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Sample records for dimethylsulfide

  1. Henry's law constants for dimethylsulfide in freshwater and seawater

    NASA Technical Reports Server (NTRS)

    Dacey, J. W. H.; Wakeham, S. G.; Howes, B. L.

    1984-01-01

    Distilled water and several waters of varying salinity were subjected, over a 0-32 C temperature range, to measurements for Henry's law constants for dimethylsulfide. Values for distilled water and seawater of the solubility parameters A and C are obtained which support the concept that the concentration of dimethylsulfide in the atmosphere is far from equilibrium with seawater.

  2. Factors controlling dimethylsulfide emission from salt marshes

    NASA Technical Reports Server (NTRS)

    Dacey, John W. H.; Wakeham, S. G.; Howes, B. L.

    1985-01-01

    The factors that control the emission of methylated gases from salt marshes are being studied. Research focusses on dimethylsulfide (DMS) formation and the mechanism of DMS and CH4 emission to the atmosphere. The approach is to consider the plants as valves regulating the emission of methylated gases to the atmosphere with the goal of developing appropriate methods for emission measurement. In the case of CH4, the sediment is the source and transport to the atmosphere occurs primarily through the internal gas spaces in the plants. The source of DMS appears to be dimethyl sulfoniopropionate (DMSP) which may play a role in osmoregulation in plant tissues. Concentrations of DMSP in leaves are typically several-fold higher than in roots and rhizomes. Even so, the large below ground biomass of this plant means that 2/3 of the DMSP in the ecosystem is below ground on the aerial basis. Upon introduction to sediment water, DMSP rapidly decomposes to DMS and acrylic acid. The solubility of a gas (its equilibrium vapor pressure) is a fundamental aspect of gas exchange kinetics. The first comprehensive study was conducted of DMS solubility in freshwater and seawater. Data suggest that the Setchenow relation holds for H at intermediate salinities collected. These data support the concept that the concentration of DMS in the atmosphere is far from equilibrium with seawater.

  3. Impact of dimethylsulfide chemistry on sulfate over the Northern Hemisphere

    EPA Science Inventory

    Sulfate aerosol forms from the gas- and aqueous-phase oxidation of sulfur dioxide and is an important component of atmospheric aerosols. Dimethylsulfide (DMS) present in sea-water can be emitted into the atmosphere which can then react with atmospheric oxidants to produce sulfur ...

  4. Dimethylsulfide chemistry: annual, seasonal, and spatial impacts on SO_4^(2-)

    EPA Science Inventory

    We incorporated oceanic emissions and atmospheric chemistry of dimethylsulfide (DMS) into the hemispheric Community Multiscale Air Quality model and performed annual model simulations without and with DMS chemistry. The model without DMS chemistry predicts higher concentrations o...

  5. Enhancement of dimethylsulfide production by anoxic stress in natural seawater

    NASA Astrophysics Data System (ADS)

    Omori, Yuko; Tanimoto, Hiroshi; Inomata, Satoshi; Wada, Shigeki; Thume, Kathleen; Pohnert, Georg

    2015-05-01

    Dimethylsulfide (DMS) is produced by phytoplankton in the ocean and plays an important role in biogeochemical cycles and climate system of the Earth. Previous field studies reported a possible relationship between DMS enhancement and anoxic condition, although the governing processes are still to be identified. Here we show the first direct evidence for the enhancement of DMS production by natural planktonic assemblages caused by anoxic stress. Under the anoxic condition, DMS production was considerably enhanced and DMS bacterial consumption was inhibited, resulting in an eightfold higher rate of gross DMS production than that under the oxic condition. Our results demonstrated that anoxic stress is one of important "environmental factors" in the marine DMS dynamics, suggesting the possible global importance due to ubiquity of anoxic conditions in the coastal oceans. This process would become more important in the future due to expansion of coastal hypoxic and anoxic zones by global warming.

  6. Anaerobic oxidation of dimethylsulfide and methanethiol in mangrove sediments is dominated by sulfate-reducing bacteria.

    PubMed

    Lyimo, Thomas J; Pol, Arjan; Harhangi, Harry R; Jetten, Mike S M; Op den Camp, Huub J M

    2009-12-01

    The oxidation of dimethylsulfide and methanethiol by sulfate-reducing bacteria (SRB) was investigated in Tanzanian mangrove sediments. The rate of dimethylsulfide and methanethiol accumulation in nonamended sediment slurry (control) incubations was very low while in the presence of the inhibitors tungstate and bromoethanesulfonic acid (BES), the accumulation rates ranged from 0.02-0.34 to 0.2-0.4 nmol g FW sediment(-1) h(-1), respectively. Degradation rates of methanethiol and dimethylsulfide added were 2-10-fold higher. These results point to a balance of production and degradation. Degradation was inhibited much stronger by tungstate than by BES, which implied that SRB were more important. In addition, a new species of SRB, designated strain SD1, was isolated. The isolate was a short rod able to utilize a narrow range of substrates including dimethylsulfide, methanethiol, pyruvate and butyrate. Strain SD1 oxidized dimethylsulfide and methanethiol to carbon dioxide and hydrogen sulfide with sulfate as the electron acceptor and exhibited a low specific growth rate of 0.010 +/- 0.002 h(-1), but a high affinity for its substrates. The isolated microorganism could be placed in the genus Desulfosarcina (the most closely related cultured species was Desulfosarcina variabilis, 97% identity). Strain SD1 represents a member of the dimethylsulfide/methanethiol-consuming SRB population in mangrove sediments.

  7. Mechanism of the Thermal Decomposition of Ethanethiol and Dimethylsulfide

    NASA Astrophysics Data System (ADS)

    Melhado, William Francis; Whitman, Jared Connor; Kong, Jessica; Anderson, Daniel Easton; Vasiliou, AnGayle (AJ)

    2016-06-01

    Combustion of organosulfur contaminants in petroleum-based fuels and biofuels produces sulfur oxides (SO_x). These pollutants are highly regulated by the EPA because they have been linked to poor respiratory health and negative environmental impacts. Therefore much effort has been made to remove sulfur compounds in petroleum-based fuels and biofuels. Currently desulfurization methods used in the fuel industry are costly and inefficient. Research of the thermal decomposition mechanisms of organosulfur species can be implemented via engineering simulations to modify existing refining technologies to design more efficient sulfur removal processes. We have used a resistively-heated SiC tubular reactor to study the thermal decomposition of ethanethiol (CH_3CH_2SH) and dimethylsulfide (CH_3SCH_3). The decomposition products are identified by two independent techniques: 118.2 nm VUV photoionization mass spectroscopy and infrared spectroscopy. The thermal cracking products for CH_3CH_2SH are CH_2CH_2, SH, and H_2S and the thermal cracking products from CH_3SCH_3 are CH_3S, CH_2S, and CH_3.

  8. Methanethiol and dimethylsulfide formation from 3-methylthiopropionate in human and rat hepatocytes.

    PubMed

    Blom, H J; van den Elzen, J P; Yap, S H; Tangerman, A

    1988-11-18

    This study was designed to investigate the metabolism of methanethiol, and the involvement of methanethiol and its metabolites in the transamination pathway of methionine. Gaseous methanethiol, methanethiol-mixed disulfides and dimethylsulfide were formed from 3-methylthiopropionate, a metabolite in the transamination pathway of methionine, during incubation with human and rat hepatocytes. An increase of the 3-methylthiopropionate concentration resulted in an increased formation of the products, up to a substrate concentration of 4.4 mM. Higher substrate levels resulted in a decreased methanethiol formation, probably due to poisoning of the system. However, in human hepatocytes the formation of dimethylsulfide increased up to a 3-methylthiopropionate concentration of 12.5 mM. The formation of methanethiol, dimethylsulfide and methanethiol-mixed disulfides from 3-methylthiopropionate in hepatocytes of both human and rat support the hypothesis that methanethiol can be formed from methionine via the transamination pathway.

  9. Marine microbial production of dimethylsulfide from dissolved dimethylsulfoniopropionate. Doctoral thesis

    SciTech Connect

    Ledyard, K.M.

