the mass conversion efficiency (nu) of fuel sulfur to gaseous and particulate sulfuric acid; (3) To constrain models of volatile particle nucleation and growth by measuring the particle size distribution between 3 and 100 nm at aircraft plume ages ranging from 10(exp -1) to 10(exp 3) s; (4) To determine microphysical and optical properties and bulk chemical composition of soot particles in aircraft exhaust; and (5) To investigate the differences in particle properties between aircraft plumes in contrail and non-contrail situations. The experiment focused on emissions from the ATTAS research aircraft (a well characterized, but older technology turbojet) and from an in-service Boeing 737-300 aircraft provided by Lufthansa, with modem, high-bypass turbofan engines. Measurements were made from the DLR Dassault Falcon 900 aircraft, a modified business jet. The Atmospheric Effects of Aviation Program (AEAP) provided funding to operate an instrument, the nucleation-mode aerosol size spectrometer (N-MASS), during the SULFUR 6 campaign and to analyze the data. The N-MASS was developed at the University of Denver with the support of

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

Sulfur-impregnated disordered carbon nanotubes cathode for lithium-sulfur batteries.

PubMed

Guo, Juchen; Xu, Yunhua; Wang, Chunsheng

2011-10-12

The commercialization of lithium-sulfur batteries is hindered by low cycle stability and low efficiency, which are induced by sulfur active material loss and polysulfide shuttle reaction through dissolution into electrolyte. In this study, sulfur-impregnated disordered carbon nanotubes are synthesized as cathode material for the lithium-sulfur battery. The obtained sulfur-carbon tube cathodes demonstrate superior cyclability and Coulombic efficiency. More importantly, the electrochemical characterization indicates a new stabilization mechanism of sulfur in carbon induced by heat treatment.

The Role of Perturbations in the B-X UV Spectrum of S_{2} in a Temperature-Dependent Mechanism for Sulfur Mass Independent Fractionation

NASA Astrophysics Data System (ADS)

Hull, Alexander W.; Field, Robert W.; Ono, Shuhei

2017-06-01

Sulfur mass independent fractionation (S-MIF) describes anomalous sulfur isotope ratios commonly found in sedimentary rocks older than 2.45 billion years. These anomalies likely originate from photochemistry of small, sulfur-containing molecules in the atmosphere, and their sudden disappearance from rock samples younger than 2.45 years is thought to be correlated with a sharp rise in atmospheric oxygen levels. The emergence of atmospheric oxygen is an important milestone in the development of life on Earth, but the mechanism for sulfur MIF in an anoxic atmosphere is not well understood. In this context, we present an analysis of the B-X UV spectrum of S_{2}, an extension of work presented last year. The B state of S_{2} is strongly perturbed by the nearby B" state, as originally described by Green and Western (1996). Our analysis suggests that a doorway-mediated transfer mechanism shifts excited state population from the short-lifetime B state to the longer-lifetime B" state. Furthermore, access to the perturbed doorway states is strongly dependent on the population distribution in the ground state. This suggests that the temperature of the Achaean atmosphere may have played a significant role in determining the extent of S-MIF.

High-voltage electrical apparatus utilizing an insulating gas of sulfur hexafluoride and helium

DOEpatents

Wootton, Roy E.

1980-01-01

High-voltage electrical apparatus includes an outer housing at low potential, an inner electrode disposed within the outer housing at high potential with respect thereto, and support means for insulatably supporting the inner electrode within the outer housing. Conducting particles contaminate the interior of the outer housing, and an insulating gas electrically insulates the inner electrode from the outer housing even in the presence of the conducting particles. The insulating gas is comprised of sulfur hexafluoride at a partial pressure of from about 2.9 to about 3.4 atmospheres absolute, and helium at a partial pressure from about 1.1 to about 11.4 atmospheres absolute. The sulfur hexafluoride comprises between 20 and 65 volume percent of the insulating gas.

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. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

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.

Simultaneous capture of metal, sulfur and chlorine by sorbents during fluidized bed incineration.

PubMed

Ho, T C; Chuang, T C; Chelluri, S; Lee, Y; Hopper, J R

2001-01-01

Metal capture experiments were carried out in an atmospheric fluidized bed incinerator to investigate the effect of sulfur and chlorine on metal capture efficiency and the potential for simultaneous capture of metal, sulfur and chlorine by sorbents. In addition to experimental investigation, the effect of sulfur and chlorine on the metal capture process was also theoretically investigated through performing equilibrium calculations based on the minimization of system free energy. The observed results have indicated that, in general, the existence of sulfur and chlorine enhances the efficiency of metal capture especially at low to medium combustion temperatures. The capture mechanisms appear to include particulate scrubbing and chemisorption depending on the type of sorbents. Among the three sorbents tested, calcined limestone is capable of capturing all the three air pollutants simultaneously. The results also indicate that a mixture of the three sorbents, in general, captures more metals than a single sorbent during the process. In addition, the existence of sulfur and chlorine apparently enhances the metal capture process.

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).

Variability in morphology, hygroscopicity, and optical properties of soot aerosols during atmospheric processing

PubMed Central

Zhang, Renyi; Khalizov, Alexei F.; Pagels, Joakim; Zhang, Dan; Xue, Huaxin; McMurry, Peter H.

2008-01-01

The atmospheric effects of soot aerosols include interference with radiative transfer, visibility impairment, and alteration of cloud formation and are highly sensitive to the manner by which soot is internally mixed with other aerosol constituents. We present experimental studies to show that soot particles acquire a large mass fraction of sulfuric acid during atmospheric aging, considerably altering their properties. Soot particles exposed to subsaturated sulfuric acid vapor exhibit a marked change in morphology, characterized by a decreased mobility-based diameter but an increased fractal dimension and effective density. These particles experience large hygroscopic size and mass growth at subsaturated conditions (<90% relative humidity) and act efficiently as cloud-condensation nuclei. Coating with sulfuric acid and subsequent hygroscopic growth enhance the optical properties of soot aerosols, increasing scattering by ≈10-fold and absorption by nearly 2-fold at 80% relative humidity relative to fresh particles. In addition, condensation of sulfuric acid is shown to occur at a similar rate on ambient aerosols of various types of a given mobility size, regardless of their chemical compositions and microphysical structures. Representing an important mechanism of atmospheric aging, internal mixing of soot with sulfuric acid has profound implications on visibility, human health, and direct and indirect climate forcing. PMID:18645179

Estimation of laser beam pointing parameters in the presence of atmospheric turbulence.

PubMed

Borah, Deva K; Voelz, David G

2007-08-10

The problem of estimating mechanical boresight and jitter performance of a laser pointing system in the presence of atmospheric turbulence is considered. A novel estimator based on maximizing an average probability density function (pdf) of the received signal is presented. The proposed estimator uses a Gaussian far-field mean irradiance profile, and the irradiance pdf is assumed to be lognormal. The estimates are obtained using a sequence of return signal values from the intended target. Alternatively, one can think of the estimates being made by a cooperative target using the received signal samples directly. The estimator does not require sample-to-sample atmospheric turbulence parameter information. The approach is evaluated using wave optics simulation for both weak and strong turbulence conditions. Our results show that very good boresight and jitter estimation performance can be obtained under the weak turbulence regime. We also propose a novel technique to include the effect of very low received intensity values that cannot be measured well by the receiving device. The proposed technique provides significant improvement over a conventional approach where such samples are simply ignored. Since our method is derived from the lognormal irradiance pdf, the performance under strong turbulence is degraded. However, the ideas can be extended with appropriate pdf models to obtain more accurate results under strong turbulence conditions.

Sulfur Dioxide and Material Damage

ERIC Educational Resources Information Center

Gillette, Donald G.

1975-01-01

This study relates sulfur dioxide levels with material damage in heavily populated or polluted areas. Estimates of loss were determined from increased maintenance and replacement costs. The data indicate a decrease in losses during the past five years probably due to decline in pollution levels established by air quality standards. (MR)

Effect of sulfur content in a sulfur-activated carbon composite on the electrochemical properties of a lithium/sulfur battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Jin-Woo; Kim, Changhyeon; Ryu, Ho-Suk

2015-09-15

Highlights: • The content of sulfur in activated carbon was controlled by solution process. • The sulfur electrode with low sulfur content shows the best performance. • The Li/S battery has capacity of 1360 mAh/g at 1 C and 702 mAh/g at 10 C. - Abstract: The content of sulfur in sulfur/activated carbon composite is controlled from 32.37 wt.% to 55.33 wt.% by a one-step solution-based process. When the sulfur content is limited to 41.21 wt.%, it can be loaded into the pores of an activated carbon matrix in a highly dispersed state. On the contrary, when the sulfur contentmore » is 55.33 wt.%, crystalline sulfur can be detected on the surface of the activated carbon matrix. The best electrochemical performance can be obtained for a sulfur electrode with the lowest sulfur content. The sulfur/activated carbon composite with 32.37 wt.% sulfur afforded the highest first discharge capacity of 1360 mAh g{sup −1} at 1 C rate and a large reversible capacity of 702 mAh g{sup −1} at 10 C (16.75 A/g)« less

A Sulfur Dioxide Climate Feedback on Early Mars

NASA Astrophysics Data System (ADS)

Halevy, I.; Pierrehumbert, R. T.; Schrag, D. P.

2007-12-01

Reconciling evidence for persistent liquid water during the late Noachian with our understanding of the evolution of the Martian atmosphere and of solar luminosity remains a challenge, despite several decades of research. An optically-thicker atmosphere to supply the necessary radiative forcing would result in the existence of a carbon cycle similar to Earth's, where the release of CO2 from volcanoes is balanced by burial of calcium carbonate through silicate weathering reactions that remove protons and release alkalinity to surface waters. Existence of such a carbon cycle on Mars, even for tens of millions of years, would yield carbonate sediments in far greater abundance than has been observed, as well as residual clay minerals. The high concentration of sulfur in Martian soils and rocks indicates that Martian volcanic emissions contained abundant sulfur volatiles in addition to CO2. However, the atmospheric and aquatic chemistry of SO2 under the reducing conditions of early Mars, in contrast with the presently oxidizing and biologically-catalyzed Earth, has not been thoroughly examined. We argue that these conditions may have allowed atmospheric concentrations of SO2 high enough to augment a thick CO2-H2O greenhouse. Furthermore, early Martian climate may have been stabilized by a feedback mechanism involving SO2 and the solubility of sulfite minerals instead of CO2 and the solubility of carbonates. We present the results of a one-dimensional radiative-convective model, demonstrating the radiative importance of SO2 to the planetary energy budget. We also use a simple geochemical model to show that the presence of SO2 in the early Martian atmosphere would have dominated the aquatic chemistry on the planet's surface, and may provide an explanation for how water could have persisted for millions of years without forming massive carbonate sediments, yet allowing the formation of clay minerals.

The Hurst Phenomenon in Error Estimates Related to Atmospheric Turbulence

NASA Astrophysics Data System (ADS)

Dias, Nelson Luís; Crivellaro, Bianca Luhm; Chamecki, Marcelo

2018-05-01

The Hurst phenomenon is a well-known feature of long-range persistence first observed in hydrological and geophysical time series by E. Hurst in the 1950s. It has also been found in several cases in turbulence time series measured in the wind tunnel, the atmosphere, and in rivers. Here, we conduct a systematic investigation of the value of the Hurst coefficient H in atmospheric surface-layer data, and its impact on the estimation of random errors. We show that usually H > 0.5 , which implies the non-existence (in the statistical sense) of the integral time scale. Since the integral time scale is present in the Lumley-Panofsky equation for the estimation of random errors, this has important practical consequences. We estimated H in two principal ways: (1) with an extension of the recently proposed filtering method to estimate the random error (H_p ), and (2) with the classical rescaled range introduced by Hurst (H_R ). Other estimators were tried but were found less able to capture the statistical behaviour of the large scales of turbulence. Using data from three micrometeorological campaigns we found that both first- and second-order turbulence statistics display the Hurst phenomenon. Usually, H_R is larger than H_p for the same dataset, raising the question that one, or even both, of these estimators, may be biased. For the relative error, we found that the errors estimated with the approach adopted by us, that we call the relaxed filtering method, and that takes into account the occurrence of the Hurst phenomenon, are larger than both the filtering method and the classical Lumley-Panofsky estimates. Finally, we found that there is no apparent relationship between H and the Obukhov stability parameter. The relative errors, however, do show stability dependence, particularly in the case of the error of the kinematic momentum flux in unstable conditions, and that of the kinematic sensible heat flux in stable conditions.

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 CO 2 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) andmore » fitting. 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 CO 2 (ffCO 2) 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 ffCO 2 emissions and synthetic observations of ffCO 2 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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Atmospheric inversions are frequently used to estimate fluxes of atmospheric greenhouse gases (e.g., biospheric CO 2 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) andmore » fitting. 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 CO 2 (ffCO 2) 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 ffCO 2 emissions and synthetic observations of ffCO 2 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

SPARC's Stratospheric Sulfur and its Role in Climate Activity (SSiRC)

NASA Technical Reports Server (NTRS)

Thomason, Larry

2015-01-01

The stratospheric aerosol layer is a key component in the climate system. It affects the radiative balance of the atmosphere directly through interactions with solar and terrestrial radiation, and indirectly through its effect on stratospheric ozone. Because the stratospheric aerosol layer is prescribed in many climate models and Chemistry-Climate Models (CCMs), model simulations of future atmospheric conditions and climate generally do not account for the interaction between the aerosol-sulfur cycle and changes in the climate system. The present understanding of how the stratospheric aerosol layer may be affected by future climate change and how the stratospheric aerosol layer may drive climate change is, therefore, very limited. The purposes of SSiRC (Stratospheric Sulfur and its Role in Climate) include: (i) providing a coordinating structure for the various individual activities already underway in different research centers; (ii) encouraging and supporting new instrumentation and measurements of sulfur containing compounds, such as COS, DMS, and non-volcanic SO2 in the UT/LS globally; and (iii) initiating new model/data inter-comparisons. SSiRC is developing collaborations with a number of other SPARC activities including CCMI and ACAM. This presentation will highlight the scientific goals of this project and on-going activities and propose potential interactions between SSiRC and ACAM.

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.

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.

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

Atmospheric Deposition of Nitrogen and Sulfur in the Yellow Sea Region

NASA Astrophysics Data System (ADS)

Ghim, Y.; Kim, J.; Lee, S.; Moon, K.; Won, J.; Yoon, S.

2002-05-01

The Yellow Sea is a semi-enclosed, shelf-type shallow basin with reduced water exchange with the open ocean. The rim of the Yellow Sea--the west side is China and the east side is Korea--is one of the fastest developing zones in the world. During the past several years, considerable measurements have been made both around and over the Yellow Sea in order to study the pollutant transport in the region. Fine particles as well as gaseous pollutants have been routinely measured at three national background monitoring stations on the Korean side. Two ground stations have been operated for supplementing these monitoring stations; one is on the Korean side and the other is on the Chinese side. Aircraft and shipboard measurements were also made during selected intensive measurement periods. However, not all these measurements have been made for a common object. Rather, several research teams carried out their measurements for their own purposes according to separate plans. In the present work, the amounts of nitrogen and sulfur deposited in the region of the Yellow Sea in both dry and wet forms were estimated. Concentration data available from each measurement were reviewed to choose adequate ones. Meteorological data at ground stations were readily obtained either from a collocated automatic weather station or from a surface weather station in the nearby area. However, those over the sea were estimated from the output of RDAPS (Regional Data Assimilation and Prediction System), which were provided by the Korea Meteorological Administration. Precipitation data were only available from several routinely operated ground stations since intensive measurements accompanying aircraft or shipboard measurements were not made on rainy days. The amounts of dry and wet depositions were compared at these stations. (This work was supported in part by the Korea Ministry of Science and Technology under grant 98-LO-01-01-A-003 and in part by the Sustainable Water Resources Research Center

Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

NASA Astrophysics Data System (ADS)

Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro

2016-04-01

Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

Method of preparing graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

DOEpatents

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuliang; Li, Xiaolin

2015-04-07

A method of preparing a graphene-sulfur nanocomposite for a cathode in a rechargeable lithium-sulfur battery comprising thermally expanding graphite oxide to yield graphene layers, mixing the graphene layers with a first solution comprising sulfur and carbon disulfide, evaporating the carbon disulfide to yield a solid nanocomposite, and grinding the solid nanocomposite to yield the graphene-sulfur nanocomposite. Rechargeable-lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter of less than 50 nm.

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

Online air analysis of reduced sulfur compounds at a swine facility

USDA-ARS?s Scientific Manuscript database

Reduced sulfur compounds are emitted from waste management handling and can be important in odor production and atmospheric chemistry. Data on the emissions of these compounds have been obtained using off-line sampling and analysis methods, but on-line methods providing information on temporal chang...