    1993-02-01

    Dimethylsulfide (DMS) plays a central role in the transfer of sulfur from the ocean to the atmosphere, and ultimately to land. The most abundant volatile organosulfur compound in seawater, DMS is believed to account for the bulk of the sea-to-air biogenic sulfur flux. DMS has also been implicated as the major precursor of submicron-sized sulfate aerosol over the ocean. This aerosol acts as an effective site for cloud droplet condensation, suggesting a possibly important role for DMS in marine cloud formation. In the ocean, the precursor of DMS is presumed to be the zwitterionic sulfonium compound dimethylsulfoniopropionate (DMSP), a common osmoticum in certain classes of marine algae. While some algae can cleave DMSP intracellularly to form DMS, correlation of DMS concentrations with indicators of algal productivity on a local scale is poor. This thesis focuses on an alternative pathway of DMS formation: microbial cleavage of dissolved (extracellular) DMSP. In laboratory studies, bacteria able to cleave DMSP to form DMS were isolated from seawater by a DMSP enrichment technique, and the kinetics of DMSP uptake and DMS production were examined closely in pure cultures of a bacterial isolate from the Sargasso Sea. The isolate could grow with both DMSP and acrylic acid, one of the products of DMSP cleavage, as the sole source of carbon and energy, and the enzyme catalyzing DMSP cleavage appeared to be induced by both of these compounds. Kinetic parameters were estimated for DMSP uptake and cleavage by whole cells. Comparison of the 16S rRNA sequence of this isolate with that of known eubacteria showed that it was most closely related to Erythrobacter longus, an aerobic, bacteriochlorophyll-containing member of the alpha proteobacteria.

  10. Physiological Ecology of Dimethylsulfoniopropionate (DMSP) and Dimethylsulfide (DMS) Production by Phytoplankton

    NASA Technical Reports Server (NTRS)

    1998-01-01

    The main objectives of the previously funded work were: (1) to determine the rates of DMSP and DMS production as a function of phytoplankton growth rate; (2) to determine the light dependence (quantity and quality) of DiMethylSulfonioPropionate (DMSP) and DiMethylSulfide (DMS) production by phytoplankton; and (3) to study intraspecific differences in DMSP and DMS production by phytoplankton.

  11. Coherent phase control of the product branching ratio in the photodissociation of dimethylsulfide

    SciTech Connect

    Nagai, Hidekazu; Ohmura, Hideki; Ito, Fumiyuki; Nakanaga, Taisuke; Tachiya, Masanori

    2006-01-21

    Coherent phase control of the photodissociation reaction of the dimethylsulfide has been achieved by means of quantum-mechanical interference between one- and three-photon transitions. Dimethylsulfide was irradiated by fundamental and frequency-tripled outputs of a visible laser (600.5-602.5 nm), simultaneously to yield CH{sub 3}S{sup +} and CH{sub 3}SCH{sub 2}{sup +} fragment ions. The branching ratio of the two product channels could be modulated with variation of the phase difference between the light fields. This accounted for the difference between the molecular phases of the two product channels. The phase lag was observed to have a maximum value of 8 deg. at 601.5 nm. This is the first result of a selective bond breaking in a polyatomic molecule by the coherent phase control.

  12. Dimethylsulfide is an energy source for the heterotrophic marine bacterium Sagittula stellata.

    PubMed

    Boden, Rich; Murrell, J Colin; Schäfer, Hendrik

    2011-09-01

    Dimethylsulfide (DMS) is a volatile organosulfur compound, ubiquitous in the oceans, that has been credited with various roles in biogeochemical cycling and in climate control. Various oceanic sinks of DMS are known - both chemical and biological - although they are poorly understood. In addition to the utilization of DMS as a carbon or a sulfur source, some Bacteria are known to oxidize it to dimethylsulfoxide (DMSO). Sagittula stellata is a heterotrophic member of the Alphaproteobacteria found in marine environments. It has been shown to oxidize DMS during heterotrophic growth on sugars, but the reasons for and the mechanisms of this oxidation have not been investigated. Here, we show that the oxidation of DMS to DMSO is coupled to ATP synthesis in S. stellata and that DMS acts as an energy source during chemoorganoheterotrophic growth of the organism on fructose and on succinate. DMS dehydrogenase (which is responsible for the oxidation of DMS to DMSO in other marine Bacteria) and DMSO reductase activities were absent from cells grown in the presence of DMS, indicating an alternative route of DMS oxidation in this organism.

  13. Biosynthesis of dimethylsulfide and dimethylpropiothetin by Hymenomonas carterae in relation to sulfur source and salinity variations

    SciTech Connect

    Vairavamurthy, A.; Andreae, M.O.; Iverson, R.L.

    1985-01-01

    The marine coccolithophoroid phytoplankton species Hymenomonas carterae (class Prymnesiophyceae) produces both dimethylpropiothetin (DMPT) and dimethylsulfide (DMS) in axenic cultures. The rate of DMS production is closely regulated by the cell; it remains independent of environmental sulfate concentration down to levels of 2.5% of the seawater value. Below this sulfate level, DMS production decreases with decreasing sulfate concentration, but significant amounts of DMS are released even under conditions of sulfate-limited growth. Hymenomonas carterae can grow on sulfite, thiosulfate, and cysteine as sulfur sources, but not on methionine. The rate of DMS output is similar for the different sulfur sources. Both the intracellular concentration of DMPT and the rate of output of DMS by H. carterae increase with increasing salinity of the medium. This increase is observed when either salt or sucrose is used to control the osmolarity of the growth medium. Variations in DMPT levels and DMS output were observed within hours after transferring cells to a medium of different osmotic pressure. These results suggest that DMPT plays an important role in osmoregulation by H. carterae.

  14. Vertical distribution of dimethylsulfide, sulfur dioxide, aerosol ions, and radon over the northeast Pacific Ocean

    NASA Technical Reports Server (NTRS)

    Andreae, M. O.; Berresheim, H.; Andreae, T. W.; Kritz, M. A.; Bates, T. S.

    1988-01-01

    The vertical distributions, in temperate latitudes, of dimethylsulfide (DMS), SO2, radon, methanesulfonate (MSA), nonsea-salt sulfate (nss-sulfate), and aerosol Na(+), NH4(+), and NO(-) ions were determined in samples collected by an aircraft over the northeast Pacific Ocean during May 3-12, 1985. DMS was also determined in surface seawater. It was found that DMS concentrations, both in seawater and in the atmospheric boundary layer, were significantly lower than the values reported previously for subtropical and tropical regions, reflecting the seasonal variability in the temperate North Pacific. The vertical profiles of DMS, MSA, SO2, and nss-sulfate were found to be strongly dependent on the convective stability of the atmosphere and on air mass origin. Biogenic sulfur emissions could account for most of the sulfur budget in the boundary layer, while the long-range transport of continentally derived air masses was mainly responsible for the elevated levels of both SO2 and nss-sulfate in the free troposphere.

  15. Airborne sulfur trace species intercomparison campaign: Sulfur dioxide, dimethylsulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide

    NASA Technical Reports Server (NTRS)

    Gregory, Gerald L.; Hoell, James M., Jr.; Davis, Douglas D.

    1991-01-01

    Results from an airborne intercomparison of techniques to measure tropospheric levels of sulfur trace gases are presented. The intercomparison was part of the NASA Global Tropospheric Experiment (GTE) and was conducted during the summer of 1989. The intercomparisons were conducted on the Wallops Electra aircraft during flights from Wallops Island, Virginia, and Natal, Brazil. Sulfur measurements intercompared included sulfur dioxide (SO2), dimethylsulfide (DMS), hydrogen sulfide (H2S), carbon disulfide (CS2), and carbonyl sulfide (OCS). Measurement techniques ranged from filter collection systems with post-flight analyses to mass spectrometer and gas chromatograph systems employing various methods for measuring and identifying the sulfur gases during flight. Sampling schedules for the techniques ranged from integrated collections over periods as long as 50 minutes to one- to three-minute samples every ten or fifteen minutes. Several of the techniques provided measurements of more than one sulfur gas. Instruments employing different detection principles were involved in each of the sulfur intercomparisons. Also included in the intercomparison measurement scenario were a host of supporting measurements (i.e., ozone, nitrogen oxides, carbon monoxide, total sulfur, aerosols, etc.) for purposes of: (1) interpreting results (i.e., correlation of any noted instrument disagreement with the chemical composition of the measurement environment); and (2) providing supporting chemical data to meet CITE-3 science objectives of studying ozone/sulfur photochemistry, diurnal cycles, etc. The results of the intercomparison study are briefly discussed.

  16. Measurements of atmospheric dimethylsulfide, hydrogen sulfide, and carbon disulfide during GTE/CITE 3

    NASA Technical Reports Server (NTRS)

    Cooper, David J.; Saltzman, Eric S.

    1993-01-01

    Measurements of atmospheric dimethylsulfide (DMS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were made over the North and South Atlantic Ocean as part of the Global Tropospheric Experiment/Chemical Instrumentation Test and Evaluation (GTE/CITE 3) project. DMS and CS2 samples were collected and analyzed using an automated gas chromatography/flame photometric detection system with a sampling frequency of 10 min. H2S samples were collected using silver nitrate impregnated filters and analyzed by fluorescence quenching. The DMS data from both hemispheres have a bimodal distribution. Over the North Atlantic this reflects the difference between marine and continental air masses. Over the South Atlantic it may reflect differences in the sea surface source of DMS, corresponding to different air mass source regions. The median boundary layer H2S and CS2 levels were significantly higher in the northern hemisphere than the southern hemisphere, reflecting the higher frequency of samples influenced by pollutant and/or coastal emissions. Composite vertical profiles of DMS and H2S are similar to each other, are consistent with a sea surface source. Vertical profiles of CS2 have maxima in the free troposphere, implicating a continental source. The low levels of H2S and CS2 found in the southern hemisphere constrain the role of these compounds in global budgets to significantly less than previously estimated.

  17. Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

    NASA Astrophysics Data System (ADS)

    Hopkins, Frances E.; Bell, Thomas G.; Yang, Mingxi; Suggett, David J.; Steinke, Michael

    2016-10-01

    Corals are prolific producers of dimethylsulfoniopropionate (DMSP). High atmospheric concentrations of the DMSP breakdown product dimethylsulfide (DMS) have been linked to coral reefs during low tides. DMS is a potentially key sulfur source to the tropical atmosphere, but DMS emission from corals during tidal exposure is not well quantified. Here we show that gas phase DMS concentrations (DMSgas) increased by an order of magnitude when three Indo-Pacific corals were exposed to air in laboratory experiments. Upon re-submersion, an additional rapid rise in DMSgas was observed, reflecting increased production by the coral and/or dissolution of DMS-rich mucus formed by the coral during air exposure. Depletion in DMS following re-submersion was likely due to biologically-driven conversion of DMS to dimethylsulfoxide (DMSO). Fast Repetition Rate fluorometry showed downregulated photosynthesis during air exposure but rapid recovery upon re-submersion, suggesting that DMS enhances coral tolerance to oxidative stress during a process that can induce photoinhibition. We estimate that DMS emission from exposed coral reefs may be comparable in magnitude to emissions from other marine DMS hotspots. Coral DMS emission likely comprises a regular and significant source of sulfur to the tropical marine atmosphere, which is currently unrecognised in global DMS emission estimates and Earth System Models.

  18. Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

    PubMed Central

    Hopkins, Frances E.; Bell, Thomas G.; Yang, Mingxi; Suggett, David J.; Steinke, Michael

    2016-01-01

    Corals are prolific producers of dimethylsulfoniopropionate (DMSP). High atmospheric concentrations of the DMSP breakdown product dimethylsulfide (DMS) have been linked to coral reefs during low tides. DMS is a potentially key sulfur source to the tropical atmosphere, but DMS emission from corals during tidal exposure is not well quantified. Here we show that gas phase DMS concentrations (DMSgas) increased by an order of magnitude when three Indo-Pacific corals were exposed to air in laboratory experiments. Upon re-submersion, an additional rapid rise in DMSgas was observed, reflecting increased production by the coral and/or dissolution of DMS-rich mucus formed by the coral during air exposure. Depletion in DMS following re-submersion was likely due to biologically-driven conversion of DMS to dimethylsulfoxide (DMSO). Fast Repetition Rate fluorometry showed downregulated photosynthesis during air exposure but rapid recovery upon re-submersion, suggesting that DMS enhances coral tolerance to oxidative stress during a process that can induce photoinhibition. We estimate that DMS emission from exposed coral reefs may be comparable in magnitude to emissions from other marine DMS hotspots. Coral DMS emission likely comprises a regular and significant source of sulfur to the tropical marine atmosphere, which is currently unrecognised in global DMS emission estimates and Earth System Models. PMID:27796323

  19. Measurements of atmospheric dimethylsulfide, hydrogen sulfide, and carbon disulfide during GTE/CITE 3

    NASA Astrophysics Data System (ADS)

    Cooper, David J.; Saltzman, Eric S.

    1993-12-01

    Measurements of atmospheric dimethylsulfide (DMS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were made over the North and South Atlantic Ocean as part of the Global Tropospheric Experiment/Chemical Instrumentation Test and Evaluation (GTE/CITE 3) project. DMS and CS2 samples were collected and analyzed using an automated gas chromatography/flame photometric detection system with a sampling frequency of 10 min. H2S samples were collected using silver nitrate impregnated filters and analyzed by fluorescence quenching. The DMS data from both hemispheres have a bimodal distribution. Over the North Atlantic this reflects the difference between marine and continental air masses. Over the South Atlantic it may reflect differences in the sea surface source of DMS, corresponding to different air mass source regions. The median boundary layer H2S and CS2 levels were significantly higher in the northern hemisphere than the southern hemisphere, reflecting the higher frequency of samples influenced by pollutant and/or coastal emissions. Composite vertical profiles of DMS and H2S are similar to each other, and are consistent with a sea surface source. Vertical profiles of CS2 have maxima in the free troposphere, implicating a continental source. The low levels of H2S and CS2 found in the southern hemisphere constrain the role of these compounds in global budgets to significantly less than previously estimated.

  20. Release of Dimethylsulfide from Dimethylsulfoniopropionate by Plant-Associated Salt Marsh Fungi

    PubMed Central

    Bacic, M. K.; Newell, S. Y.; Yoch, D. C.

    1998-01-01

    The range of types of microbes with dimethylsulfoniopropionate (DMSP) lyase capability (enzymatic release of dimethylsulfide [DMS] from DMSP) has recently been expanded from bacteria and eukaryotic algae to include fungi (a species of the genus Fusarium [M. K. Bacic and D. C. Yoch, Appl. Environ. Microbiol. 64:106–111, 1998]). Fungi (especially ascomycetes) are the predominant decomposers of shoots of smooth cordgrass, the principal grass of Atlantic salt marshes of the United States. Since the high rates of release of DMS from smooth cordgrass marshes have a temporal peak that coincides with peak shoot death, we hypothesized that cordgrass fungi were involved in this DMS release. We tested seven species of the known smooth cordgrass ascomycetes and discovered that six of them exhibited DMSP lyase activity. We also tested two species of ascomycetes from other DMSP-containing plants, and both were DMSP lyase competent. For comparison, we tested 11 species of ascomycetes and mitosporic fungi from halophytes that do not contain DMSP; of these 11, only 3 were positive for DMSP lyase. A third group tested, marine oomycotes (four species of the genera Halophytophthora and Pythium, mostly from mangroves), showed no DMSP lyase activity. Two of the strains of fungi found to be positive for DMSP lyase also exhibited uptake of DMS, an apparently rare combination of capabilities. In conclusion, a strong correlation exists between a fungal decomposer’s ability to catabolize DMSP via the DMSP lyase pathway and the host plant’s production of DMSP as a secondary product. PMID:16349548

  1. Vernal distribution and turnover of dimethylsulfide (DMS) in the surface water of the Yellow Sea

    NASA Astrophysics Data System (ADS)

    Li, Cheng-Xuan; Yang, Gui-Peng; Wang, Bao-Dong; Xu, Zong-Jun

    2016-10-01

    The spatial and interannual variations of dimethylsulfide (DMS) and its precursors, dissolved and particulate dimethylsulfoniopropionate (DMSP), were discussed on the basis of field observations in the surface waters of the Yellow Sea during spring 2007. Maxima of dimethylated sulfur compounds and low chlorophyll a concentrations were found in the central southern Yellow Sea, whereas low concentrations of DMS and DMSP were detected at the boundary between the northern and southern parts of the Yellow Sea. This frontal region is influenced by active water currents, air-sea interface exchanges, and biological turnover. The horizontal variations in DMS production and consumption rates showed a decreasing tendency from the coastal to offshore areas mainly due to the complicated biological features. DMS positively correlated with dissolved CH4 and CO2 but negatively correlated with nutrients (nitrite and phosphate). Particulate DMSP concentrations and DMS production rates positively correlated with dinoflagellate abundances but negatively correlated with diatom cell densities. DMS and DMSP concentrations, as well as DMS production and consumption rates, exhibited approximately 2.0-2.8 fold increases from 2005 to 2012. This finding was likely caused by shifts in the phytoplankton communities from diatoms to dinoflagellates and the increases in abundances of zooplankton and bacteria. Average sea-to-air DMS fluxes were estimated to be 8.12 ± 1.24 µmol·(m-2·d-1), and DMS microbial consumption was approximately 1.68 times faster than the DMS sea-air exchange. These findings imply that biological consumption, relative to ventilation, is a predominant mechanism in DMS removal from the surface water.