Rhodanese Functions as Sulfur Supplier for Key Enzymes in Sulfur Energy Metabolism

PubMed Central

Aussignargues, Clément; Giuliani, Marie-Cécile; Infossi, Pascale; Lojou, Elisabeth; Guiral, Marianne; Giudici-Orticoni, Marie-Thérèse; Ilbert, Marianne

2012-01-01

How microorganisms obtain energy is a challenging topic, and there have been numerous studies on the mechanisms involved. Here, we focus on the energy substrate traffic in the hyperthermophilic bacterium Aquifex aeolicus. This bacterium can use insoluble sulfur as an energy substrate and has an intricate sulfur energy metabolism involving several sulfur-reducing and -oxidizing supercomplexes and enzymes. We demonstrate that the cytoplasmic rhodanese SbdP participates in this sulfur energy metabolism. Rhodaneses are a widespread family of proteins known to transfer sulfur atoms. We show that SbdP has also some unusual characteristics compared with other rhodaneses; it can load a long sulfur chain, and it can interact with more than one partner. Its partners (sulfur reductase and sulfur oxygenase reductase) are key enzymes of the sulfur energy metabolism of A. aeolicus and share the capacity to use long sulfur chains as substrate. We demonstrate a positive effect of SbdP, once loaded with sulfur chains, on sulfur reductase activity, most likely by optimizing substrate uptake. Taken together, these results lead us to propose a physiological role for SbdP as a carrier and sulfur chain donor to these key enzymes, therefore enabling channeling of sulfur substrate in the cell as well as greater efficiency of the sulfur energy metabolism of A. aeolicus. PMID:22496367

Determination of total sulfur content via sulfur-specific chemiluminescence detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kubala, S.W.; Campbell, D.N.; DiSanzo, F.P.

A specially designed system, based upon sulfur-specific chemiluminescence detection (SSCD), was developed to permit the determination of total sulfur content in a variety of samples. This type of detection system possesses several advantages such as excellent linearity and selectivity, low minimum detectable levels, and an equimolar response to various sulfur compounds. This paper will focus on the design and application of a sulfur-specific chemiluminescence detection system for use in determining total sulfur content in gasoline.

New Parameterizations for Neutral and Ion-Induced Sulfuric Acid-Water Particle Formation in Nucleation and Kinetic Regimes

NASA Astrophysics Data System (ADS)

Määttänen, Anni; Merikanto, Joonas; Henschel, Henning; Duplissy, Jonathan; Makkonen, Risto; Ortega, Ismael K.; Vehkamäki, Hanna

2018-01-01

We have developed new parameterizations of electrically neutral homogeneous and ion-induced sulfuric acid-water particle formation for large ranges of environmental conditions, based on an improved model that has been validated against a particle formation rate data set produced by Cosmics Leaving OUtdoor Droplets (CLOUD) experiments at European Organization for Nuclear Research (CERN). The model uses a thermodynamically consistent version of the Classical Nucleation Theory normalized using quantum chemical data. Unlike the earlier parameterizations for H2SO4-H2O nucleation, the model is applicable to extreme dry conditions where the one-component sulfuric acid limit is approached. Parameterizations are presented for the critical cluster sulfuric acid mole fraction, the critical cluster radius, the total number of molecules in the critical cluster, and the particle formation rate. If the critical cluster contains only one sulfuric acid molecule, a simple formula for kinetic particle formation can be used: this threshold has also been parameterized. The parameterization for electrically neutral particle formation is valid for the following ranges: temperatures 165-400 K, sulfuric acid concentrations 104-1013 cm-3, and relative humidities 0.001-100%. The ion-induced particle formation parameterization is valid for temperatures 195-400 K, sulfuric acid concentrations 104-1016 cm-3, and relative humidities 10-5-100%. The new parameterizations are thus applicable for the full range of conditions in the Earth's atmosphere relevant for binary sulfuric acid-water particle formation, including both tropospheric and stratospheric conditions. They are also suitable for describing particle formation in the atmosphere of Venus.

Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Elizabeth C.; Kasse, Robert M.; Heath, Khloe N.

Here, a novel cross-sectional battery cell was developed to characterize lithium-sulfur batteries using X-ray spectromicroscopy. Chemically sensitive X-ray maps were collected operando at energies relevant to the expected sulfur species and were used to correlate changes in sulfur species with electrochemistry. Significant changes in the sulfur/carbon composite electrode were observed from cycle to cycle including rearrangement of the elemental sulfur matrix and PEO10LiTFSI binder. Polysulfide concentration and area of spatial diffusion increased with cycling, indicating that some polysulfide dissolution is irreversible, leading to polysulfide shuttle. Fitting of the maps using standard sulfur and polysulfide XANES spectra indicated that upon subsequentmore » discharge/charge cycles, the initial sulfur concentration was not fully recovered; polysulfides and lithium sulfide remained at the cathodes with higher order polysulfides as the primary species in the region of interest. Quantification of the polysulfide concentration across the electrolyte and electrode interfaces shows that the polysulfide concentration before the first discharge and after the third charge is constant within the electrolyte, but while cycling, a significant increase in polysulfides and a gradient toward the lithium metal anode forms. Finally, this chemically and spatially sensitive characterization and analysis provides a foundation for further operando spectromicroscopy of lithium-sulfur batteries.« less

Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries

DOE PAGES

Miller, Elizabeth C.; Kasse, Robert M.; Heath, Khloe N.; ...

2017-11-03

Here, a novel cross-sectional battery cell was developed to characterize lithium-sulfur batteries using X-ray spectromicroscopy. Chemically sensitive X-ray maps were collected operando at energies relevant to the expected sulfur species and were used to correlate changes in sulfur species with electrochemistry. Significant changes in the sulfur/carbon composite electrode were observed from cycle to cycle including rearrangement of the elemental sulfur matrix and PEO10LiTFSI binder. Polysulfide concentration and area of spatial diffusion increased with cycling, indicating that some polysulfide dissolution is irreversible, leading to polysulfide shuttle. Fitting of the maps using standard sulfur and polysulfide XANES spectra indicated that upon subsequentmore » discharge/charge cycles, the initial sulfur concentration was not fully recovered; polysulfides and lithium sulfide remained at the cathodes with higher order polysulfides as the primary species in the region of interest. Quantification of the polysulfide concentration across the electrolyte and electrode interfaces shows that the polysulfide concentration before the first discharge and after the third charge is constant within the electrolyte, but while cycling, a significant increase in polysulfides and a gradient toward the lithium metal anode forms. Finally, this chemically and spatially sensitive characterization and analysis provides a foundation for further operando spectromicroscopy of lithium-sulfur batteries.« less

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.

Lunar sulfur

NASA Technical Reports Server (NTRS)

Kuck, David L.

1991-01-01

Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

Lunar sulfur

NASA Astrophysics Data System (ADS)

Kuck, David L.

Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

Cytochromes and iron sulfur proteins in sulfur metabolism of phototrophic bacteria

NASA Technical Reports Server (NTRS)

Fischer, U.

1985-01-01

Dissimilatory sulfur metabolism in phototrophic sulfur bacteria provides the bacteria with electrons for photosynthetic electron transport chain and, with energy. Assimilatory sulfate reduction is necessary for the biosynthesis of sulfur-containing cell components. Sulfide, thiosulfate, and elemental sulfur are the sulfur compounds most commonly used by phototrophic bacteria as electron donors for anoxygenic photosynthesis. Cytochromes or other electron transfer proteins, like high-potential-iron-sulfur protein (HIPIP) function as electron acceptors or donors for most enzymatic steps during the oxidation pathways of sulfide or thiosulfate. Yet, heme- or siroheme-containing proteins themselves undergo enzymatic activities in sulfur metabolism. Sirohemes comprise a porphyrin-like prosthetic group of sulfate reductase. eenzymatic reactions involve electron transfer. Electron donors or acceptors are necessary for each reaction. Cytochromes and iron sulfur problems, are able to transfer electrons.

UAV remote sensing atmospheric degradation image restoration based on multiple scattering APSF estimation

NASA Astrophysics Data System (ADS)

Qiu, Xiang; Dai, Ming; Yin, Chuan-li

2017-09-01

Unmanned aerial vehicle (UAV) remote imaging is affected by the bad weather, and the obtained images have the disadvantages of low contrast, complex texture and blurring. In this paper, we propose a blind deconvolution model based on multiple scattering atmosphere point spread function (APSF) estimation to recovery the remote sensing image. According to Narasimhan analytical theory, a new multiple scattering restoration model is established based on the improved dichromatic model. Then using the L0 norm sparse priors of gradient and dark channel to estimate APSF blur kernel, the fast Fourier transform is used to recover the original clear image by Wiener filtering. By comparing with other state-of-the-art methods, the proposed method can correctly estimate blur kernel, effectively remove the atmospheric degradation phenomena, preserve image detail information and increase the quality evaluation indexes.

Formation of Multilayer Graphene Domains with Strong Sulfur-Carbon Interaction and Enhanced Sulfur Reduction Zones for Lithium-Sulfur Battery Cathodes.

PubMed

Perez Beltran, Saul; Balbuena, Perla B

2018-02-12

A newly designed sulfur/graphene computational model emulates the electrochemical behavior of a Li-S battery cathode, promoting the S-C interaction through the edges of graphene sheets. A random mixture of eight-membered sulfur rings mixed with small graphene sheets is simulated at 64 wt %sulfur loading. Structural stabilization and sulfur reduction calculations are performed with classical reactive molecular dynamics. This methodology allowed the collective behavior of the sulfur and graphene structures to be accounted for. The sulfur encapsulation induces ring opening and the sulfur phase evolves into a distribution of small chain-like structures interacting with C through the graphene edges. This new arrangement of the sulfur phase not only leads to a less pronounced volume expansion during sulfur reduction but also to a different discharge voltage profile, in qualitative agreement with earlier reports on sulfur encapsulation in microporous carbon structures. The Li 2 S phase grows around ensembles of parallel graphene nanosheets during sulfur reduction. No diffusion of sulfur or lithium between graphene nanosheets is observed, and extended Li 2 S domains bridging the space between carbon ensembles are suppressed. The results emphasize the importance of morphology on the electrochemical performance of the composite material. The sulfur/graphene model outlined here provides new understanding of the graphene effects on the sulfur reduction behavior and the role that van der Waals interactions may play in promoting formation of multilayer graphene ensembles and small Li 2 S domains during sulfur reduction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of the sulfur isotope ratio in carbonyl sulfide using gas chromatography/isotope ratio mass spectrometry on fragment ions 32S+, 33S+, and 34S+.

PubMed

Hattori, Shohei; Toyoda, Akari; Toyoda, Sakae; Ishino, Sakiko; Ueno, Yuichiro; Yoshida, Naohiro

2015-01-06

Little is known about the sulfur isotopic composition of carbonyl sulfide (OCS), the most abundant atmospheric sulfur species. We present a promising new analytical method for measuring the stable sulfur isotopic compositions (δ(33)S, δ(34)S, and Δ(33)S) of OCS using nanomole level samples. The direct isotopic analytical technique consists of two parts: a concentration line and online gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions (32)S(+), (33)S(+), and (34)S(+). The current levels of measurement precision for OCS samples greater than 8 nmol are 0.42‰, 0.62‰, and 0.23‰ for δ(33)S, δ(34)S, and Δ(33)S, respectively. These δ and Δ values show a slight dependence on the amount of injected OCS for volumes smaller than 8 nmol. The isotope values obtained from the GC-IRMS method were calibrated against those measured by a conventional SF6 method. We report the first measurement of the sulfur isotopic composition of OCS in air collected at Kawasaki, Kanagawa, Japan. The δ(34)S value obtained for OCS (4.9 ± 0.3‰) was lower than the previous estimate of 11‰. When the δ(34)S value for OCS from the atmospheric sample is postulated as the global signal, this finding, coupled with isotopic fractionation for OCS sink reactions in the stratosphere, explains the reported δ(34)S for background stratospheric sulfate. This suggests that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols.

Understanding Sulfur Systematics in Large Igneous Provinces Using Sulfur Isotopes

NASA Astrophysics Data System (ADS)

Novikova, S.; Edmonds, M.; Turchyn, A. V.; Maclennan, J.; Svensen, H.; Frost, D. J.; Yallup, C.

2013-12-01

The eruption of the Siberian Traps coincided with perhaps the greatest environmental catastrophe in Earth's history, at the Permo-Triassic boundary. The source and magnitude of the volatile emissions, including sulfur, associated with the eruption remain poorly understood yet were critical in forcing environmental change. Two of the primary questions are how much sulfur gases were emitted during the eruptions and from where they were sourced. Primary melts carry dissolved sulfur from the mantle. Magmas ponding in sills and ascending through dykes may also assimilate sulfur from country rocks, as well as heat the country rocks and generate fluids through contact metamorphism. If the magmas interacted thermally, for prolonged periods, with sulfur-rich country rocks then it is probable that the sulfur budget of these eruptions might have been augmented considerably. This is exactly what we have shown recently for a basaltic sill emplaced in oil shale that fed eruptions of the British Tertiary Province, where surrounding sediments showed extensive desulfurization (Yallup et al. Geoch. Cosmochim. Acta, online, 2013). In the current study sulfur isotopes and trace element abundances are used to discriminate sulfur sources and to model magmatic processes for a suite of Siberian Traps sill and lava samples. Our bulk rock and pyrite geochemical analyses illustrate clearly their high abundance of 34S over 32S. The high 34S/32S has been noted previously and linked to assimilation of sulfur from sediments but may alternatively be inherited from the mantle plume source. With the aim of investigating the sulfur isotopic signature in the melt prior to devolatilization, we use secondary ion mass spectrometry (SIMS), for which a specific set of glass standards was synthesised. In order to understand how sulfur isotopes fractionate during degassing we have also conducted a parallel study of well-characterized tephras from Kilauea Volcano, where sulfur degassing behavior is well

Sulfur in vacuum - Sublimation effects on frozen melts, and applications to Io's surface and torus

NASA Technical Reports Server (NTRS)

Nash, Douglas B.

1987-01-01

Vacuum sublimation effects on solid sulfur yield a form of the element that is white at room temperature, is fluffy in texture, and forms on frozen sulfur in vacuum through differential evaporation of molecular species in the solid. This vacuum sulfur should exist in large quantity on Io, if the solid free sulfur there has solidified from a melt; a sulfur volcanism model for Io is accordingly developed on this basis which implies that the color and spectra of different sulfur regions of Io could indicate their relative crystallization ages and cooling histories. The flux of sublimating hotspot sulfur appears consistent with estimated turnover rates of the Io surface.

The Biogeochemistry of Sulfur in Hydrothermal Systems

NASA Technical Reports Server (NTRS)

Schulte, Mitchell; Rogers, K. L.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. Understanding how sulfur became prevalent in biochemical processes and many biomolecules requires knowledge of the reaction properties of sulfur-bearing compounds. We have previously estimated thermodynamic data for thiols, the simplest organic sulfur compounds, at elevated temperatures and pressures. If life began in hydrothermal environments, it is especially important to understand reactions at elevated temperatures among sulfur-bearing compounds and other organic molecules essential for the origin and persistence of life. Here we examine reactions that may have formed amino acids with thiols as reaction intermediates in hypothetical early Earth hydrothermal environments. (There are two amino acids, cysteine and methionine, that contain sulfur.) Our calculations suggest that significant amounts of some amino acids were produced in early Earth hydrothermal fluids, given reasonable concentrations H2, NH3, H2S and CO. For example, preliminary results indicate that glycine activities as high as 1 mmol can be reached in these systems at 100 C. Alanine formation from propanethiol is also a favorable reaction. On the other hand, the calculated equilibrium log activities of cysteine and serine from propanethiol are -21 and -19, respectively, at 100 C. These results

Sulfur partitioning applied to LIP magmatism - A new approach for quantifying sulfur concentration in basaltic melts

NASA Astrophysics Data System (ADS)

Marzoli, A.; Callegaro, S.; Baker, D. R.; De Min, A.; Cavazzini, G.; Martin, W.; Renne, P. R.; Svensen, H.

2017-12-01

Magmatism from Large Igneous Provinces (LIPs) has often been demonstrated synchronous with mass extinctions. Prominent examples in the Phanerozoic are the end-Permian, end-Triassic and end-Cretaceous extinctions, associated with, respectively, the Siberian Traps, the CAMP and the Deccan Traps. Despite the growing body of evidence for causal and temporal links between these events, it is not yet entirely clear how a LIP can severly affect the global environment. Degassing of volatile species such as S, C and halogen compounds directly from LIP magmas, and from contact metamorphism of volatile-rich sediments heated by the intrusions appears as the most realistic mechanism. Modeling the atmospheric response to LIP gas loads requires quantitative constraints on the degassed volatiles and emission rates, but these are challenging to obtain for magmatic systems from the geologic past. We therefore propose a new method to calculate the sulfur load of basaltic melts, by measuring sulfur content in natural minerals (clinopyroxene and plagioclase) and combining it with an experimentally determined partition coefficients (KD). We measured partitioning of sulfur between crystals and melt by ion microprobe (Nordsim, Stockholm) on experimentally produced crystals and glasses. Piston cylinder experiments were performed with conditions typical of basaltic, andesitic and dacitic melts (800 or 1000 MPa; 1000°-1350°C), to constrain KD variations as a function of melt composition, oxidation state and water content. We obtained a clinopyroxene/melt sulfur KD of 0.001 for basaltic melts, which can be applied to natural continental flood basalts. Preliminary results from thoroughly-dated lava piles from the Deccan Traps and from the Siberian Traps sills confirm that most of the basalts were at or close to sulfide saturation (ca. 2000 ppm for low fO2 melts). These results can be compared with the scenario modeled by Schmidt et al. (2016) for Deccan Traps magmatism, for which sulfur from

Dissolved organic sulfur in the ocean: Biogeochemistry of a petagram inventory

NASA Astrophysics Data System (ADS)

Ksionzek, Kerstin B.; Lechtenfeld, Oliver J.; McCallister, S. Leigh; Schmitt-Kopplin, Philippe; Geuer, Jana K.; Geibert, Walter; Koch, Boris P.