  2. Marine microbial production of dimethylsulfide from dissolved dimethylsulfoniopropionate. Ph. D. Thesis

    SciTech Connect

    Ledyard, K.M.

    1993-02-01

    Dimethylsulfide (DMS) plays a central role in the transfer of sulfur from the ocean to the atmosphere and ultimately to land. The most abundant volatile organosulfur compound in seawater, DMS is believed to account for the bulk of the sea-to-air biogenic sulfur flux. DMS has also been implicated as the major precursor of submicron-sized sulfate aerosol over the ocean. This aerosol acts as an effective site for cloud droplet condensation suggesting a possibly important role for DMS in marine cloud formation. In the ocean, the precursor of DMS is presumed to be the zwitterionic sulfonium compound dimethylsulfoniopropionate (DMSP), a common osmoticum in certain classes of marine algae. While some algae can cleave DMSP intracellularly to form DMS, correlation of DMS concentrations with indicators of algal productivity on a local scale is poor. This thesis focuses on an alternative pathway of DMS formation: microbial cleavage of dissolved (extracellular) DMSP. In laboratory studies, bacteria able to cleave DMSP to form DMS were isolated from seawater by a DMSP enrichment technique, and the kinetics of DMSP uptake and DMS production were examined closely in pure cultures of a bacterial isolate from the Sargasso Sea. The isolate could grow with both DMSP and acrylic acid, one of the products of DMSP cleavage, as the sole source of carbon and energy, and the enzyme catalyzing DMSP cleavage appeared to be induced by both of these compounds. Kinetic parameters were estimated for DMSP uptake and cleavage by whole cells. Comparison of the 16S rRNA sequence of this isolate with that of known eubacteria showed that it was most closely related to Erythrobacter longus, an aerobic, bacteriochlorophyll-containing member of the alpha proteobacteria.

  3. Origin of dimethylsulfide, non-sea-salt sulfate, and methanesulfonic acid in eastern Antarctica

    NASA Astrophysics Data System (ADS)

    Cosme, E.; Hourdin, F.; Genthon, C.; Martinerie, P.

    2005-02-01

    Ignoring the origin of atmospheric chemicals is often a strong limitation to the full interpretation of their measurement. In this article, this question is addressed in the case of the sulfur species in Antarctica, with an original method of retrotransport of tracers. The retrotransport model is derived from the Laboratoire de Météorologie Dynamique Zoom-Tracers (LMD-ZT) atmospheric general circulation model, optimized for polar climate and expanded to simulate atmospheric sulfur chemistry. For two East Antarctic scientific stations (Dumont d'Urville and Vostok) the effects of transport and chemistry and the influence of oceanic, volcanic, and anthropogenic sources on dimethylsulfide (DMS), non-sea-salt (nss) sulfate, and methanesulfonic acid (MSA) concentrations are evaluated in summer and winter. The oceanic source largely dominates, but other sources can episodically be significant. The meridional origin and the age of DMS, MSA, and biogenic nss sulfate are also estimated. The latitudes of origin of MSA and nss sulfate are similar in summer, but they differ markedly in winter. This is a signature of their different chemical production scheme. Also, the interannual variability of the origin of the sulfur species at Vostok is weak compared to that at Dumont d'Urville. Acknowledging that the DMS concentrations in the ocean have no interannual variability in the model, this result suggests unsurprisingly that inland Antarctic stations may be better observation sites to monitor large-scale DMS bioproductivity variability than coastal sites are. The combination of slower chemistry and more intense atmospheric circulation in winter leads to unexpected results, such as a younger DMS in winter than in summer at Vostok.

  4. Effects of Harpacticus sp. (Harpacticoida, copepod) grazing on dimethylsulfoniopropionate and dimethylsulfide concentrations in seawater

    NASA Astrophysics Data System (ADS)

    Yu, Juan; Tian, Ji-Yuan; Yang, Gui-Peng

    2015-05-01

    We conducted 9 d and 24 h ingestion experiments to investigate the effects of copepod grazing on the concentrations of dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) in seawater. Data from the 9 d trial showed that copepod Harpacticus sp. (Harpacticoida, copepod) grazing increased DMS (0-20%) and dissolved DMSP (DMSPd) (0-128%) apparently, accompanied by a significant reduction of particulate DMSP (DMSPp) in algal culture (0-30%). Ingestion rates (IRs) and pellet production rates (PPRs) of Harpacticus sp. varied with diet species (Platymonas subcordiformis (PS), Nitzschia closterium (NC), Skeletonema costatum (SC), Isochrysis galbana (IG), Prymnesium parvum (PP) or Heterosigma akashiwo (HA)), algal concentration, salinity and temperature. Harpacticus sp. fed on PP showed the lowest IRs (female/male, 0.72/0.53 × 104cells copepod- 1 h- 1) and PPRs (female/male, 0.75/0.5 pellets copepod- 1 h- 1), accompanied with the largest amounts of DMS and DMSPd,p (sum of DMSPd and DMSPp). IRs, PPRs, DMS and DMSPf (DMSP in fecal pellet) increased with the increase of food concentration and peaked at 25 × 104 cells mL- 1I. galbana. High salinity decreased IRs, PPRs, DMS and DMSPf and increased DMSPz (DMSP in copepod body) and DMSPd,p. IRs, PPRs, DMS and DMSPf increased with the increase of temperature from 15 to 25 °C, whereas DMSPz and DMSPd,p contents decreased. Pearson correlation analysis results showed that DMS concentrations presented positive relationships with IRs in algal concentration, salinity and temperature experiments (r = 0.746; P < 0.01). The contribution of DMSPz, DMSPf, DMS and DMSPd,p concentration to the total amounts (DMSPz + DMSPf + DMS + DMSPd,p) was 4-37%, 3-36%, 8-42% and 9-89%, respectively, indicating that DMSP was transferred to copepod tissue and fecal pellet via grazing. Our results are helpful for further understanding of the role of copepod grazing on DMS biogeochemical cycle.

  5. Weak response of oceanic dimethylsulfide to upper mixing shoaling induced by global warming.

    PubMed

    Vallina, S M; Simó, R; Manizza, M

    2007-10-09

    The solar radiation dose in the oceanic upper mixed layer (SRD) has recently been identified as the main climatic force driving global dimethylsulfide (DMS) dynamics and seasonality. Because DMS is suggested to exert a cooling effect on the earth radiative budget through its involvement in the formation and optical properties of tropospheric clouds over the ocean, a positive relationship between DMS and the SRD supports the occurrence of a negative feedback between the oceanic biosphere and climate, as postulated 20 years ago. Such a natural feedback might partly counteract anthropogenic global warming through a shoaling of the mixed layer depth (MLD) and a consequent increase of the SRD and DMS concentrations and emission. By applying two globally derived DMS diagnostic models to global fields of MLD and chlorophyll simulated with an Ocean General Circulation Model coupled to a biogeochemistry model for a 50% increase of atmospheric CO(2) and an unperturbed control run, we have estimated the response of the DMS-producing pelagic ocean to global warming. Our results show a net global increase in surface DMS concentrations, especially in summer. This increase, however, is so weak (globally 1.2%) that it can hardly be relevant as compared with the radiative forcing of the increase of greenhouse gases. This contrasts with the seasonal variability of DMS (1000-2000% summer-to-winter ratio). We suggest that the "plankton-DMS-clouds-earth albedo feedback" hypothesis is less strong a long-term thermostatic system than a seasonal mechanism that contributes to regulate the solar radiation doses reaching the earth's biosphere.

  6. Coral reef origins of atmospheric dimethylsulfide at Heron Island, southern Great Barrier Reef, Australia

    NASA Astrophysics Data System (ADS)

    Swan, Hilton B.; Jones, Graham B.; Deschaseaux, Elisabeth S. M.; Eyre, Bradley D.

    2017-01-01

    Atmospheric dimethylsulfide (DMSa), continually derived from the world's oceans, is a feed gas for the tropospheric production of new sulfate particles, leading to cloud condensation nuclei that influence the formation and properties of marine clouds and ultimately the Earth's radiation budget. Previous studies on the Great Barrier Reef (GBR), Australia, have indicated coral reefs are significant sessile sources of DMSa capable of enhancing the tropospheric DMSa burden mainly derived from phytoplankton in the surface ocean; however, specific environmental evidence of coral reef DMS emissions and their characteristics is lacking. By using on-site automated continuous analysis of DMSa and meteorological parameters at Heron Island in the southern GBR, we show that the coral reef was the source of occasional spikes of DMSa identified above the oceanic DMSa background signal. In most instances, these DMSa spikes were detected at low tide under low wind speeds, indicating they originated from the lagoonal platform reef surrounding the island, although evidence of longer-range transport of DMSa from a 70 km stretch of coral reefs in the southern GBR was also observed. The most intense DMSa spike occurred in the winter dry season at low tide when convective precipitation fell onto the aerially exposed platform reef. This co-occurrence of events appeared to biologically shock the coral resulting in a seasonally aberrant extreme DMSa spike concentration of 45.9 nmol m-3 (1122 ppt). Seasonal DMS emission fluxes for the 2012 wet season and 2013 dry season campaigns at Heron Island were 5.0 and 1.4 µmol m-2 day-1, respectively, of which the coral reef was estimated to contribute 4 % during the wet season and 14 % during the dry season to the dominant oceanic flux.

  7. Diagnostic modeling of dimethylsulfide production in coastal water west of the Antarctic Peninsula

    NASA Technical Reports Server (NTRS)

    Hermann, Maria; Najjar, Raymond G.; Neeley, Aimee R.; Vila-Costa, Maria; Dacey, John W. H.; DiTullio, Giacomo, R.; Kieber, David J.; Kiene, Ronald P.; Matrai, Patricia A.; Simo, Rafel; Vernet, Maria

    2012-01-01

    The rate of gross biological dimethylsulfide (DMS) production at two coastal sites west of the Antarctic Peninsula, off Anvers Island, near Palmer Station, was estimated using a diagnostic approach that combined field measurements from 1 January 2006 through 1 March 2006 and a one-dimensional physical model of ocean mixing. The average DMS production rate in the upper water column (0-60 m) was estimated to be 3.1 +/- 0.6 nM/d at station B (closer to shore) and 2.7 +/- 0.6 nM/d1 at station E (further from shore). The estimated DMS replacement time was on the order of 1 d at both stations. DMS production was greater in the mixed layer than it was below the mixed layer. The average DMS production normalized to chlorophyll was 0.5 +/- nM/d)/(mg cubic m) at station B and 0.7 +/- 0.2 (nM/d)/(mg/cubic m3) at station E. When the diagnosed production rates were normalized to the observed concentrations of total dimethylsulfoniopropionate (DMSPt, the biogenic precursor of DMS), we found a remarkable similarity between our estimates at stations B and E (0.06 +/- 0.02 and 0.04 +/- 0.01 (nM DMS / d1)/(nM DMSP), respectively) and the results obtained in a previous study from a contrasting biogeochemical environment in the North Atlantic subtropical gyre (0.047 =/- 0.006 and 0.087 +/- 0.014 (nM DMS d1)/(nM DMSP) in a cyclonic and anticyclonic eddy, respectively).We propose that gross biological DMS production normalized to DMSPt might be relatively independent of the biogeochemical environment, and place our average estimate at 0.06 +/- 0.01 (nM DMS / d)/(nM DMSPt). The significance of this finding is that it can provide a means to use DMSPt measurements to extrapolate gross biological DMS production, which is extremely difficult to measure experimentally under realistic in situ conditions.

  8. Variation of dimethylsulfide mixing ratio over the Southern Ocean from 36°S to 70°S

    NASA Astrophysics Data System (ADS)

    Koga, Seizi; Nomura, Daiki; Wada, Makoto

    2014-09-01

    Atmospheric dimethylsulfide (DMS) was measured to investigate the variation in its concentration over sea ice free oceans and sea ice regions of the Southern Ocean, using a proton transfer reaction-mass spectrometer (PTR-MS) on board the icebreaker Shirase from 1 December 2009 to 16 March 2010. In general, DMS concentrations over sea ice regions were very low compared with those over the sea ice free ocean. However, abrupt increases in DMS concentrations occurred over sea ice regions while the ship was moving and crushing the sea ice. Undoubtedly, the elevated DMS concentrations were caused by large DMS emissions from gaps in the ice made by the ship. During the period when Shirase had anchored off Syowa Station (69°00.4‧S, 39°35.3‧E), Antarctica, DMS concentrations were not detected. At this time, the surrounding sea of East Ongul island, on which Syowa Station is located, was completely covered with multi-year fast ice. Sea ice probably inhibits DMS emission from the ocean to the atmosphere. In addition, there was no evidence that chlorophyll a concentration in the sea water or wind speed above the sea surface affect atmospheric DMS concentrations over the sea ice free ocean regions.

  9. Formation and Release of H2S, Methanethiol, and Dimethylsulfide during the Anoxic Storage of Wines at Room Temperature.

    PubMed

    Franco-Luesma, Ernesto; Ferreira, Vicente

    2016-08-17

    A total of 21 different wines (13 reds, 5 whites, and 3 rosés) were kept at 25 °C in anoxia for 379 days. Free and total forms of H2S and methanethiol (MeSH) and dimethylsulfide (DMS) were measured initially and after 117, 221, and 379 days of storage. Levels of free H2S, free and total MeSH, and DMS continuously increased during storage, while levels of total H2S remained essentially unchanged. Average increases of free H2S amount to 6.2 μg/L (from 1.1 to 12.9 μg/L), those of free MeSH to 1.6 μg/L (from 0.7 to 3.5 μg/L), and those of total MeSH to 1.9 μg/L (from 1.1 to 3.0 μg/L), whereas those of DMS were 27.8 μg/L (from 11 to 69 μg/L). The fraction of H2S under free forms significantly increased, suggesting that release is a major factor explaining H2S increases. All increases can be satisfactorily predicted from data obtained at 50 °C.

  10. A dynamic model of oceanic sulfur (DMOS) applied to the Sargasso Sea: Simulating the dimethylsulfide (DMS) summer paradox

    NASA Astrophysics Data System (ADS)

    Vallina, S. M.; Simó, R.; Anderson, T. R.; Gabric, A.; Cropp, R.; Pacheco, J. M.

    2008-03-01

    A new one-dimensional model of DMSP/DMS dynamics (DMOS) is developed and applied to the Sargasso Sea in order to explain what drives the observed dimethylsulfide (DMS) summer paradox: a summer DMS concentration maximum concurrent with a minimum in the biomass of phytoplankton, the producers of the DMS precursor dimethylsulfoniopropionate (DMSP). Several mechanisms have been postulated to explain this mismatch: a succession in phytoplankton species composition towards higher relative abundances of DMSP producers in summer; inhibition of bacterial DMS consumption by ultraviolet radiation (UVR); and direct DMS production by phytoplankton due to UVR-induced oxidative stress. None of these hypothetical mechanisms, except for the first one, has been tested with a dynamic model. We have coupled a new sulfur cycle model that incorporates the latest knowledge on DMSP/DMS dynamics to a preexisting nitrogen/carbon-based ecological model that explicitly simulates the microbial-loop. This allows the role of bacteria in DMS production and consumption to be represented and quantified. The main improvements of DMOS with respect to previous DMSP/DMS models are the explicit inclusion of: solar-radiation inhibition of bacterial sulfur uptakes; DMS exudation by phytoplankton caused by solar-radiation-induced stress; and uptake of dissolved DMSP by phytoplankton. We have conducted a series of modeling experiments where some of the DMOS sulfur paths are turned "off" or "on," and the results on chlorophyll-a, bacteria, DMS, and DMSP (particulate and dissolved) concentrations have been compared with climatological data of these same variables. The simulated rate of sulfur cycling processes are also compared with the scarce data available from previous works. All processes seem to play a role in driving DMS seasonality. Among them, however, solar-radiation-induced DMS exudation by phytoplankton stands out as the process without which the model is unable to produce realistic DMS simulations

  11. The dimethylsulfide cycle in the eutrophied Southern North Sea: a model study integrating phytoplankton and bacterial processes

    NASA Astrophysics Data System (ADS)

    Gypens, Nathalie; Borges, Alberto V.; Speeckaert, Gaelle; Lancelot, Christiane

    2014-05-01

    We developed a module describing the dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) dynamics, including biological transformations by phytoplankton and bacteria, and physico-chemical processes (including DMS air-sea exchange). This module was integrated in the MIRO ecological model and applied in a 0D frame in the Southern North Sea (SNS). The DMS(P) module is built on parameterizations derived from available knowledge on DMS(P) sources, transformations and sinks, and provides an explicit representation of bacterial activity in contrast to most of existing models that only include phytoplankton process (and abiotic transformations). The model is tested in a highly productive coastal ecosystem (the Belgian coastal zone, BCZ) dominated by diatoms and the Haptophyceae Phaeocystis, respectively low and high DMSP producers. On an annual basis, the particulate DMSP (DMSPp) production simulated in 1989 is mainly related to Phaeocystis colonies (78%) rather than diatoms (13%) and nanoflagellates (9%). Accordingly, sensitivity analysis shows that the model responds more to changes in the sulfur:carbon (S:C) quota and lyase yield of Phaeocystis. DMS originates equally from phytoplankton and bacterial DMSP-lyase activity and only 3% of the DMS is emitted to the atmosphere. Model analysis demonstrates the sensitivity of DMS emission towards the atmosphere to the description and parameterization of biological processes emphasizing the need of adequately representing in models both phytoplankton and bacterial processes affecting DMS(P) dynamics. This is particularly important in eutrophied coastal environments such as the SNS dominated by high non-diatom blooms and where empirical models developed from data-sets biased towards open ocean conditions do not satisfactorily predict the timing and amplitude of the DMS seasonal cycle. In order to predict future feedbacks of DMS emissions on climate, it is needed to account for hotspots of DMS emissions from coastal