2016-10-01

Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of nonvolatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid-phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. Although molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (sulfur/nitrogen ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 petagrams of sulfur, exceeding all other marine organic sulfur reservoirs by an order of magnitude.

Method for removing sulfur oxide from waste gases and recovering elemental sulfur

DOEpatents

Moore, Raymond H.

1977-01-01

A continuous catalytic fused salt extraction process is described for removing sulfur oxides from gaseous streams. The gaseous stream is contacted with a molten potassium sulfate salt mixture having a dissolved catalyst to oxidize sulfur dioxide to sulfur trioxide and molten potassium normal sulfate to solvate the sulfur trioxide to remove the sulfur trioxide from the gaseous stream. A portion of the sulfur trioxide loaded salt mixture is then dissociated to produce sulfur trioxide gas and thereby regenerate potassium normal sulfate. The evolved sulfur trioxide is reacted with hydrogen sulfide as in a Claus reactor to produce elemental sulfur. The process may be advantageously used to clean waste stack gas from industrial plants, such as copper smelters, where a supply of hydrogen sulfide is readily available.

An Inequality Constrained Least-Squares Approach as an Alternative Estimation Procedure for Atmospheric Parameters from VLBI Observations

NASA Astrophysics Data System (ADS)

Halsig, Sebastian; Artz, Thomas; Iddink, Andreas; Nothnagel, Axel

2016-12-01

On its way through the atmosphere, radio signals are delayed and affected by bending and attenuation effects relative to a theoretical path in vacuum. In particular, the neutral part of the atmosphere contributes considerably to the error budget of space-geodetic observations. At the same time, space-geodetic techniques become more and more important in the understanding of the Earth's atmosphere, because atmospheric parameters can be linked to the water vapor content in the atmosphere. The tropospheric delay is usually taken into account by applying an adequate model for the hydrostatic component and by additionally estimating zenith wet delays for the highly variable wet component. Sometimes, the Ordinary Least Squares (OLS) approach leads to negative estimates, which would be equivalent to negative water vapor in the atmosphere and does, of course, not reflect meteorological and physical conditions in a plausible way. To cope with this phenomenon, we introduce an Inequality Constrained Least Squares (ICLS) method from the field of convex optimization and use inequality constraints to force the tropospheric parameters to be non-negative allowing for a more realistic tropospheric parameter estimation in a meteorological sense. Because deficiencies in the a priori hydrostatic modeling are almost fully compensated by the tropospheric estimates, the ICLS approach urgently requires suitable a priori hydrostatic delays. In this paper, we briefly describe the ICLS method and validate its impact with regard to station positions.

PROCEEDINGS ON SYNCHROTRON RADIATION: Transfer characterization of sulfur from coal-burning emission to plant leaves by PIXE and XANES

NASA Astrophysics Data System (ADS)

Bao, Liang-Man; Zhang, Gui-Lin; Zhang, Yuan-Xim; Li, Yan; Lin, Jun; Liu, Wei; Cao, Qing-Chen; Zhao, Yi-Dong; Ma, Chen-Yan; Han, Yong

2009-11-01

The impact of coal-burning emission on sulfur in camphor leaves was investigated using Proton Induced X-ray Emission (PIXE) and synchrotron radiation technique X-ray Absorption Near-Edge Structure (XANES) spectroscopy. The PIXE results show that the sulfur concentrations in the leaves collected at the polluted site are significantly higher than those in controls. The Sulfur XANES spectra show the presence of organic (disulfides, thiols, thioethers, sulfonates and sulfoxides) and inorganic sulfur (sulfates) in the leaves. The inorganic sulfur in the leaves of camphor tree polluted by coal combustion is 15% more than that of the control site. The results suggest that the long-term coal-burning pollution resulted in an enhanced content of the total sulfur and sulfate in the leaves, and the uptake of sulfur by leaves had exceeded the metabolic requirement of plants and the excess of sulfur was stored as SO2-4. It can monitor the sulfur pollution in atmosphere.

Sulfur in vacuum - Sublimation effects on frozen melts, and applications to Io's surface and torus

NASA Astrophysics Data System (ADS)

Nash, D. B.

1987-10-01

The author has found from laboratory experiments that vacuum sublimation has a profound effect on the molecular composition, microtexture, bulk density (porosity), and the UV/visible spectral reflectance of the surface of solid sulfur samples, both when the sulfur is in the form of frozen or quenched melts and as laboratory-grade sulfur powder. These sublimation effects produce a unique surface material, the understanding of which may have important implications for deciphering the many enigmatic optical and textural properties of the surface of Jupiter's satellite Io. This planetary body is thought to have a surface greatly enriched in volcanically produced elemental sulfur and sulfur compounds and to have a surface atmospheric pressure with an upper limit of ≡10-7atm, comparable to a good laboratory vacuum, and surface hotspots at temperatures of about 300K covering about 0.3% of its global surface.

Sulfur isotope variability of oceanic DMSP generation and its contributions to marine biogenic sulfur emissions

NASA Astrophysics Data System (ADS)

Oduro, Harry; Van Alstyne, Kathryn L.; Farquhar, James

2012-06-01

Oceanic dimethylsulfoniopropionate (DMSP) is the precursor to dimethylsulfide (DMS), which plays a role in climate regulation through transformation to methanesulfonic acid (MSA) and non-seasalt sulfate (NSS-SO42-) aerosols. Here, we report measurements of the abundance and sulfur isotope compositions of DMSP from one phytoplankton species (Prorocentrum minimum) and five intertidal macroalgal species (Ulva lactuca, Ulva linza, Ulvaria obscura, Ulva prolifera, and Polysiphonia hendryi) in marine waters. We show that the sulfur isotope compositions (δ34S) of DMSP are depleted in 34S relative to the source seawater sulfate by ∼1-3‰ and are correlated with the observed intracellular content of methionine, suggesting a link to metabolic pathways of methionine production. We suggest that this variability of δ34S is transferred to atmospheric geochemical products of DMSP degradation (DMS, MSA, and NSS-SO42-), carrying implications for the interpretation of variability in δ34S of MSA and NSS-SO42- that links them to changes in growth conditions and populations of DMSP producers rather than to the contributions of DMS and non-DMS sources.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

Medical aspects of atmosphere pollution in Tbilisi, Georgia.

PubMed

Lagidze, Lamzira; Matchavariani, Lia; Tsivtsivadze, Nodar; Khidasheli, Nargiz; Paichadze, Nino; Motsonelidze, Nargiz; Vakhtangishvili, Maia

2015-01-01

Climate change and its impact on ecosystems is one of the main problem of 21st century. Increase in green house gas in the atmosphere was regarded as an important cause. Atmospheric composition had significantly changed due to intensive technogenic pollution. Increase in aerosol (solid, liquid and gas) concentration had serious impact on human health and raised the level of risk factors for longevity of life. Despite, global character of climatic change and its intensity in numerous ways was influenced by local specificity of regions, their geographical location and meteorological factors. A study on the atmospheric quality (quantitative and percentage estimation of aerosols) of Georgia was carried out. Also the assessment of impact of meteorological and ecological conditions on human health was made for Tbilisi city. A relation between contaminants and meteorological factors was evaluated, particularly gas pollutants were strongly correlated with each other due to their photochemical activity; positive correlation (0.65; 0.69) between air temperature and pollutants. All the contaminants showed negative correlation with relative humidity, due to hydrolyzing ability. On the basis of multi-factorial statistical analysis, correlation between ambulance call, weather type, atmosphere pollution index, change in ground ozone quantity and earth magnetic field were determined. Atmospheric pollution due to dust, carbon, sulfur and nitrogen oxides, ground ozone quantity in Tbilisi significantly exceeded maximum permissible level, that effected human health.

Interaction of sulfur dioxide and carbon dioxide with clean silver in ultrahigh vacuum.

NASA Technical Reports Server (NTRS)

Lassiter, W. S.

1972-01-01

It is shown that when a clean polycrystalline silver surface is subjected to sulfur dioxide at a pressure of 1 nanotorr, sulfur is chemisorbed to the silver. Heating the contaminated silver leads to an estimation of the minimum heat of desorption of 59 kcal/mol. Sulfur Auger peak height and relative function measurements of the surface during exposure show that adsorption occurs during 6 microtorr/sec exposure at 1 nanotorr.

Properties of Sulfur Concrete.

DTIC Science & Technology

1979-07-06

36 Thermal Contraction . . . . . . . . . . . 37 Summary of Sulfur Concrete (unmodified) . . . 39 Modified Sulfur Concrete............ 40...Compressive strength of PCPD- modified sulfur concrete 47 20 Functional connection between reaction time and temperature in making DCPD- modified sulfur concrete...39 MODIFIED SULFUR CONCRETE In the previous section it was shown that sulfur concrete exhibits several undesirable properties, such as 1 poor

Sulfur-Containing Agrochemicals.

PubMed

Devendar, Ponnam; Yang, Guang-Fu

2017-10-09

Modern agricultural chemistry has to support farmers by providing innovative agrochemicals. In this context, the introduction of sulfur atoms into an active ingredient is still an important tool in modulating the properties of new crop-protection compounds. More than 30% of today's agrochemicals contain at least one sulfur atom, mainly in fungicides, herbicides and insecticides. A number of recently developed sulfur-containing agrochemical candidates represent a novel class of chemical compounds with new modes of action, so we intend to highlight the emerging interest in commercially active sulfur-containing compounds. This chapter gives a comprehensive overview of selected leading sulfur-containing pesticidal chemical families namely: sulfonylureas, sulfonamides, sulfur-containing heterocyclics, thioureas, sulfides, sulfones, sulfoxides and sulfoximines. Also, the most suitable large-scale synthetic methods of the recently launched or provisionally approved sulfur-containing agrochemicals from respective chemical families have been highlighted.

Stabilization of sulfuric acid dimers by ammonia, methylamine, dimethylamine, and trimethylamine

NASA Astrophysics Data System (ADS)

Jen, Coty N.; McMurry, Peter H.; Hanson, David R.

2014-06-01

This study experimentally explores how ammonia (NH3), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA) affect the chemical formation mechanisms of electrically neutral clusters that contain two sulfuric acid molecules (dimers). Dimers may also contain undetectable compounds, such as water or bases, that evaporate upon ionization and sampling. Measurements were conducted using a glass flow reactor which contained a steady flow of humidified nitrogen with sulfuric acid concentrations of 107 to 109 cm-3. A known molar flow rate of a basic gas was injected into the flow reactor. The University of Minnesota Cluster Chemical Ionization Mass Spectrometer was used to measure the resulting sulfuric acid vapor and cluster concentrations. It was found that, for a given concentration of sulfuric acid vapor, the dimer concentration increases with increasing concentration of the basic gas, eventually reaching a plateau. The base concentrations at which the dimer concentrations saturate suggest NH3 < MA < TMA ≲ DMA in forming stabilized sulfuric acid dimers. Two heuristic models for cluster formation by acid-base reactions are developed to interpret the data. The models provide ranges of evaporation rate constants that are consistent with observations and leads to an analytic expression for nucleation rates that is consistent with atmospheric observations.

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.

Emission of volatile organic sulfur compounds (VOSCs) during aerobic decomposition of food wastes

NASA Astrophysics Data System (ADS)

Wu, Ting; Wang, Xinming; Li, Dejun; Yi, Zhigang

2010-12-01

Food wastes collected from typical urban residential communities were investigated for the emission of volatile organic sulfur compounds (VOSCs) during laboratory-controlled aerobic decomposition in an incubator for a period of 41 days. Emission of VOSCs from the food wastes totaled 409.9 mg kg -1 (dry weight), and dimethyl disulfide (DMDS), dimethyl sulfide (DMS), methyl 2-propenyl disulfide, carbonyl sulfide and methyl 1-propenyl sulfide were the five most abundant VOSCs, with shares of 75.5%, 13.5%, 4.8%, 2.2% and 1.3% in total 15 VOSCs released, respectively. The emission fluxes of major VOSCs were very low at the beginning (day 0). They peaked at days 2-4 and then decreased sharply until they leveled off after 10 days of incubation. For most VOSCs, over 95% of their emission occurred in the first 10 days. The time series of VOSC emission fluxes, as well as their significant correlation with internal food waste temperature ( p < 0.05) during incubation, suggested that production of VOSC species was induced mainly by microbial activities during the aerobic decomposition instead of as inherited. Released VOSCs accounted for 5.3% of sulfur content in the food wastes, implying that during aerobic decomposition considerable portion of sulfur in food wastes would be released into the atmosphere as VOSCs, primarily as DMDS, which is very short-lived in the atmosphere and thus usually less considered in the sources and sinks of reduced sulfur gases.

Emissions of biogenic sulfur gases from Alaskan tundra

NASA Technical Reports Server (NTRS)

Hines, Mark E.; Morrison, Michael C.

1992-01-01

Fluxes of the biogenic sulfur gases carbonyl sulfide (COS), dimethyl sulfide (DMS), methyl mercaptan (MeSH), and carbon disulfide (CS2) were determined for several freshwater and coastal marine tundra habitats using a dynamic enclosure method and gas chromatography. In the freshwater tundra sites, highest emissions, with a mean of 6.0 nmol/m(sup -2)H(sup -1) (1.5-10) occurred in the water-saturated wet meadow areas inhabited by grasses, sedges, and Sphagnum mosses. In the drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/m(sup -2)h(sup -1) (0-8.3) and lowest fluxes were from lichen-dominated areas at 0.9 nmol/m(sup -2)h(sup -1). Sulfur emissions from a lake surface were also low at 0.8 nmol/m(sup -2)h(sup -1). Of the compounds measured, DMS was the dominant gas emitted from all of these sites. Sulfure emissions from the marine sites were up to 20-fold greater than fluxes in the freshwater habitats and were also dominated by DMS. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea (150-250 nmol/m(sup -2)h(sup -1)). This Carex sp. was grazed thoroughly by geese and DMS fluxes doubled when goose feces were left within the flux chamber. Emissions were much lower from other types of vegetation which were more spatially dominant. Sulfure emissions from tundra were among the lowest reported in the literature. When emission data were extrapolated to include all tundra globally, the global flux of biogenic sulfur from this biome is 2-3 x 10(exp 8) g/yr. This represents less than 0.001 percent of the estimated annual global flux (approximately 50 Tg) of biogenic sulfur and less than 0.01 percent of the estimated terrestrial flux. The low emissions are attributed to the low availability of sulfate, certain hydrological characteristics of tundra, and the tendency for tundra to accumulate organic matter.

Atmospheric sulfur cycling in the Southeastern Pacific - longitudinal distribution, vertical profile, and diel variability observed during VOCALS-REx

NASA Astrophysics Data System (ADS)

Yang, M.; Huebert, B. J.; Blomquist, B. W.; Howell, S. G.; Shank, L. M.; McNaughton, C. S.; Clarke, A. D.; Hawkins, L. N.; Russell, L. M.; Covert, D. S.; Coffman, D. J.; Bates, T. S.; Quinn, P. K.; Zagorac, N.; Bandy, A. R.; de Szoeke, S. P.; Zuidema, P. D.; Tucker, S. C.; Brewer, W. A.; Benedict, K. B.; Collett, J. L.

2011-01-01

Dimethylsulfide (DMS) emitted from the ocean is a biogenic precursor gas for sulfur dioxide (SO2) and non-sea-salt sulfate aerosols (SO42). During the VAMOS-Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) in 2008, multiple instrumented platforms were deployed in the Southeastern Pacific (SEP) off the coast of Chile and Peru to study the linkage between aerosols and stratocumulus clouds. We present here observations from the NOAA Ship Ronald H. Brown and the NSF/NCAR C-130 aircraft along ~20° S from the coast (70° W) to a remote marine region (85° W). While SO42- and SO2 concentrations were distinctly elevated above background levels in the coastal marine boundary layer (MBL) due to anthropogenic influence (~800 and 80 pptv, respectively), their concentrations rapidly decreased offshore (~100and 25 pptv). Compared to the "mass" entrainment fluxes of SO42- and SO2 from the free troposphere (0.5 ± 0.3 and 0.3 ± 0.2 μmoles m-2 day-1), the sea-to-air DMS flux (3.8 ± 0.1 μmoles m-2 day-1) remained the predominant source of sulfur mass to the MBL. In-cloud oxidation was found to be the most important mechanism for SO2 removal and in situ SO42- production. Surface SO42- loading in the remote region displayed pronounced diel variability, increasing rapidly in the first few hours after sunset and then decaying for the rest of the time. We theorize that the increase in SO42- was due to nighttime recoupling of the MBL that mixed down cloud-processed air, while decoupling and sporadic precipitation scavenging were responsible for the daytime decline in SO42-.

Catalyst for elemental sulfur recovery process

DOEpatents

Flytzani-Stephanopoulos, Maria; Liu, Wei

1995-01-01

A catalytic reduction process for the direct recovery of elemental sulfur from various SO.sub.2 -containing industrial gas streams. The catalytic process provides high activity and selectivity, as well as stability in the reaction atmosphere, for the reduction of SO.sub.2 to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over a metal oxide composite catalyst having one of the following empirical formulas: [(OF.sub.2).sub.1-n (RO.sub.1)n].sub.1-k M.sub.k, [(FO.sub.2).sub.1-n (RO.sub.1.5).sub.n ].sub.1-k M.sub.k, or [Ln.sub.x Zr.sub.1-x O.sub.2-0.5x ].sub.1-k M.sub.k wherein FO.sub.2 is a fluorite-type oxide; RO represents an alkaline earth oxide; RO.sub.1.5 is a Group IIIB or rare earth oxide; Ln is a rare earth element having an atomic number from 57 to 65 or mixtures thereof; M is a transition metal or a mixture of transition metals; n is a number having a value from 0.0 to 0.35; k is a number having a value from 0.0 to about 0.5; and x is a number having a value from about 0.45 to about 0.55.