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

    NASA Astrophysics Data System (ADS)

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

    1995-06-01

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

  13. Biogenic emission of dimethylsulfide (DMS) from the North Yellow Sea, China and its contribution to sulfate in aerosol during summer

    NASA Astrophysics Data System (ADS)

    Yang, Gui-Peng; Zhang, Hong-Hai; Su, Lu-Ping; Zhou, Li-Min

    Seawater, atmospheric dimethylsulfide (DMS) and aerosol compounds, potentially linked with DMS oxidation, such as methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO 42-) were determined in the North Yellow Sea, China during July-August, 2006. The concentrations of seawater and atmospheric DMS ranged from 2.01 to 11.79 nmol l -1 and from 1.68 to 8.26 nmol m -3, with average values of 6.20 nmol l -1 and 5.01 nmol m -3, respectively. Owing to the appreciable concentration gradient, DMS accumulated in the surface water was transferred into the atmosphere, leading to a net sea-to-air flux of 6.87 μmol m -2 d -1 during summer. In the surface seawater, high DMS values corresponded well with the concurrent increases in chlorophyll a levels and a significant correlation was observed between integrated DMS and chlorophyll a concentrations. In addition, the concentrations of MSA and nss-SO 42- measured in the aerosol samples ranged from 0.012 to 0.079 μg m -3 and from 3.82 to 11.72 μg m -3, with average values of 0.039 and 7.40 μg m -3, respectively. Based on the observed MSA, nss-SO 42- and their ratio, the relative biogenic sulfur contribution was estimated to range from 1.2% to 11.5%, implying the major contribution of anthropogenic source to sulfur budget in the study area.

  14. Assessing the potential for dimethylsulfide enrichment at the sea surface and its influence on air-sea flux

    NASA Astrophysics Data System (ADS)

    Walker, Carolyn F.; Harvey, Mike J.; Smith, Murray J.; Bell, Thomas G.; Saltzman, Eric S.; Marriner, Andrew S.; McGregor, John A.; Law, Cliff S.

    2016-09-01

    The flux of dimethylsulfide (DMS) to the atmosphere is generally inferred using water sampled at or below 2 m depth, thereby excluding any concentration anomalies at the air-sea interface. Two independent techniques were used to assess the potential for near-surface DMS enrichment to influence DMS emissions and also identify the factors influencing enrichment. DMS measurements in productive frontal waters over the Chatham Rise, east of New Zealand, did not identify any significant gradients between 0.01 and 6 m in sub-surface seawater, whereas DMS enrichment in the sea-surface microlayer was variable, with a mean enrichment factor (EF; the concentration ratio between DMS in the sea-surface microlayer and in sub-surface water) of 1.7. Physical and biological factors influenced sea-surface microlayer DMS concentration, with high enrichment (EF > 1.3) only recorded in a dinoflagellate-dominated bloom, and associated with low to medium wind speeds and near-surface temperature gradients. On occasion, high DMS enrichment preceded periods when the air-sea DMS flux, measured by eddy covariance, exceeded the flux calculated using National Oceanic and Atmospheric Administration (NOAA) Coupled-Ocean Atmospheric Response Experiment (COARE) parameterized gas transfer velocities and measured sub-surface seawater DMS concentrations. The results of these two independent approaches suggest that air-sea emissions may be influenced by near-surface DMS production under certain conditions, and highlight the need for further study to constrain the magnitude and mechanisms of DMS production in the sea-surface microlayer.

  15. Dimethylsulfide/cloud condensation nuclei/climate system - Relevant size-resolved measurements of the chemical and physical properties of atmospheric aerosol particles

    NASA Technical Reports Server (NTRS)

    Quinn, P. K.; Covert, D. S.; Bates, T. S.; Kapustin, V. N.; Ramsey-Bell, D. C.; Mcinnes, L. M.

    1993-01-01

    The mass and number relationships occurring within the atmospheric dimethylsulfide/cloud condensation nuclei (CCN)/climate system, using simultaneous measurements of particulate phase mass size distributions of nss SO4(2-), methanesulfonic acid (MSA), and NH4(+); number size distributions of particles having diameters between 0.02 and 9.6 microns; CCN concentrations at a supersaturation of 0.3 percent; relative humidity; and temperature, obtained for the northeastern Pacific Ocean in April and May 1991. Based on these measurements, particulate nss SO4(2-), MSA, and NH4(+) mass appeared to be correlated with both particle effective surface area and number in the accumulation mode size range (0.16 to 0.5 micron). No correlations were found in the size range below 0.16 micron. A correlation was also found between nss SO4(2-) mass and the CCN number concentration, such that a doubling of the SO4(2-) mass corresponded to a 40 percent increase in the CCN number concentration. However, no correlation was found between MSA mass and CCN concentration.

  16. The influence of the nitrate radical on the dimethylsulfide oxidation derived from field measurements during NEAQS (New England Air Quality Study)

    NASA Astrophysics Data System (ADS)

    Stark, H.; Goldan, P. D.; Brown, S. S.; Aldener, M.; Kuster, W. C.; Williams, E. J.; Lerner, B. M.; Degouw, J. A.; Warneke, C.; Fehsenfeld, F. C.; Ravishankara, A. R.

    2003-12-01

    We present simultaneous measurements of nitrate radical (NO3) and dimethylsulfide (DMS) from NEAQS (New England Air Quality Study). DMS is emitted from the ocean surface as a result of phytoplankton activity, whereas NO3 is produced by reaction of ozone (O3) and nitrogen dioxide (NO2) in polluted air. Photolysis by visible light and rapid reaction with NO during daytime prevent NO3 from building to significant concentration, except at night. The rapid reaction between NO3 and DMS constitutes an important sink for the latter in the polluted marine boundary layer. We will show nocturnal profiles of both compounds as well as the anticorrelations between them. These data indicate that nighttime DMS oxidation by NO3 under polluted conditions with high NO3 concentrations in the north-east coastal region of the US and daytime oxidation by OH are comparable. We will discuss the influence of transport and mixing of fresh emissions into marine air on the observed anticorrelations based on trajectory calculations and tracer measurements to distinguish between transport effects and reactions.

  17. Differential response of planktonic primary, bacterial, and dimethylsulfide production rates to vertically-moving and static incubations in upper mixed-layer summer sea waters

    NASA Astrophysics Data System (ADS)

    Galí, M.; Simó, R.; Pérez, G. L.; Ruiz-González, C.; Sarmento, H.; Royer, S.-J.; Fuentes-Lema, A.; Gasol, J. M.

    2013-05-01

    Microbial plankton experience fluctuations in total solar irradiance and in its spectral composition as they are vertically moved by turbulence in the oceanic upper mixed layer (UML). The fact that the light exposure is not static but dynamic may have important consequences for biogeochemical processes and ocean-atmosphere fluxes. However, most biogeochemical processes other than primary production, like bacterial production or dimethylsulfide (DMS) production, are seldom measured in sunlight and even less often in dynamic light fields. We conducted four experiments in oligotrophic summer stratified Mediterranean waters, where a sample from the UML was incubated in ultraviolet (UV)-transparent bottles at three fixed depths within the UML and on a vertically-moving basket across the same depth range. We assessed the response of the phyto- and bacterioplankton community with physiological indicators based on flow cytometry singe-cell measurements, Fast Repetition Rate fluorometry (FRRf), phytoplankton pigment concentrations and particulate light absorption. Dynamic light exposure caused a disruption of the photoinhibition and photoacclimation processes associated to ultraviolet radiation (UVR), which slightly alleviated bacterial photoinhibition but did not favor primary production. Gross DMS production (GPDMS) decreased sharply with depth in parallel to shortwave UVR, and displayed a dose-dependent response that mixing did not significantly disrupt. To our knowledge, we provide the first measurements of GPDMS under in situ UV-inclusive optical conditions.