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. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Cathode Loading Effect on Sulfur Utilization in Lithium–Sulfur Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Ke; Liu, Helen; Gan, Hong

The Lithium-Sulfur (Li-S) battery is under intensive research in recent years due to its potential to provide higher energy density and lower cost than the current state-of-the-art lithium-ion battery technology. To meet cost target for transportation application, high sulfur loading up to 8 mAh cm -2 is predicted by modeling. In this work, we have investigated the sulfur loading effect on the galvanostatic charge/discharge cycling performance of Li-S cells with theoretical sulfur loading ranging from 0.5 mAh cm -2 to 7.5 mAh cm -2. We found that the low sulfur utilization of electrodes with sulfur loading of > 3.0 mAhmore » cm-2 is due to their inability to deliver capacities at the 2.1V voltage plateau, which corresponds to the conversion of soluble Li 2S 4 to insoluble Li 2S 2/Li 2S. This electrochemical conversion process recovers to deliver the expected sulfur utilization after several activation cycles for electrodes with sulfur loading up to 4.5 mAh cm -2. For electrodes with 7.0 mAh cm -2 loading, no sulfur utilization recovery was observed for 100 cycles. The root cause of this phenomenon is elucidated by SEM/EDS and EIS investigation. Carbon interlayer cell design and low rate discharge activation are demonstrated to be effective mitigation methods.« less

Cathode Loading Effect on Sulfur Utilization in Lithium–Sulfur Battery

DOE PAGES

Sun, Ke; Liu, Helen; Gan, Hong

2016-05-01

The Lithium-Sulfur (Li-S) battery is under intensive research in recent years due to its potential to provide higher energy density and lower cost than the current state-of-the-art lithium-ion battery technology. To meet cost target for transportation application, high sulfur loading up to 8 mAh cm -2 is predicted by modeling. In this work, we have investigated the sulfur loading effect on the galvanostatic charge/discharge cycling performance of Li-S cells with theoretical sulfur loading ranging from 0.5 mAh cm -2 to 7.5 mAh cm -2. We found that the low sulfur utilization of electrodes with sulfur loading of > 3.0 mAhmore » cm-2 is due to their inability to deliver capacities at the 2.1V voltage plateau, which corresponds to the conversion of soluble Li 2S 4 to insoluble Li 2S 2/Li 2S. This electrochemical conversion process recovers to deliver the expected sulfur utilization after several activation cycles for electrodes with sulfur loading up to 4.5 mAh cm -2. For electrodes with 7.0 mAh cm -2 loading, no sulfur utilization recovery was observed for 100 cycles. The root cause of this phenomenon is elucidated by SEM/EDS and EIS investigation. Carbon interlayer cell design and low rate discharge activation are demonstrated to be effective mitigation methods.« less

Effects of different annealing atmospheres on the properties of cadmium sulfide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yücel, E., E-mail: dr.ersinyucel@gmail.com; Kahraman, S.; Güder, H.S.

2015-08-15

Graphical abstract: The effects of different annealing atmospheres (air and sulfur) on the structural, morphological and optical properties of CdS thin films were studied at three different pH values. - Highlights: • Compactness and smoothness of the films were enhanced after sulfur annealing. • Micro-strain values of some films were improved after sulfur annealing. • Dislocation density values of some films were improved after sulfur annealing. • Band gap values of the films were improved after sulfur annealing. - Abstract: Cadmium sulfide (CdS) thin films were prepared on glass substrates by using chemical bath deposition (CBD) technique. The effects ofmore » different annealing atmospheres (air and sulfur) on the structural, morphological and optical properties of CdS thin films were studied at three different pH values. Compactness and smoothness of the films (especially for pH 10.5 and 11) enhanced after sulfur annealing. pH value of the precursor solution remarkably affected the roughness, uniformity and particle sizes of the films. Based on the analysis of X-ray diffraction (XRD) patterns of the films, micro-strain and dislocation density values of the sulfur-annealed films (pH 10.5 and 11) were found to be lower than those of air-annealed films. Air-annealed films (pH 10.5, 11 and 11.5) exhibited higher transmittance than sulfur-annealed films in the wavelength region of 550–800 nm. Optical band gap values of the films were found between 2.31 eV and 2.36 eV.« less

Atmospheric composition - Influence of biology

NASA Technical Reports Server (NTRS)

Mcelroy, M. B.

1983-01-01

The variability of atmospheric constituents influenced by biological organisms over various time scales is examined, together with the human contribution to atmospheric sulfur. The biogeochemistry of nitrogen is discussed, with an emphasis on N2O, NO, and microbially mediated reactions in soil and water. Carbon species are bound up mainly in sediments and the deep ocean, but human activities involving combustion may cause a doubling of the atmospheric levels of CO2 in the near future, which could produce a general low-level atmospheric warming. Longer term measurements are required to assess the effects of CH4 augmentation in the atmosphere through fuel combustion. Coal burning effectively doubles the amount of SO2 produced by natural sources, and reduces the pH of rainwater, thus posing hazards to fish, plankton, and mollusc life.

The Boston Methane Project: Mapping Surface Emissions to Inform Atmospheric Estimation of Urban Methane Flux

NASA Astrophysics Data System (ADS)

Phillips, N.; Crosson, E.; Down, A.; Hutyra, L.; Jackson, R. B.; McKain, K.; Rella, C.; Raciti, S. M.; Wofsy, S. C.

2012-12-01

Lost and unaccounted natural gas can amount to over 6% of Massachusetts' total annual greenhouse gas inventory (expressed as equivalent CO2 tonnage). An unknown portion of this loss is due to natural gas leaks in pipeline distribution systems. The objective of the Boston Methane Project is to estimate the overall leak rate from natural gas systems in metropolitan Boston, and to compare this flux with fluxes from the other primary methane emissions sources. Companion talks at this meeting describe the atmospheric measurement and modeling framework, and chemical and isotopic tracers that can partition total atmospheric methane flux into natural gas and non-natural gas components. This talk focuses on estimation of surface emissions that inform the atmospheric modeling and partitioning. These surface emissions include over 3,300 pipeline natural gas leaks in Boston. For the state of Massachusetts as a whole, the amount of natural gas reported as lost and unaccounted for by utility companies was greater than estimated landfill emissions by an order of magnitude. Moreover, these landfill emissions were overwhelmingly located outside of metro Boston, while gas leaks are concentrated in exactly the opposite pattern, increasing from suburban Boston toward the urban core. Work is in progress to estimate spatial distribution of methane emissions from wetlands and sewer systems. We conclude with a description of how these spatial data sets will be combined and represented for application in atmospheric modeling.

Method for preparing a sodium/sulfur cell

DOEpatents

Weiner, Steven A.

1978-01-01

A method for preparing a sodium/sulfur cell comprising (A) inserting a solid sodium slug, adapted to be connected to an external circuit, into the anodic reaction zone of a cell subassembly maintained within an inert atmosphere, said cell subassembly comprising a cell container and a tubular cation-permeable barrier disposed within said container such that a first reaction zone is located within cation-permeable barrier and a second reaction zone is located between the outer surface of said cation-permeable barrier and the inner surface of said container, one of said reaction zones being said anodic reaction zone and the other of said reaction zone being a cathodic reaction zone containing a precast composite cathodic reactant comprising a sulfur impregnated porous conductive material connected to said cation permeable barrier and adapted to be connected to said external circuit; and (B) providing closure means for said subassembly and sealing the same to said subassembly at a temperature less than about 100.degree. C. The method of the invention overcomes deficiencies of the prior art methods by allowing preparation of a sodium/sulfur cell without the use of molten reactants and the fill spouts which are required when the cell is filled with molten reactants.

The importance of atmospheric correction for airborne hyperspectral remote sensing of shallow waters: application to depth estimation

NASA Astrophysics Data System (ADS)

Castillo-López, Elena; Dominguez, Jose Antonio; Pereda, Raúl; de Luis, Julio Manuel; Pérez, Ruben; Piña, Felipe

2017-10-01

Accurate determination of water depth is indispensable in multiple aspects of civil engineering (dock construction, dikes, submarines outfalls, trench control, etc.). To determine the type of atmospheric correction most appropriate for the depth estimation, different accuracies are required. Accuracy in bathymetric information is highly dependent on the atmospheric correction made to the imagery. The reduction of effects such as glint and cross-track illumination in homogeneous shallow-water areas improves the results of the depth estimations. The aim of this work is to assess the best atmospheric correction method for the estimation of depth in shallow waters, considering that reflectance values cannot be greater than 1.5 % because otherwise the background would not be seen. This paper addresses the use of hyperspectral imagery to quantitative bathymetric mapping and explores one of the most common problems when attempting to extract depth information in conditions of variable water types and bottom reflectances. The current work assesses the accuracy of some classical bathymetric algorithms (Polcyn-Lyzenga, Philpot, Benny-Dawson, Hamilton, principal component analysis) when four different atmospheric correction methods are applied and water depth is derived. No atmospheric correction is valid for all type of coastal waters, but in heterogeneous shallow water the model of atmospheric correction 6S offers good results.

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.

Factors controlling sulfur gas exchange in Sphagnum-dominated wetlands

NASA Technical Reports Server (NTRS)

Demello, William Zamboni; Hines, Mark E.; Bayley, Suzanne E.

1992-01-01

Atmosphere-peatland exchange of reduced sulfur gases was determined seasonally in fen in NH, and in an artificially-acidified fen at the Experimental Lakes Area (ELA) in Canada. Dimethyl sulfide (DMS) dominated gas fluxes at rates as high as 400 nmol/m(sup -2)hr(sup -1). DMS fluxes measured using enclosures were much higher than those calculated using a stagnant-film model, suggesting that Sphagnum regulated efflux. Temperature controlled diel and seasonal variability in DMS emissions. Use of differing enclosure techniques indicated that vegetated peatlands consume atmospheric carbonyl sulfide. Sulfate amendments caused DMS and methane thiol concentrations in near-surface pore waters to increase rapidly, but fluxes of these gases to the atmosphere were not affected. However, emission data from sites experiencing large differences in rates of sulfate deposition from the atmosphere suggested that chronic elevated sulfate inputs enhance DMS emissions from northern wetlands.

Estimated congener specific gas-phase atmospheric behavior and fractionation of perfluoroalkyl compounds: rates of reaction with atmospheric oxidants, air-water partitioning, and wet/dry deposition lifetimes.

PubMed

Rayne, Sierra; Forest, Kaya; Friesen, Ken J

2009-08-01

A quantitative structure-activity model has been validated for estimating congener specific gas-phase hydroxyl radical reaction rates for perfluoroalkyl sulfonic acids (PFSAs), carboxylic acids (PFCAs), aldehydes (PFAls) and dihydrates, fluorotelomer olefins (FTOls), alcohols (FTOHs), aldehydes (FTAls), and acids (FTAcs), and sulfonamides (SAs), sulfonamidoethanols (SEs), and sulfonamido carboxylic acids (SAAs), and their alkylated derivatives based on calculated semi-empirical PM6 method ionization potentials. Corresponding gas-phase reaction rates with nitrate radicals and ozone have also been estimated using the computationally derived ionization potentials. Henry's law constants for these classes of perfluorinated compounds also appear to be reasonably approximated by the SPARC software program, thereby allowing estimation of wet and dry atmospheric deposition rates. Both congener specific gas-phase atmospheric and air-water interface fractionation of these compounds is expected, complicating current source apportionment perspectives and necessitating integration of such differential partitioning influences into future multimedia models. The findings will allow development and refinement of more accurate and detailed local through global scale atmospheric models for the atmospheric fate of perfluoroalkyl compounds.

Uses of lunar sulfur

NASA Technical Reports Server (NTRS)

Vaniman, D.; Pettit, D.; Heiken, G.

1992-01-01

Sulfur and sulfur compounds have a wide range of applications for their fluid, electrical, chemical, and biochemical properties. Although known abundances on the Moon are limited (approximately 0.1 percent in mare soils), sulfur is relatively extractable by heating. Coproduction of sulfur during oxygen extraction from ilmenite-rich mare soils could yield sulfur in masses up to 10 percent of the mass of oxygen produced. Sulfur deserves serious consideration as a lunar resource.

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.;

Toward Synchronous Evaluation of Source Apportionments for Atmospheric Concentration and Deposition of Sulfate Aerosol Over East Asia

NASA Astrophysics Data System (ADS)

Itahashi, S.

2018-03-01

Source apportionments for atmospheric concentration, dry deposition, and wet deposition of sulfate aerosol (SO42-) were synchronously evaluated over East Asia, a main source of anthropogenic sulfur dioxide (SO2) emissions. Estimating dry deposition was difficult owing to the difficulty of measuring deposition velocity directly; therefore, sensitivity simulations using two dry deposition schemes were conducted. Moreover, sensitivity simulations for different emission inventories, the largest uncertainty source in the air quality model, were also conducted. In total, four experimental settings were used. Model performance was verified for atmospheric concentration and wet deposition using a ground-based observation network in China, Korea, and Japan, and all four model settings captured the observations. The underestimation of wet deposition over China was improved by an adjusted approach that linearly scaled the modeled precipitation values to observations. The synchronous evaluation of source apportionments for atmospheric concentration and dry and wet deposition showed the dominant contribution of anthropogenic emissions from China to the atmospheric concentration and deposition in Japan. The contributions of emissions from volcanoes were more important for wet deposition than for atmospheric concentration. Differences in the dry deposition scheme and emission inventory did not substantially influence the relative ratio of source apportionments over Japan. Because the dry deposition was more attributed to local factors, the differences in dry deposition may be an important determinant of the source contributions from China to Japan. Verification of these findings, including the dry deposition velocity, is necessary for better understanding of the behavior of sulfur compound in East Asia.

Abundance and modes of occurrence of mercury in some low-sulfur coals from China

USGS Publications Warehouse

Zheng, Lingyun; Liu, Gaisheng; Chou, C.-L.

2008-01-01

Mercury (Hg) is one of the hazardous trace elements in coal. Mercury in coal is almost totally emitted into the atmosphere during coal combustion. Especially for utilities burning low-sulfur coals that do not require scrubbers, Hg reduction will be neglected. Hg abundances of 52 low-sulfur coal samples from different coalfields in six provinces of China were determined by a flow injection mercury system (FIMS). The results show that Hg abundances in selected low-sulfur coals range from 0.03??ppm to 0.79??ppm, with an arithmetic mean of 0.24??ppm, which is higher than that of average Chinese coals (0.19??ppm). Correlation analysis and sequential extraction procedures are performed to study possible modes of occurrence of Hg in low-sulfur coals. Modes of occurrence of Hg are variable in low-sulfur coals, and the sulfide-bound and organic-bound Hg may be the dominant forms. In addition, the silicate-bound Hg may be the main form in some of these coals because of magmatic intrusion. ?? 2007 Elsevier B.V. All rights reserved.

Multi-year Estimates of Methane Fluxes in Alaska from an Atmospheric Inverse Model

NASA Astrophysics Data System (ADS)

Miller, S. M.; Commane, R.; Chang, R. Y. W.; Miller, C. E.; Michalak, A. M.; Dinardo, S. J.; Dlugokencky, E. J.; Hartery, S.; Karion, A.; Lindaas, J.; Sweeney, C.; Wofsy, S. C.

2015-12-01

We estimate methane fluxes across Alaska over a multi-year period using observations from a three-year aircraft campaign, the Carbon Arctic Reservoirs Vulnerability Experiment (CARVE). Existing estimates of methane from Alaska and other Arctic regions disagree in both magnitude and distribution, and before the CARVE campaign, atmospheric observations in the region were sparse. We combine these observations with an atmospheric particle trajectory model and a geostatistical inversion to estimate surface fluxes at the model grid scale. We first use this framework to estimate the spatial distribution of methane fluxes across the state. We find the largest fluxes in the south-east and North Slope regions of Alaska. This distribution is consistent with several estimates of wetland extent but contrasts with the distribution in most existing flux models. These flux models concentrate methane in warmer or more southerly regions of Alaska compared to the estimate presented here. This result suggests a discrepancy in how existing bottom-up models translate wetland area into methane fluxes across the state. We next use the inversion framework to explore inter-annual variability in regional-scale methane fluxes for 2012-2014. We examine the extent to which this variability correlates with weather or other environmental conditions. These results indicate the possible sensitivity of wetland fluxes to near-term variability in climate.

Estimation of mercury emission from different sources to atmosphere in Chongqing, China.

PubMed

Wang, Dingyong; He, Lei; Wei, Shiqiang; Feng, Xinbin

2006-08-01

This investigation presents a first assessment of the contribution to the regional mercury budget from anthropogenic and natural sources in Chongqing, an important industrial region in southwest China. The emissions of mercury to atmosphere from anthropogenic sources in the region were estimated through indirect approaches, i.e. using commonly acceptable emission factors method, which based on annual process throughputs or consumption for these sources. The natural mercury emissions were estimated from selected natural sources by the dynamic flux chamber technique. The results indicated that the anthropogenic mercury emissions totaled approximately 8.85 tons (t), more than 50% of this total originated in coal combustion and 23.7% of this total emission in the industrial process (include cement production, metal smelting and chemical industry). The natural emissions represented approximately 17% of total emissions (1.78 t yr(-1)). The total mercury emission to atmosphere in Chongqing in 2001 was 10.63 t.

Freeze-Dried Sulfur-Graphene Oxide-Carbon Nanotube Nanocomposite for High Sulfur-Loading Lithium/Sulfur Cells.

PubMed

Hwa, Yoon; Seo, Hyeon Kook; Yuk, Jong-Min; Cairns, Elton J

2017-11-08

The ambient-temperature rechargeable lithium/sulfur (Li/S) cell is a strong candidate for the beyond lithium ion cell since significant progress on developing advanced sulfur electrodes with high sulfur loading has been made. Here we report on a new sulfur electrode active material consisting of a cetyltrimethylammonium bromide-modified sulfur-graphene oxide-carbon nanotube (S-GO-CTA-CNT) nanocomposite prepared by freeze-drying. We show the real-time formation of nanocrystalline lithium sulfide (Li 2 S) at the interface between the S-GO-CTA-CNT nanocomposite and the liquid electrolyte by in situ TEM observation of the reaction. The combination of GO and CNT helps to maintain the structural integrity of the S-GO-CTA-CNT nanocomposite during lithiation/delithiation. A high S loading (11.1 mgS/cm 2 , 75% S) S-GO-CTA-CNT electrode was successfully prepared using a three-dimensional structured Al foam as a substrate and showed good S utilization (1128 mAh/g S corresponding to 12.5 mAh/cm 2 ), even with a very low electrolyte to sulfur weight ratio of 4. Moreover, it was demonstrated that the ionic liquid in the electrolyte improves the Coulombic efficiency and stabilizes the morphology of the Li metal anode.

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.

Catalyst for the reduction of sulfur dioxide to elemental sulfur

DOEpatents

Jin, Y.; Yu, Q.; Chang, S.G.

1996-02-27

The inventive catalysts allow for the reduction of sulfur dioxide to elemental sulfur in smokestack scrubber environments. The catalysts have a very high sulfur yield of over 90% and space velocity of 10,000 h{sup {minus}1}. They also have the capacity to convert waste gases generated during the initial conversion into elemental sulfur. The catalysts have inexpensive components, and are inexpensive to produce. The net impact of the invention is to make this technology practically available to industrial applications. 21 figs.

Catalyst for the reduction of sulfur dioxide to elemental sulfur

DOEpatents

Jin, Yun; Yu, Qiquan; Chang, Shih-Ger

1996-01-01

The inventive catalysts allow for the reduction of sulfur dioxide to elemental sulfur in smokestack scrubber environments. The catalysts have a very high sulfur yield of over 90% and space velocity of 10,000 h.sup.-1. They also have the capacity to convert waste gases generated during the initial conversion into elemental sulfur. The catalysts have inexpensive components, and are inexpensive to produce. The net impact of the invention is to make this technology practically available to industrial applications.

Limits to sulfur accumulation in transgenic lupin seeds expressing a foreign sulfur-rich protein.

PubMed

Tabe, Linda M; Droux, Michel

2002-03-01

The low sulfur amino acid content of legume seeds restricts their nutritive value for animals. We have investigated the limitations to the accumulation of sulfur amino acids in the storage proteins of narrow leaf lupin (Lupinus angustifolius) seeds. Variation in sulfur supply to lupin plants affected the sulfur amino acid accumulation in the mature seed. However, when sulfur was in abundant supply, it accumulated to a large extent in oxidized form, rather than reduced form, in the seeds. At all but severely limiting sulfur supply, addition of a transgenic (Tg) sink for organic sulfur resulted in an increase in seed sulfur amino acid content. We hypothesize that demand, or sink strength for organic sulfur, which is itself responsive to environmental sulfur supply, was the first limit to the methionine (Met) and cysteine (Cys) content of wild-type lupin seed protein under most growing conditions. In Tg, soil-grown seeds expressing a foreign Met- and Cys-rich protein, decreased pools of free Met, free Cys, and glutathione indicated that the rate of synthesis of sulfur amino acids in the cotyledon had become limiting. Homeostatic mechanisms similar to those mediating the responses of plants to environmental sulfur stress resulted in an adjustment of endogenous protein composition in Tg seeds, even when grown at adequate sulfur supply. Uptake of sulfur by lupin cotyledons, as indicated by total seed sulfur at maturity, responded positively to increased sulfur supply, but not to increased demand in the Tg seeds.

Limits to Sulfur Accumulation in Transgenic Lupin Seeds Expressing a Foreign Sulfur-Rich Protein

PubMed Central

Tabe, Linda M.; Droux, Michel

2002-01-01

The low sulfur amino acid content of legume seeds restricts their nutritive value for animals. We have investigated the limitations to the accumulation of sulfur amino acids in the storage proteins of narrow leaf lupin (Lupinus angustifolius) seeds. Variation in sulfur supply to lupin plants affected the sulfur amino acid accumulation in the mature seed. However, when sulfur was in abundant supply, it accumulated to a large extent in oxidized form, rather than reduced form, in the seeds. At all but severely limiting sulfur supply, addition of a transgenic (Tg) sink for organic sulfur resulted in an increase in seed sulfur amino acid content. We hypothesize that demand, or sink strength for organic sulfur, which is itself responsive to environmental sulfur supply, was the first limit to the methionine (Met) and cysteine (Cys) content of wild-type lupin seed protein under most growing conditions. In Tg, soil-grown seeds expressing a foreign Met- and Cys-rich protein, decreased pools of free Met, free Cys, and glutathione indicated that the rate of synthesis of sulfur amino acids in the cotyledon had become limiting. Homeostatic mechanisms similar to those mediating the responses of plants to environmental sulfur stress resulted in an adjustment of endogenous protein composition in Tg seeds, even when grown at adequate sulfur supply. Uptake of sulfur by lupin cotyledons, as indicated by total seed sulfur at maturity, responded positively to increased sulfur supply, but not to increased demand in the Tg seeds. PMID:11891268

Evaluation of sulfur dioxide emissions from explosive volcanism: the 1982-1983 eruptions of Galunggung, Java, Indonesia

USGS Publications Warehouse

Bluth, G.J.S.; Casadevall, T.J.; Schnetzler, C.C.; Doiron, S.D.; Walter, Louis S.; Krueger, A.J.; Badruddin, M.

1994-01-01

Galunggung volcano, Java, awoke from a 63-year quiescence in April 1982, and erupted sporadically through January 1983. During its most violent period from April to October, the Cikasasah Volcano Observatory reported 32 large and 56 moderate to small eruptions. From April 5 through September 19 the Total Ozone Mapping Spectrometer (TOMS), carried on NASA's Nimbus-7 satellite, detected and measured 24 different sulfur dioxide clouds; an estimated 1730 kilotons (kt) of SO2 were outgassed by these explosive eruptions. The trajectories, and rapid dispersion rates, of the SO2 clouds were consistent with injection altitudes below the tropopause. An additional 300 kt of SO2 were estimated to have come from 64 smaller explosive eruptions, based on the detection limit of the TOMS instrument. For the first time, an extended period of volcanic activity was monitored by remote sensing techniques which enabled observations of both the entire SO2 clouds produced by large explosive eruptions (using TOMS), and the relatively lower levels of SO2 emissions during non-explosive outgassing (using the Correlation Spectrometer, or COSPEC). Based on COSPEC measurements from August 1982 to January 1983, and on the relationship between explosive and non-explosive degassing, approximately 400 kt of SO2 were emitted during non-explosive activity. The total sulfur dioxide outgassed from Galunggung volcano from April 1982 to January 1983 is calculated to be 2500 kt (?? 30%) from both explosive and non-explosive activity. While Galunggung added large quantities of sulfur dioxide to the atmosphere, its sporadic emissions occurred in relatively small events distributed over several months, and reached relatively low altitudes, and are unlikely to have significantly affected aerosol loading of the stratosphere in 1982 by volcanic activity. ?? 1994.

Systemic swings in end-Permian environments from Siberian Traps carbon and sulfur outgassing

NASA Astrophysics Data System (ADS)

Black, B. A.; Neely, R.; Lamarque, J. F.; Elkins-Tanton, L. T.; Kiehl, J. T.; Shields, C. A.; Mills, M. J.; Bardeen, C.

2017-12-01

U-Pb geochronology has revealed that Siberian Traps flood basalt magmatism coincided with the 252 Ma end-Permian mass extinction. Most environmental consequences of magmatism follow directly or indirectly from the release of sulfur and some combination of magmatic and metamorphic carbon to the atmosphere (exceptions include ozone depletion from halogen emissions, release of toxic metals, and enhanced weathering of fresh volcanic rocks). However, the critical combinations of forcing and stress that trigger global mass extinction remain unknown. In particular, the combined and competing effects of sulfur and carbon outgassing on Earth systems remain to be quantified. Here we present results from global climate model simulations of flood basalt outgassing that account for sulfur chemistry and aerosol microphysics. We consider the effects of sulfur and carbon in isolation and in tandem, and find that carbon and sulfur emissions combine to generate swings in climate, ocean circulation, and hydrology. Our simulations provide a self-consistent framework to quantitatively explain observed features of the end-Permian including surface warming, fluctuating ocean oxygenation, intense weathering, and carbon cycle perturbation, unifying observed changes in climate and geochemical cycles with feedbacks initiated by Siberian Traps magmatism.

Development of an atmospheric N2O isotopocule model and optimization procedure, and application to source estimation

NASA Astrophysics Data System (ADS)

Ishijima, K.; Takigawa, M.; Sudo, K.; Toyoda, S.; Yoshida, N.; Röckmann, T.; Kaiser, J.; Aoki, S.; Morimoto, S.; Sugawara, S.; Nakazawa, T.

2015-07-01

This paper presents the development of an atmospheric N2O isotopocule model based on a chemistry-coupled atmospheric general circulation model (ACTM). We also describe a simple method to optimize the model and present its use in estimating the isotopic signatures of surface sources at the hemispheric scale. Data obtained from ground-based observations, measurements of firn air, and balloon and aircraft flights were used to optimize the long-term trends, interhemispheric gradients, and photolytic fractionation, respectively, in the model. This optimization successfully reproduced realistic spatial and temporal variations of atmospheric N2O isotopocules throughout the atmosphere from the surface to the stratosphere. The very small gradients associated with vertical profiles through the troposphere and the latitudinal and vertical distributions within each hemisphere were also reasonably simulated. The results of the isotopic characterization of the global total sources were generally consistent with previous one-box model estimates, indicating that the observed atmospheric trend is the dominant factor controlling the source isotopic signature. However, hemispheric estimates were different from those generated by a previous two-box model study, mainly due to the model accounting for the interhemispheric transport and latitudinal and vertical distributions of tropospheric N2O isotopocules. Comparisons of time series of atmospheric N2O isotopocule ratios between our model and observational data from several laboratories revealed the need for a more systematic and elaborate intercalibration of the standard scales used in N2O isotopic measurements in order to capture a more complete and precise picture of the temporal and spatial variations in atmospheric N2O isotopocule ratios. This study highlights the possibility that inverse estimation of surface N2O fluxes, including the isotopic information as additional constraints, could be realized.

Development of an atmospheric N2O isotopocule model and optimization procedure, and application to source estimation

NASA Astrophysics Data System (ADS)

Ishijima, K.; Takigawa, M.; Sudo, K.; Toyoda, S.; Yoshida, N.; Röckmann, T.; Kaiser, J.; Aoki, S.; Morimoto, S.; Sugawara, S.; Nakazawa, T.

2015-12-01

This work presents the development of an atmospheric N2O isotopocule model based on a chemistry-coupled atmospheric general circulation model (ACTM). We also describe a simple method to optimize the model and present its use in estimating the isotopic signatures of surface sources at the hemispheric scale. Data obtained from ground-based observations, measurements of firn air, and balloon and aircraft flights were used to optimize the long-term trends, interhemispheric gradients, and photolytic fractionation, respectively, in the model. This optimization successfully reproduced realistic spatial and temporal variations of atmospheric N2O isotopocules throughout the atmosphere from the surface to the stratosphere. The very small gradients associated with vertical profiles through the troposphere and the latitudinal and vertical distributions within each hemisphere were also reasonably simulated. The results of the isotopic characterization of the global total sources were generally consistent with previous one-box model estimates, indicating that the observed atmospheric trend is the dominant factor controlling the source isotopic signature. However, hemispheric estimates were different from those generated by a previous two-box model study, mainly due to the model accounting for the interhemispheric transport and latitudinal and vertical distributions of tropospheric N2O isotopocules. Comparisons of time series of atmospheric N2O isotopocule ratios between our model and observational data from several laboratories revealed the need for a more systematic and elaborate intercalibration of the standard scales used in N2O isotopic measurements in order to capture a more complete and precise picture of the temporal and spatial variations in atmospheric N2O isotopocule ratios. This study highlights the possibility that inverse estimation of surface N2O fluxes, including the isotopic information as additional constraints, could be realized.

Characterization of Sulfur and Nanostructured Sulfur Battery Cathodes in Electron Microscopy Without Sublimation Artifacts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levin, Barnaby D. A.; Zachman, Michael J.; Werner, Jörg G.

Abstract Lithium sulfur (Li–S) batteries have the potential to provide higher energy storage density at lower cost than conventional lithium ion batteries. A key challenge for Li–S batteries is the loss of sulfur to the electrolyte during cycling. This loss can be mitigated by sequestering the sulfur in nanostructured carbon–sulfur composites. The nanoscale characterization of the sulfur distribution within these complex nanostructured electrodes is normally performed by electron microscopy, but sulfur sublimates and redistributes in the high-vacuum conditions of conventional electron microscopes. The resulting sublimation artifacts render characterization of sulfur in conventional electron microscopes problematic and unreliable. Here, we demonstratemore » two techniques, cryogenic transmission electron microscopy (cryo-TEM) and scanning electron microscopy in air (airSEM), that enable the reliable characterization of sulfur across multiple length scales by suppressing sulfur sublimation. We use cryo-TEM and airSEM to examine carbon–sulfur composites synthesized for use as Li–S battery cathodes, noting several cases where the commonly employed sulfur melt infusion method is highly inefficient at infiltrating sulfur into porous carbon hosts.« less

Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

NASA Astrophysics Data System (ADS)

Hartgers, Walter A.; Lòpez, Jordi F.; Sinninghe Damsté, Jaap S.; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

1997-11-01

Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron monosulfides, iron hydroxides) results in a depletion of reactive sulfur which is accompanied by a virtual absence of organo-sulfur compounds, both in low (LMW) and high molecular-weight (HMW) fractions. Small amounts of phytanyl and highly branched isoprenoid (HBI) thiophenes in the extract demonstrate that these molecules exhibit a higher reactivity towards reduced sulfur species as compared to detrital iron. Euxinic sediments from Lake Cisó are characterised by an excess of reduced sulfur species which can rapidly trap reactive iron. High concentrations of H 2S results in the formation of organo-sulfur compounds which were encountered in both LMW and HMW fractions. The major part of the organic sulfur is bound to the carbohydrate portion of woody tissues, whose presence was revealed by a specific alkylthiophene distribution in the flash pyrolysate and by Li/EtNH 2 desulfurisation of the kerogen which resulted in the solubilisation of the sulfur-enriched hemicellulose fraction. Relatively high amounts of sulfurised C 25 HBI compounds in the sediment extract of Lake Cisó reflect the incorporation of sulfur into algal derived organic matter upon early diagenesis. The combined approach of the speciation of iron and sulfur species and the molecular analysis of sedimentary fractions demonstrates that abiotic sulfur binding to organic matter occurs at the earliest stages of diagenesis under specific depositional conditions (anoxic, stratified water column) in which an excess of reduced sulfur species relative to the amount of reactive iron is a controlling factor.

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

DOEpatents

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

Sulfur vesicles from Thermococcales: A possible role in sulfur detoxifying mechanisms

PubMed Central

Gorlas, A.; Marguet, E.; Gill, S.; Geslin, C.; Guigner, J.-M.; Guyot, F.; Forterre, P.

2015-01-01

The euryarchaeon Thermococcus prieurii inhabits deep-sea hydrothermal vents, one of the most extreme environments on Earth, which is reduced and enriched with heavy metals. Transmission electron microscopy and cryo-electron microscopy imaging of T. prieurii revealed the production of a plethora of diverse membrane vesicles (MVs) (from 50 nm to 400 nm), as is the case for other Thermococcales. T. prieurii also produces particularly long nanopods/nanotubes, some of them containing more than 35 vesicles encased in a S-layer coat. Notably, cryo-electron microscopy of T. prieurii cells revealed the presence of numerous intracellular dark vesicles that bud from the host cells via interaction with the cytoplasmic membrane. These dark vesicles are exclusively found in conjunction with T. prieurii cells and never observed in the purified membrane vesicles preparations. Energy-Dispersive-X-Ray analyses revealed that these dark vesicles are filled with sulfur. Furthermore, the presence of these sulfur vesicles (SVs) is exclusively observed when elemental sulfur was added into the growth medium. In this report, we suggest that these atypical vesicles sequester the excess sulfur not used for growth, thus preventing the accumulation of toxic levels of sulfur in the host's cytoplasm. These SVs transport elemental sulfur out of the cell where they are rapidly degraded. Intriguingly, closely related archaeal species, Thermococcus nautili and Thermococcus kodakaraensis, show some differences about the production of sulfur vesicles. Whereas T. kodakaraensis produces less sulfur vesicles than T. prieurii, T. nautili does not produce such sulfur vesicles, suggesting that Thermococcales species exhibit significant differences in their sulfur metabolic pathways. PMID:26234734

Links Between Ethylene and Sulfur Nutrition-A Regulatory Interplay or Just Metabolite Association?