  18. Differential response of planktonic primary, bacterial, and dimethylsulfide production rates to static vs. dynamic light exposure in upper mixed-layer summer sea waters

    NASA Astrophysics Data System (ADS)

    Galí, M.; Simó, R.; Pérez, G. L.; Ruiz-González, C.; Sarmento, H.; Royer, S.-J.; Fuentes-Lema, A.; Gasol, J. M.

    2013-12-01

    Microbial plankton experience short-term fluctuations in total solar irradiance and in its spectral composition as they are vertically moved by turbulence in the oceanic upper mixed layer (UML). The fact that the light exposure is not static but dynamic may have important consequences for biogeochemical processes and ocean-atmosphere fluxes. However, most biogeochemical processes other than primary production, like bacterial production or dimethylsulfide (DMS) production, are seldom measured in sunlight and even less often in dynamic light fields. We conducted four experiments in oligotrophic summer stratified Mediterranean waters, where a sample from the UML was incubated in ultraviolet (UV)-transparent bottles at three fixed depths within the UML and on a vertically moving basket across the same depth range. We assessed the response of the phyto- and bacterioplankton community with physiological indicators based on flow cytometry singe-cell measurements, fast repetition rate fluorometry (FRRf), phytoplankton pigment concentrations and particulate light absorption. Dynamic light exposure caused a subtle disruption of the photoinhibition and photoacclimation processes associated with ultraviolet radiation (UVR), which slightly alleviated bacterial photoinhibition but did not favor primary production. Gross DMS production (GPDMS) decreased sharply with depth in parallel to shortwave UVR, and displayed a dose-dependent response that mixing did not significantly disrupt. To our knowledge, we provide the first measurements of GPDMS under in situ UV-inclusive optical conditions.

  19. On the biogenic origin of dimethylsulfide: Relation between chlorophyll, ATP, organismic DMSP, phytoplankton species, and DMS distribution in Atlantic surface water and atmosphere

    SciTech Connect

    Buergermeister, S.; Zimmermann, R.L.; Georgii, H.W. ); Bingemer, H.G. ); Kirst, G.O.; Janssen, M. ); Ernst, W. )

    1990-11-20

    During a cruise over the Atlantic from 40{degree}S to 50{degree}N in March-April 1987 the concentrations of dimethylsulfide (DMS) in the ocean and atmosphere were measured as well as the distribution of its precursor, dimethylsulfoniopropionate (DMSP), and of several biological parameters such as chlorophyllm, phytoplankton species, and adenosine-5-triphosphate (ATP) in the surface water. The DMS concentration varied in the range 0.2-2 nmol DMS{sup {minus}1} (surface water) and 0.05-3 nmol DMS m{sup {minus}3} (atmosphere) in the region of the remote tropical and subtropical Atlantic and increased to 2-10 nmol DMS{sup {minus}1} (surface water) and 1-8 nmol DMS m{sup {minus}3} (atmosphere) north of 40{degree}N and in the English Channel. Based on these results the mean flux of DMS from the Atlantic to the atmosphere is estimated to be 4-4.65 nmol DMS m{sup {minus}2} min{sup {minus}1}. A moderate diurnal variation of atmospheric DMS was found with a minimum during daytime. The DMS concentration in seawater correlated well with the concentration of DMSP and showed a similar trend to ATP, chlorophyll, and some phytoplankton species.

  20. Air-sea exchange of dimethylsulfide in the Southern Ocean: Measurements from SO GasEx compared to temperate and tropical regions

    NASA Astrophysics Data System (ADS)

    Yang, M.; Blomquist, B. W.; Fairall, C. W.; Archer, S. D.; Huebert, B. J.

    2011-04-01

    In the Southern Ocean Gas Exchange Experiment (SO GasEx), we measured an atmospheric dimethylsulfide (DMS) concentration of 118 ± 54 pptv (1σ), a DMS sea-to-air flux of 2.9 ± 2.1 μmol m-2 d-1 by eddy covariance, and a seawater DMS concentration of 1.6 ± 0.7 nM. Dividing flux by the concurrent air-sea concentration difference yields the transfer velocity of DMS (kDMS). The kDMS in the Southern Ocean was significantly lower than previous measurements in the equatorial east Pacific, Sargasso Sea, northeast Atlantic, and southeast Pacific. Normalizing kDMS for the temperature dependence in waterside diffusivity and solubility results in better agreement among various field studies and suggests that the low kDMS in the Southern Ocean is primarily due to colder temperatures. The higher solubility of DMS at a lower temperature results in greater airside control and less transfer of the gas by bubbles formed from breaking waves. The final normalized DMS transfer velocity is similar to k of less soluble gases such as carbon dioxide in low-to-moderate winds; in high winds, DMS transfer velocity is significantly lower because of the reduced bubble-mediated transfer.

  1. Spatial variations of dimethylsulfide and dimethylsulfoniopropionate in the surface microlayer and in the subsurface waters of the South China Sea during springtime.

    PubMed

    Yang, Gui-Peng; Jing, Wei-Wen; Kang, Zhi-Qiang; Zhang, Hong-Hai; Song, Gui-Sheng

    2008-02-01

    Spatial variations in dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) were surveyed in the surface microlayer and in the subsurface waters of the low productivity South China Sea in May 2005. Overall, average subsurface water concentrations of DMS and DMSP of dissolved (DMSPd) and particulate (DMSPp) fractions were 1.74 (1.00-2.50), 3.92 (2.21-6.54) and 6.06 (3.40-8.68) nM, respectively. No enrichment in DMS and DMSPp was observed in the microlayer. In contrast, the microlayer showed a DMSPd enrichment, with an average enrichment factor (EF, defined as the ratio of the microlayer concentration to subsurface water concentration) of 1.40. In the study area, none of the sulfur components were correlated with chlorophyll a. An important finding in this study was that DMS, DMSP and chlorophyll a concentrations in the surface microlayer were respectively correlated with those in the subsurface water, suggesting a close linkage between these two water bodies. The ratios of DMS:Chl-a and DMSPp:Chl-a showed a gradually increasing trend from North to South. This might be due to changes in the proportion of DMSP producers in the phytoplankton community with the increased surface seawater temperature. A clear diurnal variation in the DMS and DMSP concentrations was observed at an anchor station with the highest concentrations appearing during the day and the lowest concentrations during the night. The higher DMS and DMSP concentrations during daytime might be attributed to the light-induced increase in both algal synthesis and exudation of DMSP and biological production of DMS. The mean flux of DMS from the investigated area to the atmosphere was estimated to be 2.06 micromo lm(-2)d(-1). This low DMS emission flux, together with the low DMS surface concentrations was attributed to the low productivity in this sea.

  2. Biogenic sulfur emissions and aerosols over the tropical South Atlantic: 1. Dimethylsulfide in sea water and in the atmospheric boundary layer

    NASA Astrophysics Data System (ADS)

    Andreae, Tracey W.; Andreae, Meinrat O.; Schebeske, Günther

    1994-11-01

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

  3. Stimulation of gross dimethylsulfide (DMS) production by solar radiation

    NASA Astrophysics Data System (ADS)

    Galí, Martí; Saló, Violeta; Almeda, Rodrigo; Calbet, Albert; Simó, Rafel

    2011-08-01

    Oceanic gross DMS production (GP) exerts a fundamental control on the concentration and the sea-air flux of this climatically-active trace gas. However, it is a poorly constrained process, owing to the complexity of the microbial food web processes involved and their interplay with physical forcing, particularly with solar radiation. The “inhibitor method”, using dimethyldisulfide (DMDS) or other compounds to inhibit bacterial DMS consumption, has been frequently used to determine GP in dark incubations. In the work presented here, DMDS addition was optimized for its use in light incubations. By comparing simultaneous dark and light measurements of GP in meso- to ultraoligotrophic waters, we found a significant enhancement of GP in natural sunlight in 7 out of 10 experiments. Such stimulation, which was generally between 30 and 80% on a daily basis, occurred throughout contrasting microbial communities and oceanographic settings.

  4. Marine Microbial Production of Dimethylsulfide From Dissolved Dimethylsulfoniopropionate

    DTIC Science & Technology

    1993-02-01

    time of DMSP was less than half a day (6-10 hours). The exception occurred on 4/23, when rates of all processes appeared depressed . tDMS, both with...questions raised by the field data in preceding chapters about the mechanism and rates of dissolved DMSP metabolism in marine microbiota , this chapter

  5. Hydroxide decomposition of dimethylsulfoniopropionate to form dimethylsulfide. [in sea water

    NASA Technical Reports Server (NTRS)

    Dacey, John W. H.; Blough, Neil V.