PubMed

Wawrzynska, Anna; Moniuszko, Grzegorz; Sirko, Agnieszka

2015-01-01

Multiple reports demonstrate associations between ethylene and sulfur metabolisms, however the details of these links have not yet been fully characterized; the links might be at the metabolic and the regulatory levels. First, sulfur-containing metabolite, methionine, is a precursor of ethylene and is a rate limiting metabolite for ethylene synthesis; the methionine cycle contributes to both sulfur and ethylene metabolism. On the other hand, ethylene is involved in the complex response networks to various stresses and it is known that S deficiency leads to photosynthesis and C metabolism disturbances that might be responsible for oxidative stress. In several plant species, ethylene increases during sulfur starvation and might serve signaling purposes to initiate the process of metabolism reprogramming during adjustment to sulfur deficit. An elevated level of ethylene might result from increased activity of enzymes involved in its synthesis. It has been demonstrated that the alleviation of cadmium stress in plants by application of S seems to be mediated by ethylene formation. On the other hand, the ethylene-insensitive Nicotiana attenuata plants are impaired in sulfur uptake, reduction and metabolism, and they invest their already limited S into methionine needed for synthesis of ethylene constitutively emitted in large amounts to the atmosphere. Regulatory links of EIN3 and SLIM1 (both from the same family of transcriptional factors) involved in the regulation of ethylene and sulfur pathway, respectively, is also quite probable as well as the reciprocal modulation of both pathways on the enzyme activity levels.

Process for removing sulfur from sulfur-containing gases

DOEpatents

Rochelle, Gary T.; Jozewicz, Wojciech

1989-01-01

The present disclosure relates to improved processes for treating hot sulfur-containing flue gas to remove sulfur therefrom. Processes in accorda The government may own certain rights in the present invention pursuant to EPA Cooperative Agreement CR 81-1531.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

DOEpatents

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-06-06

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deepmore » cycles at 0.1 C.« less

Development of a modeling approach to estimate indoor-to-outdoor sulfur ratios and predict indoor PM2.5 and black carbon concentrations for Eastern Massachusetts households

PubMed Central

Tang, Chia Hsi; Garshick, Eric; Grady, Stephanie; Coull, Brent; Schwartz, Joel; Koutrakis, Petros

2018-01-01

The effects of indoor air pollution on human health have drawn increasing attention among the scientific community as individuals spend most of their time indoors. However, indoor air sampling is labor-intensive and costly, which limits the ability to study the adverse health effects related to indoor air pollutants. To overcome this challenge, many researchers have attempted to predict indoor exposures based on outdoor pollutant concentrations, home characteristics, and weather parameters. Typically, these models require knowledge of the infiltration factor, which indicates the fraction of ambient particles that penetrates indoors. For estimating indoor fine particulate matter (PM2.5) exposure, a common approach is to use the indoor-to-outdoor sulfur ratio (Sindoor/Soutdoor) as a proxy of the infiltration factor. The objective of this study was to develop a robust model that estimates Sindoor/Soutdoor for individual households that can be incorporated into models to predict indoor PM2.5 and black carbon (BC) concentrations. Overall, our model adequately estimated Sindoor/Soutdoor with an out-of-sample by home-season R2 of 0.89. Estimated Sindoor/Soutdoor reflected behaviors that influence particle infiltration, including window opening, use of forced air heating, and air purifier. Sulfur ratio-adjusted models predicted indoor PM2.5 and BC with high precision, with out-of-sample R2 values of 0.79 and 0.76, respectively. PMID:29064481

Formaldehyde instrument development and boundary layer sulfuric acid: Implications for photochemistry

NASA Astrophysics Data System (ADS)

Case Hanks, Anne Theresa

This work presents the development of a laser-induced fluorescence technique to measure atmospheric formaldehyde. In conjunction with the technique, the design of a compact, narrow linewidth, etalon-tuned titanium: sapphire laser cavity which is pumped by the second harmonic of a kilohertz Nd:YAG laser is also presented. The fundamental tunable range is from 690-1100 nm depending on mirror reflectivities and optics kit used. The conversion efficiency is at least 25% for the fundamental, and 2-3% for intracavity frequency doubling from 3.5-4W 532 nm pump power. The linewidth is <0.1 cm-1, and the pulsewidth is 18 nsec. Applications of this cavity include the measurement of trace gas species by laser-induced fluorescence, cavity ringdown spectroscopy, and micropulse lidar in the UV-visible region. Also presented are observations of gas-phase sulfuric acid from the NEAQS-ITCT 2K4 (New England Air Quality Study--- Intercontinental Transport and Chemical Transformation) field campaign in July and August 2004. Sulfuric acid values are reported for a polluted environment and possible nucleation events as well as particle growth within the boundary layer are explored. Sulfate production rates via gas phase oxidation of sulfur dioxide are also reported. This analysis allows an important test of our ability to predict sulfuric acid concentration and probe its use as a fast time response photochemical tracer for the hydroxyl radical, OH. In comparison, the NASA time-dependent photochemical box model is used to calculate OH concentration. Nighttime H2SO4 values are examined to test our understanding of nocturnal OH levels and oxidation processes. In comparison, sulfuric acid from a large ground based mission in Tecamac, Mexico (near the northern boundary of Mexico City) during MIRAGE-Mex field campaign (March 2006) is presented. This and other measurements are used to characterize atmospheric oxidation and predict sulfuric acid and OH concentrations at the site. The

Method of removing and recovering elemental sulfur from highly reducing gas streams containing sulfur gases

DOEpatents

Gangwal, Santosh K.; Nikolopoulos, Apostolos A.; Dorchak, Thomas P.; Dorchak, Mary Anne

2005-11-08

A method is provided for removal of sulfur gases and recovery of elemental sulfur from sulfur gas containing supply streams, such as syngas or coal gas, by contacting the supply stream with a catalyst, that is either an activated carbon or an oxide based catalyst, and an oxidant, such as sulfur dioxide, in a reaction medium such as molten sulfur, to convert the sulfur gases in the supply stream to elemental sulfur, and recovering the elemental sulfur by separation from the reaction medium.

40 CFR 50.4 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2011 CFR

2011-07-01

... standards for sulfur oxides (sulfur dioxide). 50.4 Section 50.4 Protection of Environment ENVIRONMENTAL....4 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level...). (c) Sulfur oxides shall be measured in the ambient air as sulfur dioxide by the reference method...

40 CFR 50.4 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2012 CFR

2012-07-01

... standards for sulfur oxides (sulfur dioxide). 50.4 Section 50.4 Protection of Environment ENVIRONMENTAL....4 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level...). (c) Sulfur oxides shall be measured in the ambient air as sulfur dioxide by the reference method...

40 CFR 50.4 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2013 CFR

2013-07-01

... standards for sulfur oxides (sulfur dioxide). 50.4 Section 50.4 Protection of Environment ENVIRONMENTAL....4 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level...). (c) Sulfur oxides shall be measured in the ambient air as sulfur dioxide by the reference method...

40 CFR 50.4 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2014 CFR

2014-07-01

... standards for sulfur oxides (sulfur dioxide). 50.4 Section 50.4 Protection of Environment ENVIRONMENTAL....4 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level...). (c) Sulfur oxides shall be measured in the ambient air as sulfur dioxide by the reference method...

Planetary Sources for Reducing Sulfur Compounds for Cyanosulfidic Origins of Life Chemistry

NASA Astrophysics Data System (ADS)

Ranjan, S.; Todd, Z. R.; Sutherland, J.; Sasselov, D. D.

2017-12-01

A key challenge in origin-of-life studies is understanding the chemistry that lead to the origin of the key biomolecules of life, such as the components of nucleic acids, sugars, lipids, and proteins. Prebiotic reaction networks based upon reductive homologation of nitriles (e.g., Patel et al. 2015), are building a tantalizing picture of sustained abiotic synthesis of activated ribonucleotides, amino acids and lipid precursors under environmental conditions thought to have been available on early Earth. Sulfidic anions in aqueous solution (e.g., HS-, HSO3-) under near-UV irradiation play important roles in these chemical pathways. However, the sources and availability of these anions on early Earth have not yet been quantitatively constrained. Here, we evaluate the potential for the atmosphere to serve as a source of sulfidic anions, via dissolution of volcanically-outgassed SO2 and H2S into water reservoirs. We combine photochemical modeling from the literature (Hu et al. 2013) with equilibrium chemistry calculations to place constraints on the partial pressures of SO2 and H2S required to reach the elevated concentrations of sulfidic anions (≥1 μM) thought to be necessary for prebiotic chemistry. We find that micromolar levels of SO2-derived anions (HSO3-, SO3(2-)) are possible through simple exposure of aqueous reservoirs like shallow lakes to the atmosphere, assuming total sulfur emission flux comparable to today. Millimolar levels of these compounds are available during the epochs of elevated volcanism, due to elevated sulfur emission flux. Radiative transfer modeling suggests the atmospheric sulfur will not block the near-UV radiation also required for the cyanosulfidic chemistry. However, H2S-derived anions (e.g., HS-) reach only sub-micromolar levels from atmospheric sources, meaning that prebiotic chemistry invoking such molecules must invoke specialized, local sources. Prebiotic chemistry invoking SO2-derived anions may be considered more robust than

THE ANTIBACTERIAL PROPERTIES OF SULFUR

PubMed Central

Weld, Julia T.; Gunther, Anne

1947-01-01

1. Saturated solutions of sulfur in alcohol (alcohol-sulfur) when diluted with broth are inhibitory to the growth of various Gram-positive bacteria and to C. hominis. By an arbitrary method of unitage with S. aureus as the test organism, our alcohol-sulfur contains 1,600 to 2,000 units per cc. and one unit contains between 0.24 and 0.34 gamma sulfur. The activity of a preparation is in general directly proportional to its sulfur content. 2. Solutions of sulfur in carbowax (carbowax-sulfur) when diluted with broth are likewise inhibitory to the growth of various Gram-positive bacteria and to C. hominis. When S. aureus is used as test organism, 1 unit contains between 0.1 and 0.2 gamma sulfur. The activity of these preparations is also in general directly proportional to their sulfur content. 3. Carbowax-sulfur when incorporated in agar in 1–500 to 1–2,000 dilution inhibits the growth of various Gram-positive aerobic and anaerobic bacteria, C. hominis, and certain dermatophytes. 4. Our experiments appear to show that both alcohol-sulfur and carbowax-sulfur owe their inhibitory properties to the sulfur particles that are dispersed throughout the medium when these sulfur preparations are diluted with broth. The inhibitory effect of these particles may or may not be due to a combination of the sulfur particles with substances in the medium in which they are suspended. 5. Evidence suggests that the activity of both alcohol-sulfur and carbowax-sulfur is due to sulfur in the same form. The inhibitory effect is characterized by prolonged bacteriostasis with similar activity over a wide range of dilutions. There is no evidence of true bactericidal action even with the highest concentrations used. PMID:19871634

The life sulfuric: microbial ecology of sulfur cycling in marine sediments.

PubMed

Wasmund, Kenneth; Mußmann, Marc; Loy, Alexander

2017-08-01

Almost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular- and ecosystem-level processes. Sulfur-transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate-rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep-subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Sulfur Removal by Adding Iron During the Digestion Process of High-sulfur Bauxite

NASA Astrophysics Data System (ADS)

Zhanwei, Liu; Hengwei, Yan; Wenhui, Ma; Keqiang, Xie; Dunyong, Li; Licong, Zheng; Pengfei, Li

2018-04-01

This paper proposes a novel approach to sulfur removal by adding iron during the digestion process. Iron can react with high-valence sulfur (S2O3 2-, SO3 2-, SO4 2-) to generate S2- at digestion temperature, and then S2- enter red mud in the form of Na3FeS3 to be removed. As iron dosage increases, high-valence sulfur concentration decreases, but the concentration of S2- increases; sulfur digestion rate decreases while sulfur content in red mud markedly increases; the alumina digestion rate, conversely, remains fairly stable. So sulfur can be removed completely by adding iron in digestion process, which provide a theoretical basis for the effective removal of sulfur in alumina production process.

Evaluation of Sulfur Flow Emplacement on Io from Galileo Data and Numerical Modeling

NASA Technical Reports Server (NTRS)

Williams, David A.; Greeley, Ronald; Lopes, Rosaly M. C.; Davies, Ashley G.

2001-01-01

Galileo images of bright lava flows surrounding Emakong Patera have bee0 analyzed and numerical modeling has been performed to assess whether these flows could have resulted from the emplacement of sulfur lavas on Io. Images from the solid-state imaging (SSI) camera show that these bright, white to yellow Emakong flows are up to 370 km long and contain dark, sinuous features that are interpreted to be lava conduits, -300-500 m wide and >lo0 km lorig. Neiu-Infrared Mapping S estimate of 344 K f 60 G131'C) within the Bmakong caldera. We suggest that these bright flows likely resulted from either sulfur lavas or silicate lavas that have undergone extensive cooling, pyroclastic mantling, and/or alteration with bright sulfurous materials. The Emakoag bright flows have estimated volume of -250-350 km', similar to some of the smaller Columbia River Basalt flows, If the Emakong flows did result from effusive sulfur eruptions, then they are orders of magnitude reater in volume than any terrestrial sulfur flows. Our numerical modeling capable of traveling tens to hundreds of kilometers, consistent with the predictions of Sagan. Our modeled flow distances are also consistent with the measured lengths of the Emakong channels and bright flows.

40 CFR 50.5 - National secondary ambient air quality standard for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2014 CFR

2014-07-01

... standard for sulfur oxides (sulfur dioxide). 50.5 Section 50.5 Protection of Environment ENVIRONMENTAL....5 National secondary ambient air quality standard for sulfur oxides (sulfur dioxide). (a) The level... than 0.05 ppm shall be rounded up). (b) Sulfur oxides shall be measured in the ambient air as sulfur...

40 CFR 50.5 - National secondary ambient air quality standard for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2013 CFR

2013-07-01

... standard for sulfur oxides (sulfur dioxide). 50.5 Section 50.5 Protection of Environment ENVIRONMENTAL....5 National secondary ambient air quality standard for sulfur oxides (sulfur dioxide). (a) The level... than 0.05 ppm shall be rounded up). (b) Sulfur oxides shall be measured in the ambient air as sulfur...

40 CFR 50.5 - National secondary ambient air quality standard for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2012 CFR

2012-07-01

... standard for sulfur oxides (sulfur dioxide). 50.5 Section 50.5 Protection of Environment ENVIRONMENTAL....5 National secondary ambient air quality standard for sulfur oxides (sulfur dioxide). (a) The level... than 0.05 ppm shall be rounded up). (b) Sulfur oxides shall be measured in the ambient air as sulfur...

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%. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Iron dissolution of dust source materials during simulated acidic processing: the effect of sulfuric, acetic, and oxalic acids.

PubMed

Chen, Haihan; Grassian, Vicki H

2013-09-17

Atmospheric organic acids potentially display different capacities in iron (Fe) mobilization from atmospheric dust compared with inorganic acids, but few measurements have been made on this comparison. We report here a laboratory investigation of Fe mobilization of coal fly ash, a representative Fe-containing anthropogenic aerosol, and Arizona test dust, a reference source material for mineral dust, in pH 2 sulfuric acid, acetic acid, and oxalic acid, respectively. The effects of pH and solar radiation on Fe dissolution have also been explored. The relative capacities of these three acids in Fe dissolution are in the order of oxalic acid > sulfuric acid > acetic acid. Oxalate forms mononuclear bidentate ligand with surface Fe and promotes Fe dissolution to the greatest extent. Photolysis of Fe-oxalate complexes further enhances Fe dissolution with the concomitant degradation of oxalate. These results suggest that ligand-promoted dissolution of Fe may play a more significant role in mobilizing Fe from atmospheric dust compared with proton-assisted processing. The role of atmospheric organic acids should be taken into account in global-biogeochemical modeling to better access dissolved atmospheric Fe deposition flux at the ocean surface.

Sulfuric Acid on Europa

NASA Image and Video Library

1999-09-30

Frozen sulfuric acid on Jupiter's moon Europa is depicted in this image produced from data gathered by NASA's Galileo spacecraft. The brightest areas, where the yellow is most intense, represent regions of high frozen sulfuric acid concentration. Sulfuric acid is found in battery acid and in Earth's acid rain. This image is based on data gathered by Galileo's near infrared mapping spectrometer. Europa's leading hemisphere is toward the bottom right, and there are enhanced concentrations of sulfuric acid in the trailing side of Europa (the upper left side of the image). This is the face of Europa that is struck by sulfur ions coming from Jupiter's innermost moon, Io. The long, narrow features that crisscross Europa also show sulfuric acid that may be from sulfurous material extruded in cracks. http://photojournal.jpl.nasa.gov/catalog/PIA02500

Sulfur content of hybrid poplar cuttings fumigated with sulfur dioxide

Treesearch

Keith F. Jensen

1975-01-01

Hybrid poplar cuttings were fumigated with sulfur dioxide ranging in concentration from 0.1 to 5 ppm for periods of 5 to 80 hours. At the end of the fumigation periods, the cuttings were harvested and the sulfur and chlorophyll contents of the leaves were measured. At 0.1 ppm and 0.25 ppm the sulfur content initially increased, but decreased as fumigation continued. At...

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

Mesoporous hollow carbon spheres for lithium–sulfur batteries: distribution of sulfur and electrochemical performance

PubMed Central

Juhl, Anika C; Schneider, Artur; Ufer, Boris; Brezesinski, Torsten

2016-01-01

Summary Hollow carbon spheres (HCS) with a nanoporous shell are promising for the use in lithium–sulfur batteries because of the large internal void offering space for sulfur and polysulfide storage and confinement. However, there is an ongoing discussion whether the cavity is accessible for sulfur. Yet no valid proof of cavity filling has been presented, mostly due to application of unsuitable high-vacuum methods for the analysis of sulfur distribution. Here we describe the distribution of sulfur in hollow carbon spheres by powder X-ray diffraction and Raman spectroscopy along with results from scanning electron microscopy and nitrogen physisorption. The results of these methods lead to the conclusion that the cavity is not accessible for sulfur infiltration. Nevertheless, HCS/sulfur composite cathodes with areal sulfur loadings of 2.0 mg·cm−2 were investigated electrochemically, showing stable cycling performance with specific capacities of about 500 mAh·g−1 based on the mass of sulfur over 500 cycles. PMID:27826497

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

Use of wind data for estimating horizontal dilution potential of atmosphere.

PubMed

George, K V; Verma, P; Devotta, S

2007-04-01

In this study, a new methodology is suggested for estimating horizontal dilution potential of an area using wind data. The mean wind speed and wind direction variation are used as a measure of linear and angular spread of pollutants in the atmosphere. A formula is developed for estimating the potential of horizontal spread of pollutants in an area wherein only the wind speed and direction are used. The methodology is further applied to monitor wind data of one year. It is found that there is a very smooth variation of horizontal dilution potential over a year with limited dilution during post monsoon period and a high dilution in pre monsoon period.

[Pigments of green sulfur bacteria isolated from reservoirs of Iavoriv sulfur deposit].

PubMed

Baran, I M; Hudz', S P; Hnatush, S O; Fedorovych, A M

2004-01-01

The enormous amount of hydrogen sulfide (up to 11 mg/ml) is present in the Yavoriv sulfur deposit reservoirs owing to sulfur reductive bacteria activity. As a consequence the ecological situation is badly affected and requires recovering. The biological H2S decomposition by photosynthetic sulfur bacteria, which use the hydrogen sulfide as electron donor during photosynthesis, can be one of the possible ways of this toxic substance destruction. The qualitative and quantitative analysis of photosynthetic pigments composition that derived from green photosynthesizing sulfur bacteria from reservoirs of Yavoriv sulfur deposit is carried out. It was fixed that Pelodictyon sp., Chlorobium sp. and isolated consortia "Pelochromatium sp." contain the bacteriochlorophyll c and d. All the isolated cultures contained bacteriochlorophyll a in trace amounts. The obtained photosynthetic pigments (bacteriochlorophylls, carotenoids) were recognized by their absorption spectra in the visible and far-red region and by their quantity. The difference was not essential. All investigated cultures of isolated bacteria contain some carotenoid the Chlorobium sp. and obtained consortia possesses isorenieratene. The absorption maxima of extracted pigments from young cultures of isolated green sulfur bacteria are more definitely displayed than those from old cultures. Investigations of phototrophic sulfur bacteria were carried out in Ukraine up to now. Ecological problem that occurred in the Yavoriv sulfur deposit as a result of the deposit exploitation caused a necessity of the investigation of photosynthetic sulfur bacteria and bacterial photosynthesis mechanism. The photosynthetic pigments nature identification will promote the fast and precise identification of the new forms of photosynthetic sulfur bacteria and will extend our knowledge about their role in the anoxygenic photosynthesis.

The life sulfuric: microbial ecology of sulfur cycling in marine sediments

PubMed Central

Wasmund, Kenneth; Mußmann, Marc

2017-01-01

Summary Almost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular‐ and ecosystem‐level processes. Sulfur‐transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate‐rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep‐subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle. PMID:28419734

Toward understanding the effect of low-activity waste glass composition on sulfur solubility

DOE PAGES

Vienna, John D.; Kim, Dong -Sang; Muller, Isabelle S.; ...

2014-07-24

The concentration of sulfur in nuclear waste glass melter feed must be maintained below the point where salt accumulates on the melt surface. The allowable concentrations may range from 0.37 to over 2.05 weight percent (of SO 3 on a calcined oxide basis) depending on the composition of the melter feed and processing conditions. If the amount of sulfur exceeds the melt tolerance level, a molten salt will accumulate, which may upset melter operations and potentially shorten the useful life of the melter. At the Hanford site, relatively conservative limits have been placed on sulfur loading in melter feed, whichmore » in turn significantly increases the amount of glass that will be produced. Crucible-scale sulfur solubility data and scaled melter sulfur tolerance data have been collected on simulated Hanford waste glasses over the last 15 years. These data were compiled and analyzed. A model was developed to predict the solubility of SO 3 in glass based on 252 simulated Hanford low-activity waste (LAW) glass compositions. This model represents the data well, accounting for over 85% of the variation in data, and was well validated. The model was also found to accurately predict the tolerance for sulfur in melter feed for 13 scaled melter tests of simulated LAW glasses. The model can be used to help estimate glass volumes and make informed decisions on process options. The model also gives quantitative estimates of component concentration effects on sulfur solubility. The components that most increase sulfur solubility are Li 2O > V 2O 5> CaO ≈ P 2O 5 > Na 2O ≈ B 2O 3 > K 2O. The components that most decrease sulfur solubility are Cl > Cr 2O 3 > Al 2O 3 > ZrO 2 ≈ SnO 2 > Others ≈ SiO 2. As a result, the order of component effects is similar to previous literature data, in most cases.« less

Microporous novolac-derived carbon beads/sulfur hybrid cathode for lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Choudhury, Soumyadip; Krüner, Benjamin; Massuti-Ballester, Pau; Tolosa, Aura; Prehal, Christian; Grobelsek, Ingrid; Paris, Oskar; Borchardt, Lars; Presser, Volker

2017-07-01

Novolac-derived nanoporous carbon beads were used as conductive matrix for lithium-sulfur battery cathodes. We employed a facile self-emulsifying synthesis to obtain sub-micrometer novolac-derived carbon beads with nanopores. After pyrolysis, the carbon beads showed already a specific surface area of 640 m2 g-1 which was increased to 2080 m2 g-1 after physical activation. The non-activated and the activated carbon beads represent nanoporous carbon with a medium and a high surface area, respectively. This allows us to assess the influence of the porosity on the electrochemical performance of lithium-sulfur battery cathodes. The carbon/sulfur hybrids were obtained from two different approaches of sulfur infiltration: melt-infusion of sulfur (annealing) and in situ formation of sulfur from sodium thiosulfate. The best performance (∼880 mAh gsulfur-1 at low charge rate; 5th cycle) and high performance stability (>600 mAh gsulfur-1 after 100 cycles) were found for the activated carbon beads when using melt infusion of sulfur.

Sulfur assimilation and the role of sulfur in plant metabolism: a survey.

PubMed

Droux, Michel

2004-01-01

Sulfur occurs in two major amino-acids, cysteine (Cys) and methionine (Met), essential for the primary and secondary metabolism of the plant. Cys, as the first carbon/nitrogen-reduced sulfur product resulting from the sulfate assimilation pathway, serves as a sulfur donor for Met, glutathione, vitamins, co-factors, and sulfur compounds that play a major role in the growth and development of plant cells. This sulfur imprinting occurs in a myriad of fundamental processes, from photosynthesis to carbon and nitrogen metabolism. Cys and Met occur in proteins, with the former playing a wide range of functions in proteins catalysis. In addition, the sulfur atom in proteins forms part of a redox buffer, as for glutathione, through specific detoxification/protection mechanisms. In this review, a survey of sulfur assimilation from sulfate to Cys, Met and glutathione is presented with highlights on open questions on their respective biosynthetic pathways and regulations that derived from recent findings. These are addressed at the biochemical and molecular levels with respect to the fate of Cys and Met throughout the plant-cell metabolism.

Sulfur determination in concrete samples using laser-induced breakdown spectroscopy and limestone standards

NASA Astrophysics Data System (ADS)

Hrdlička, Aleš; Hegrová, Jitka; Novotný, Karel; Kanický, Viktor; Prochazka, David; Novotný, Jan; Modlitbová, Pavlína; Sládková, Lucia; Pořízka, Pavel; Kaiser, Jozef

2018-04-01

A LIBS equipment operating at 532 nm was optimized and used for sulfur determination in concrete samples. The influence of He atmosphere in a gas-tight chamber (1000-200 mbar) on S I 921.29 nm line sensitivity, signal-to-background and signal-to-noise ratio was studied at gate delays 100-2000 ns. Wide range of gate delays from 500 to about 1000 ns and pressures from several hundreds of mbar to the atmospheric pressure can be used for the desired detection of sulfur. The LIBS quantification was done using a simple calibration method. A synthetic limestone enriched by defined amounts of sodium sulfate was newly employed for direct quantification of S in concrete. This powder material was pressed into pellets and ablated with the LIBS system. The average content of sulfur as SO3 in the samples was 0.41-0.70 wt% by LIBS and 0.43-0.61 wt% by a reference standard procedure employing gravimetry and Inductively Coupled Plasma Triple Quad Mass Spectrometry (ICP-QQQMS). The uncertainty of the yielded LIBS results covers also the dispersion of the points in the calibration line and ranges from 16 to 28% at the probability level of 95%. The uncertainty of the ICP-QQQMS results was almost 10%. No correction on different signal response on the limestone and on the concrete was necessary.

Sulfur emission from Victorian brown coal under pyrolysis, oxy-fuel combustion and gasification conditions.

PubMed

Chen, Luguang; Bhattacharya, Sankar

2013-02-05

Sulfur emission from a Victorian brown coal was quantitatively determined through controlled experiments in a continuously fed drop-tube furnace under three different atmospheres: pyrolysis, oxy-fuel combustion, and carbon dioxide gasification conditions. The species measured were H(2)S, SO(2), COS, CS(2), and more importantly SO(3). The temperature (873-1273 K) and gas environment effects on the sulfur species emission were investigated. The effect of residence time on the emission of those species was also assessed under oxy-fuel condition. The emission of the sulfur species depended on the reaction environment. H(2)S, SO(2), and CS(2) are the major species during pyrolysis, oxy-fuel, and gasification. Up to 10% of coal sulfur was found to be converted to SO(3) under oxy-fuel combustion, whereas SO(3) was undetectable during pyrolysis and gasification. The trend of the experimental results was qualitatively matched by thermodynamic predictions. The residence time had little effect on the release of those species. The release of sulfur oxides, in particular both SO(2) and SO(3), is considerably high during oxy-fuel combustion even though the sulfur content in Morwell coal is only 0.80%. Therefore, for Morwell coal utilization during oxy-fuel combustion, additional sulfur removal, or polishing systems will be required in order to avoid corrosion in the boiler and in the CO(2) separation units of the CO(2) capture systems.

Vertically uniform formation pathways of tropospheric sulfate aerosols in East China detected from triple stable oxygen and radiogenic sulfur isotopes

NASA Astrophysics Data System (ADS)

Lin, Mang; Biglari, Saman; Zhang, Zhisheng; Crocker, Daniel; Tao, Jun; Su, Binbin; Liu, Lanzhong; Thiemens, Mark H.

2017-05-01

Sulfate aerosols (SO42-) in the continental outflow from East China significantly alter the atmospheric sulfur budget across the Pacific Rim, but its formation pathways, especially in the free troposphere (FT), remain poorly understood. Here we analyze stable oxygen (δ17O and δ18O) and radiogenic sulfur (35S) isotopes in SO42- collected at a mountain site in East China to investigate SO42- formation pathways at varying altitudes. We find that Δ17O (=δ17O-0.52 × δ18O) in SO42- is not correlated with 35S (a direct measure of high-altitude air masses). This pattern notably differs from the currently known 35S-Δ17O relation. The result implies that the formation pathway of tropospheric SO42- in East China is vertically uniform, likely due to large emissions and active convection in this region. Our measurements provide unambiguous isotopic constraints for reducing uncertainties in modeling SO42- in the FT over East China, which greatly affects regional climate but current models fail to accurately estimate.

Rational Design of Statically and Dynamically Stable Lithium-Sulfur Batteries with High Sulfur Loading and Low Electrolyte/Sulfur Ratio.

PubMed

Chung, Sheng-Heng; Manthiram, Arumugam

2018-02-01

The primary challenge with lithium-sulfur battery research is the design of sulfur cathodes that exhibit high electrochemical efficiency and stability while keeping the sulfur content and loading high and the electrolyte/sulfur ratio low. With a systematic investigation, a novel graphene/cotton-carbon cathode is presented here that enables sulfur loading and content as high as 46 mg cm -2 and 70 wt% with an electrolyte/sulfur ratio of as low as only 5. The graphene/cotton-carbon cathodes deliver peak capacities of 926 and 765 mA h g -1 , respectively, at C/10 and C/5 rates, which translate into high areal, gravimetric, and volumetric capacities of, respectively, 43 and 35 mA h cm -2 , 648 and 536 mA h g -1 , and 1067 and 881 mA h cm -3 with a stable cyclability. They also exhibit superior cell-storage capability with 95% capacity-retention, a low self-discharge constant of just 0.0012 per day, and stable poststorage cyclability after storing over a long period of six months. This work demonstrates a viable approach to develop lithium-sulfur batteries with practical energy densities exceeding that of lithium-ion batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

PubMed Central

Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V.

2017-01-01

Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62−) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O) of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4), acid

Atmospheric aerosol source identification and estimates of source contributions to air pollution in Dundee, UK

NASA Astrophysics Data System (ADS)

Qin, Y.; Oduyemi, K.

Anthropogenic aerosol (PM 10) emission sources sampled at an air quality monitoring station in Dundee have been analysed. However, the information on local natural aerosol emission sources was unavailable. A method that combines receptor model and atmospheric dispersion model was used to identify aerosol sources and estimate source contributions to air pollution. The receptor model identified five sources. These are aged marine aerosol source with some chlorine replaced by sulphate, secondary aerosol source of ammonium sulphate, secondary aerosol source of ammonium nitrate, soil and construction dust source, and incinerator and fuel oil burning emission source. For the vehicle emission source, which has been comprehensively described in the atmospheric emission inventory but cannot be identified by the receptor model, an atmospheric dispersion model was used to estimate its contributions. In Dundee, a significant percentage, 67.5%, of the aerosol mass sampled at the study station could be attributed to the six sources named above.

Influence of periodically changing oxidizing and reducing environment on sulfur capture under PFBC conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yrjas, P.; Hupa, M.

1997-12-31

In the literature it has been reported that sulfur capture with limestone (CaCO{sub 3}) under atmospheric fluidized bed combustion conditions reaches a maximum at about 850 C. Previously, the maximum has been attributed to the sintering of the sorbent particles which decreases the reactive surface area. Lately, also another explanation has been reported. In this case the sulfur capture decrease at higher temperatures was concluded to be due to fluctuating oxidizing/reducing conditions in the atmospheric combustor. In this paper the influence of alternating oxidizing/reducing conditions on SO{sub 2} capture at atmospheric and elevated pressure (15 bar) is reported. In themore » pressurized case, the CO{sub 2} partial pressure was kept high enough to prevent CaCO{sub 3} from calcining and therefore the CaSO{sub 4} would not form CaO but CaCO{sub 3} from calcining and therefore the CaSO{sub 4} would not form CaO but CaCO{sub 3} under reducing conditions. The experiments were done with a pressurized TGA by periodically changing the gas environment between oxidizing (O{sub 2}, SO{sub 2}, CO{sub 2} and N{sub 2}) and slightly reducing (CO, SO{sub 2}, CO{sub 2} and N{sub 2}) gas mixtures at different temperatures. The results showed that under normal pressure and slightly reducing conditions CaO formation from CaSO{sub 4} increased with temperature as expected. However, no significant amounts of CaCO{sub 3} were formed from CaSO{sub 4} at elevated pressure. It was also concluded that since the formation of CaO from CaSO{sub 4} was relatively slow it could not explain the sharp sulfur capture maximum at about 850 C. Therefore, it was assumed that the strongly reducing zones, where CaS thermodynamically is the stable compound, may play a more important role than the slightly reducing zones, concerning the sulfur capture in fluidized bed combustors.« less

Study on the total amount control of atmospheric pollutant based on GIS.

PubMed

Wang, Jian-Ping; Guo, Xi-Kun

2005-08-01

To provide effective environmental management for total amount control of atmospheric pollutants. An atmospheric diffusion model of sulfur dioxide on the surface of the earth was established and tested in Shantou of Guangdong Province on the basis of an overall assessment of regional natural environment, social economic state of development, pollution sources and atmospheric environmental quality. Compared with actual monitoring results in a studied region, simulation values fell within the range of two times of error and were evenly distributed in the two sides of the monitored values. Predicted with the largest emission model method, the largest emission of sulfur dioxide would be 54,279.792 tons per year in 2010. The mathematical model established and revised on the basis of GIS is more rational and suitable for the regional characteristics of total amount control of air pollutants.

40 CFR 50.17 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2011 CFR

2011-07-01

... standards for sulfur oxides (sulfur dioxide). 50.17 Section 50.17 Protection of Environment ENVIRONMENTAL....17 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level of the national primary 1-hour annual ambient air quality standard for oxides of sulfur is 75 parts...

40 CFR 50.17 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2012 CFR

2012-07-01

... standards for sulfur oxides (sulfur dioxide). 50.17 Section 50.17 Protection of Environment ENVIRONMENTAL....17 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level of the national primary 1-hour annual ambient air quality standard for oxides of sulfur is 75 parts...

40 CFR 50.17 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2010 CFR

2010-07-01

... standards for sulfur oxides (sulfur dioxide). 50.17 Section 50.17 Protection of Environment ENVIRONMENTAL....17 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level of the national primary 1-hour annual ambient air quality standard for oxides of sulfur is 75 parts...

40 CFR 50.17 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2013 CFR

2013-07-01

... standards for sulfur oxides (sulfur dioxide). 50.17 Section 50.17 Protection of Environment ENVIRONMENTAL....17 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level of the national primary 1-hour annual ambient air quality standard for oxides of sulfur is 75 parts...

40 CFR 50.17 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2014 CFR

2014-07-01

... standards for sulfur oxides (sulfur dioxide). 50.17 Section 50.17 Protection of Environment ENVIRONMENTAL....17 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). (a) The level of the national primary 1-hour annual ambient air quality standard for oxides of sulfur is 75 parts...

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

The Jovian atmospheric window at 2.7 microns: A search for H2S

NASA Technical Reports Server (NTRS)

Larson, H. P.; Davis, D. S.; Hofmann, R.; Bjoraker, G. L.

1984-01-01

The atmospheric transmission window at 2.7 microns in Jupiter's atmosphere was observed at a spectral resolution of 0.1/cm from the Kuiiper Airborne Observatory. From an analysis of the CH4 abundance (80 m-am) and the H2O abundance ( 0.0125 cm-am) it was determined that the penetration depth of solar flux at 2.7 microns is near the base of the NH3 cloud layer. The upper limit to H2O at 2.7 microns and other results suggest that photolytic reactions in Jupiter's lower troposphere may not be as significant as was previously thought. A search for H2S in Jupiter's atmosphere yielded an upper limit of 0.1 cm-am. The corresponding limit to the element abundance ratio S/H was approx. 1.7x10(-8), about 10(-3) times the solar value. Upon modeling the abundance and distribution of H2S in Jupiter's atmosphere it was concluded that, contrary to expectations, sulfur-bearing chromophores are not present in significant amounts in Jupiter's visible clouds. Rather, it appears that most of Jupiter's sulfur is locked up as NH4SH in a lower cloud layer. Alternatively, the global abundance of sulfur in Jupiter may be significantly depleted.

In-situ sulfuration synthesis of sandwiched spherical tin sulfide/sulfur-doped graphene composite with ultra-low sulfur content

NASA Astrophysics Data System (ADS)

Zhao, Bing; Yang, Yaqing; Wang, Zhixuan; Huang, Shoushuang; Wang, Yanyan; Wang, Shanshan; Chen, Zhiwen; Jiang, Yong

2018-02-01

SnS is widely studied as anode materials since of its superior structural stability and physicochemical property comparing with other Sn-based composites. Nevertheless, the inconvenience of phase morphology control and excessive consumption of sulfur sources during synthesis hinder the scalable application of SnS nanocomposites. Herein, we report a facile in-situ sulfuration strategy to synthesize sandwiched spherical SnS/sulfur-doped graphene (SnS/S-SG) composite. An ultra-low sulfur content with approximately stoichiometric ratio of Sn:S can effectively promote the sulfuration reaction of SnO2 to SnS and simultaneous sulfur-doping of graphene. The as-prepared SnS/S-SG composite shows a three-dimensional interconnected spherical structure as a whole, in which SnS nanoparticles are sandwiched between the multilayers of graphene sheets forming a hollow sphere. The sandwiched sphere structure and high S doping amount can improve the binding force between SnS and graphene, as well as the structural stability and electrical conductivity of the composite. Thus, a high reversibility of conversion reaction, promising specific capacity (772 mAh g-1 after 100 cycles at 0.1 C) and excellent rate performance (705 and 411 mAh g-1 at 1 C and 10 C, respectively) are exhibited in the SnS/S-SG electrode, which are much higher than that of the SnS/spherical graphene synthesized by traditional post-sulfuration method.

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.

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%).

40 CFR 50.4 - National primary ambient air quality standards for sulfur oxides (sulfur dioxide).

Code of Federal Regulations, 2010 CFR

2010-07-01

... standards for sulfur oxides (sulfur dioxide). 50.4 Section 50.4 Protection of Environment ENVIRONMENTAL....4 National primary ambient air quality standards for sulfur oxides (sulfur dioxide). Link to an... to or greater than 0.005 ppm shall be rounded up). (c) Sulfur oxides shall be measured in the ambient...

ADVANCED SULFUR CONTROL CONCEPTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael

Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce themore » number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).« less

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)

The global sulfur cycle

NASA Technical Reports Server (NTRS)

Sagan, D. (Editor)

1985-01-01

The results of the planetary biology microbial ecology's 1984 Summer Research Program, which examined various aspects of the global sulfur cycle are summarized. Ways in which sulfur flows through the many living and chemical species that inhabit the surface of the Earth were investigated. Major topics studied include: (1) sulfur cycling and metabolism of phototropic and filamentous sulfur bacteria; (2) sulfur reduction in sediments of marine and evaporite environments; (3) recent cyanobacterial mats; (4) microanalysis of community metabolism in proximity to the photic zone in potential stromatolites; and (5) formation and activity of microbial biofilms on metal sulfides and other mineral surfaces. Relationships between the global sulfur cycle and the understanding of the early evolution of the Earth and biosphere and current processes that affect global habitability are stressed.

NITROGEN BOUNDING STUDY: METHODS FOR ESTIMATING THE RELATIVE EFFECTS OF SULFUR AND NITROGEN DEPOSITION ON SURFACE WATER CHEMISTRY

EPA Science Inventory

The leaching of atmospherically deposited nitrogen from forested watersheds may acidify lakes and streams. he Nitrogen Bounding Study evaluates the potential range of such adverse effects. he study estimates bounds on changes in regional-scale surface water acidification that mig...

Sulfur cycling and metabolism of phototrophic and filamentous sulfur bacteria

NASA Technical Reports Server (NTRS)

Guerrero, R.; Brune, D.; Poplawski, R.; Schmidt, T. M.

1985-01-01

Phototrophic sulfur bacteria taken from different habitate (Alum Rock State Park, Palo Alto salt marsh, and Big Soda Lake) were grown on selective media, characterized by morphological and pigment analysis, and compared with bacteria maintained in pure culture. A study was made of the anaerobic reduction of intracellular sulfur globules by a phototrophic sulfur bacterium (Chromatium vinosum) and a filamentous aerobic sulfur bacterium (Beggiatoa alba). Buoyant densities of different bacteria were measured in Percoll gradients. This method was also used to separate different chlorobia in mixed cultures and to assess the relative homogeneity of cultures taken directly or enriched from natural samples (including the purple bacterial layer found at a depth of 20 meters at Big Soda Lake.) Interactions between sulfide oxidizing bacteria were studied.

Fibrous hybrid of graphene and sulfur nanocrystals for high-performance lithium-sulfur batteries.

PubMed

Zhou, Guangmin; Yin, Li-Chang; Wang, Da-Wei; Li, Lu; Pei, Songfeng; Gentle, Ian Ross; Li, Feng; Cheng, Hui-Ming

2013-06-25

Graphene-sulfur (G-S) hybrid materials with sulfur nanocrystals anchored on interconnected fibrous graphene are obtained by a facile one-pot strategy using a sulfur/carbon disulfide/alcohol mixed solution. The reduction of graphene oxide and the formation/binding of sulfur nanocrystals were integrated. The G-S hybrids exhibit a highly porous network structure constructed by fibrous graphene, many electrically conducting pathways, and easily tunable sulfur content, which can be cut and pressed into pellets to be directly used as lithium-sulfur battery cathodes without using a metal current-collector, binder, and conductive additive. The porous network and sulfur nanocrystals enable rapid ion transport and short Li(+) diffusion distance, the interconnected fibrous graphene provides highly conductive electron transport pathways, and the oxygen-containing (mainly hydroxyl/epoxide) groups show strong binding with polysulfides, preventing their dissolution into the electrolyte based on first-principles calculations. As a result, the G-S hybrids show a high capacity, an excellent high-rate performance, and a long life over 100 cycles. These results demonstrate the great potential of this unique hybrid structure as cathodes for high-performance lithium-sulfur batteries.

Estimating the deposition of urban atmospheric NO2 to the urban forest in Portland-Vancouver USA

NASA Astrophysics Data System (ADS)

Rao, M.; Gonzalez Abraham, R.; George, L. A.

2016-12-01

Cities are hotspots of atmospheric emissions of reactive nitrogen oxides, including nitrogen dioxide (NO2), a US EPA criteria pollutant that affects both human and environmental health. A fraction of this anthropogenic, atmospheric NO2 is deposited onto the urban forest, potentially mitigating the impact of NO2 on respiratory health within cities. However, the role of the urban forest in removal of atmospheric NO2 through deposition has not been well studied. Here, using an observationally-based statistical model, we first estimate the reduction of NO2 associated with the urban forest in Portland-Vancouver, USA, and the health benefits accruing from this reduction. In order to assess if this statistically observed reduction in NO2 associated with the urban forest is consistent with deposition, we then compare the amount of NO2 removed through deposition to the urban forest as estimated using a 4km CMAQ simulation. We further undertake a sensitivity analysis in CMAQ to estimate the range of NO2removed as a function of bulk stomatal resistance. We find that NO2 deposition estimated by CMAQ accounts for roughly one-third of the reduction in NO2 shown by the observationally-based statistical model (Figure). Our sensitivity analysis shows that a 3-10 fold increase in the bulk stomatal resistance parameter in CMAQ would align CMAQ-estimated deposition with the statistical model. The reduction of NO2 by the urban forest in the Portland-Vancouver area may yield a health benefit of at least $1.5 million USD annually, providing strong motivation to better understand the mechanism through which the urban forest may be removing air pollutants such as NO2and thus helping create healthier urban atmospheres. Figure: Comparing the amount of NO2 deposition as estimated by CMAQ and the observationally-based statistical model (LURF). Each point corresponds to a single 4 x 4km CMAQ grid cell.

Microporous Carbon Polyhedrons Encapsulated Polyacrylonitrile Nanofibers as Sulfur Immobilizer for Lithium-Sulfur Battery.

PubMed

Zhang, Ye-Zheng; Wu, Zhen-Zhen; Pan, Gui-Ling; Liu, Sheng; Gao, Xue-Ping

2017-04-12

Microporous carbon polyhedrons (MCPs) are encapsulated into polyacrylonitrile (PAN) nanofibers by electrospinning the mixture of MCPs and PAN. Subsequently, the as-prepared MCPs-PAN nanofibers are employed as sulfur immobilizer for lithium-sulfur battery. Here, the S/MCPs-PAN multicomposites integrate the advantage of sulfur/microporous carbon and sulfurized PAN. Specifically, with large pore volume, MCPs inside PAN nanofibers provide a sufficient sulfur loading. While PAN-based nanofibers offer a conductive path and matrix. Therefore, the electrochemical performance is significantly improved for the S/MCPs-PAN multicomposite with a suitable sulfur content in carbonate-based electrolyte. At the current density of 160 mA g -1 sulfur , the S/MPCPs-PAN composite delivers a large discharge capacity of 789.7 mAh g -1 composite , high Coulombic efficiency of about 100% except in the first cycle, and good capacity retention after 200 cycles. In particular, even at 4 C rate, the S/MCPs-PAN composite can still release the discharge capacity of 370 mAh g -1 composite . On the contrary, the formation of the thick SEI layer on the surface of nanofibers with a high sulfur content are observed, which is responsible for the quick capacity deterioration of the sulfur-based composite in carbonate-based electrolyte. This design of the S/MCPs-PAN multicomposite is helpful for the fabrication of stable Li-S battery.

The Oceanic Cycle and Global Atmospheric Budget of Carbonyl Sulfide.

NASA Astrophysics Data System (ADS)

Weiss, Peter Scott

1995-01-01

A significant portion of stratospheric air chemistry is influenced by the existence of carbonyl sulfide (COS). This ubiquitous sulfur gas represents a major source of sulfur to the stratosphere where it is converted to sulfuric acid aerosol particles. Stratospheric aerosols are climatically important because they scatter incoming solar radiation back to space and are able to increase the catalytic destruction of ozone through gas phase reactions on particle surfaces. COS is primarily formed at the surface of the earth, in both marine and terrestrial environments, and is strongly linked to natural biological processes. However, many gaps in the understanding of the global COS cycle still exist, which has led to a global atmospheric budget that is out of balance by a factor of two or more, and a lack of understanding of how human activity has affected the cycling of this gas. The goal of this study was to focus on COS in the marine environment by investigating production/destruction mechanisms and recalculating the ocean-atmosphere flux. Analytical work was carried out using the electron capture sulfur detector (ECD-S) for gas chromatography. This system was optimized for COS so that air and seawater-equilibrated air samples could be directly injected without preconcentration. This research was carried out on two cruises aboard the NOAA ship Surveyor during long meridional transects between 55^circN and 70 ^circS along 140^circ W in the Pacific Ocean. The major findings of these research activities are: (1) Photoproduction of COS is at a maximum between 313 and 336 nm in natural sunlit waters. Tropical water surface and column production rates are 68 pM/day and 360 nmol/m^2/day, respectively. Antarctic surface and column production rates are 101 pM/day and 620 nmol/m^2/day, respectively. (2) Wide regions of the open ocean were found to be undersaturated with respect to atmospheric equilibrium of COS. The global open ocean sea-air flux of COS was found to be -0

Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

DOEpatents

Liang, Chengdu; Dudney, Nancy J; Howe, Jane Y

2015-05-05

The invention is directed in a first aspect to a sulfur-carbon composite material comprising: (i) a bimodal porous carbon component containing therein a first mode of pores which are mesopores, and a second mode of pores which are micropores; and (ii) elemental sulfur contained in at least a portion of said micropores. The invention is also directed to the aforesaid sulfur-carbon composite as a layer on a current collector material; a lithium ion battery containing the sulfur-carbon composite in a cathode therein; as well as a method for preparing the sulfur-composite material.

Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

DOEpatents

Liang, Chengdu; Dudney, Nancy J.; Howe, Jane Y.

2017-08-01

The invention is directed in a first aspect to a sulfur-carbon composite material comprising: (i) a bimodal porous carbon component containing therein a first mode of pores which are mesopores, and a second mode of pores which are micropores; and (ii) elemental sulfur contained in at least a portion of said micropores. The invention is also directed to the aforesaid sulfur-carbon composite as a layer on a current collector material; a lithium ion battery containing the sulfur-carbon composite in a cathode therein; as well as a method for preparing the sulfur-composite material.

Micro-Scale Sulfur and Carbon Isotope Analysis of a Neoarchean Stromatolite: Evidence for a Profound Redox Transition in Shelf Margins prior to the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Ilhardt, P.; House, C. H.; Altermann, W.

2016-12-01

Neoarchean shelf margin environments such as the Campbellrand-Malmani platform are believed to have been sites of substantial O2 accumulation and nutrient cycling prior to the Great Oxidation Event (GOE). Stromatolites in particular serve as biogeochemical "hotspots" where evidence of various metabolic pathways and bacterial lineages can be traced through geochemical fingerprints. We identified morphologically-unique, organic-rimmed pyrite grains embedded in the dolomitic lamina of a Campbellrand Subgroup stromatolite (2.6 Ga). Carbon and sulfur isotopes measured in situ revealed a multi-layered microbial community employing photoautotrophic carbon fixation, organic matter respiration, sulfate reduction, and potentially assimilation of methane. In particular, unusually high kerogen δ13Corg and pyrite δ34S compositions are consistent with a semi-aerobic ecosystem recycling photosynthetic biomass and sulfate reduction in sulfate-limited porewaters, respectively. In addition, an array of positive Δ33S values suggests incorporation of atmospherically-derived sulfur formed from volcanic SO2 photochemistry and isolated in particulate form. We argue the Δ33S-δ34S trend is best explained by mixing between a δ34S-enriched coastal marine sulfate reservoir and stratospheric Δ33S-positive sulfate or elemental sulfur aerosols. The hypothesized buildup of sulfur gases at higher altitudes agrees with prior arguments for increased subaerial felsic volcanism and intense plume activity coinciding with oxidation of the upper mantle. We suggest explosive subaerial eruptions sustained a stratospheric SO2 reservoir that underwent photochemistry via long-wavelength (250-330 nm) UV radiation to produce positive MIF-carrying aerosol particles (sulfate or sulfur) in the Neoarchean. This contrasts with Paleoarchean sulfur chemistry dominated by SO2 photolysis in the 190-220 nm excitation band and points to an evolving Archean atmosphere, culminating in a coupled biogeochemical

Sulfuric Acid on Europa