    1987-01-01

    The kinetics of DMS production resulting from reaction of OH(-) with DMSP were investigated as a function of hydroxide concentration and temperature. The reaction was first-order with respect to DMSP and OH(-). The second order rate constant at 20+/-1 C is 0.0044/M/sec. The activation energy for this reaction is 14.4 kcal/mode. The investigation indicates that the rate of reaction of DMSP with OH(-) is very slow at the pH of seawater, suggesting that DMSP, which may be a major precursor of DMS in seawater, decomposes in the ocean by other mechanisms. A bacterium which produces DMS from DMSP quantitatively at rates many orders of magnitude higher than indicated by OH(-1) decomposition has been cultured, suggesting that enzymatic processes accelerate the production of DMS from DMSP in seawater.

  6. Correlation between satellite-derived aerosol characteristics and oceanic dimethylsulfide (DMS). Master's thesis

    SciTech Connect

    Shema, R.A.

    1988-12-01

    Since the turn of the century, the earth's climate has fluctuated between warming and cooling cycles. A warming cycle has been observed in the early 1900's. The rising global temperature has been attributed to CO/sub 2/ release from the burning of fossil fuels. The absorption of IR energy emitted from the earth, or greenhouse effect , brought concern that continued warming would melt polar ice caps and permanently change global climate. However, beginning in the mid-1940's, atmospheric cooling was observed. A possible contribution to the cooling trend is an increase in the numbers of relatively small aerosol particles. These particles are efficient scatters of solar radiation. An increase in the number of scattering events causes a higher albedo, thereby creating a cooler planet. McCormick and Ludwig (1967) have presented arguments to show this relationship. Approximately forty years later, in the early 1980's, warming of the earth's climate again has been observed.

  7. Influence of wind speed averaging on estimates of dimethylsulfide emission fluxes

    DOE PAGES

    Chapman, E. G.; Shaw, W. J.; Easter, R. C.; ...

    2002-12-03

    The effect of various wind-speed-averaging periods on calculated DMS emission fluxes is quantitatively assessed. Here, a global climate model and an emission flux module were run in stand-alone mode for a full year. Twenty-minute instantaneous surface wind speeds and related variables generated by the climate model were archived, and corresponding 1-hour-, 6-hour-, daily-, and monthly-averaged quantities calculated. These various time-averaged, model-derived quantities were used as inputs in the emission flux module, and DMS emissions were calculated using two expressions for the mass transfer velocity commonly used in atmospheric models. Results indicate that the time period selected for averaging wind speedsmore » can affect the magnitude of calculated DMS emission fluxes. A number of individual marine cells within the global grid show DMS emissions fluxes that are 10-60% higher when emissions are calculated using 20-minute instantaneous model time step winds rather than monthly-averaged wind speeds, and at some locations the differences exceed 200%. Many of these cells are located in the southern hemisphere where anthropogenic sulfur emissions are low and changes in oceanic DMS emissions may significantly affect calculated aerosol concentrations and aerosol radiative forcing.« less

  8. Dimethylsulfide oxidation over the tropical South Atlantic: OH and other oxidants

    NASA Technical Reports Server (NTRS)

    Hemming, Brooke L.; Vastano, John A.; Chatfield, Robert B.; Andreae, Meinrat O.; Hildemann, Lynn M.

    1994-01-01

    The general course of events in the formation of a marine cloud begins with the emission of species which can eventually serve as nuclei around which water can condense to form a cloud droplet. In remote marine regions, cloud condensation nuclei (CCN) are primarily composed of sulfate, in either its acid or ammonium salt form. Most sulfate in these regions is the product of atmospheric oxidation of dimethyl sulfide (DMS), a reduced sulfur gas that is released by phytoplankton at the ocean surface. Therefore, in order to effectively quantify the links in the cloud-formation cycle, one must begin with a well-defined description of the atmospheric chemistry of DMS. The intent of this project has been to initiate development of a comprehensive model of the chemistry and dynamics responsible for the formation of clouds in the remote marine boundary layer. The primary tool in this work has been the Global/Regional Atmospheric Chemistry Event Simulator (GRACES), a global atmospheric chemistry model, which is under development within the Atmospheric Chemistry and Dynamics Branch of NASA-Ames Research Center. In this effort, GRACES was used to explore the first chemical link between DMS and sulfate by modeling the diurnal variation of DMS.

  9. Influence of wind speed averaging on estimates of dimethylsulfide emission fluxes

    SciTech Connect

    Chapman, E. G.; Shaw, W. J.; Easter, R. C.; Bian, X.; Ghan, S. J.

    2002-12-03

    The effect of various wind-speed-averaging periods on calculated DMS emission fluxes is quantitatively assessed. Here, a global climate model and an emission flux module were run in stand-alone mode for a full year. Twenty-minute instantaneous surface wind speeds and related variables generated by the climate model were archived, and corresponding 1-hour-, 6-hour-, daily-, and monthly-averaged quantities calculated. These various time-averaged, model-derived quantities were used as inputs in the emission flux module, and DMS emissions were calculated using two expressions for the mass transfer velocity commonly used in atmospheric models. Results indicate that the time period selected for averaging wind speeds can affect the magnitude of calculated DMS emission fluxes. A number of individual marine cells within the global grid show DMS emissions fluxes that are 10-60% higher when emissions are calculated using 20-minute instantaneous model time step winds rather than monthly-averaged wind speeds, and at some locations the differences exceed 200%. Many of these cells are located in the southern hemisphere where anthropogenic sulfur emissions are low and changes in oceanic DMS emissions may significantly affect calculated aerosol concentrations and aerosol radiative forcing.

  10. Kinetics, Mechanism and Product Yields in the Atmospheric Oxidation of Dimethylsulfide

    DTIC Science & Technology

    2016-06-14

    Rosenstiel School of Marine and Atmospheric Science University of Miami 4600 Rickenbacker Causeway Miami, Florida 33149-1098 ahynes...decomposition and reaction, b) direct confirmation of production, and quantitative product yields of potential reaction products and intermediates...School of Marine and Atmospheric Science ,4600 Rickenbacker Causeway,Miami,FL,33149 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING

  11. FIRE_AX_UW_DSCRT

    Atmospheric Science Data Center

    2015-11-25

    ... Condensation Nuclei Dimethylsulfide Droplet Concentration Effective Droplet Diameter Effective Droplet Radius ... Content Ozone Particle Diameter Particle Number Concentration Potential Temperature Sulfate Sulfur Dioxide ...

  12. Interaction of Product Analogues With the Active Site of Rhodobacter Sphaeroides Dimethyl Sulfoxide Reductase

    SciTech Connect

    George, G.N.; Nelson, K.J.; Harris, H.H.; Doonan, C.J.; Rajagopalan, K.V.; /Saskatchewan U. /Duke U. /Sydney U.

    2007-07-09

    We report a structural characterization using X-ray absorption spectroscopy of Rhodobacter sphaeroides dimethylsulfoxide (DMSO) reductase reduced with trimethylarsine, and show that this is structurally analogous to the physiologically relevant dimethylsulfide-reduced DMSO reductase. Our data unambiguously indicate that these species should be regarded as formal MoIV species, and indicate a classical coordination complex of trimethylarsine oxide, with no special structural distortions. The similarity of the trimethylarsine and dimethylsulfide complexes suggests in turn that the dimethylsulfide reduced enzyme possesses a classical coordination of DMSO with no special elongation of the S-O bond, as previously suggested.

  13. Evaluation of gas emissions from coal stockpile.

    PubMed

    Kozinc, J; Zupancic-Kralj, L; Zapusek, A

    2004-05-01

    Gas emissions of carbon dioxide, methane, dimethylsulfide, carbon monoxide and oxygen from a coal stockpile in Velenje were determined. Gases from the coal stockpile were collected in Alltech Standard sampling bags and then analysed using a capillary gas chromatograph and electrochemical sensors. A flame ionisation detector equipped with a Zr/Ni catalytic reactor was used for the determination of methane and carbon dioxide. Dimethylsulfide was detected with a flame photometric detector, and the concentrations of carbon monoxide and oxygen were determined by use of electrochemical sensors. The results showed that the main influence on gas emissions is related to the ambient temperature. Emissions of carbon dioxide during summer 2001 (average temperature during sampling period was 24 degrees C) were approximately 30-times higher than during winter 2002 (average temperature during sampling period was -2 degrees C) and were also influenced by the oxygen concentration. Carbon dioxide is mainly formed by oxidation of coal. Methane and dimethylsulfide are desorbed from coal, and are present in higher concentrations in stockpile emissions when stockpiles are renewed. The dimethylsulfide concentration, in contrast to laboratory experiments in stockpile emissions, falls immediately due to photo-degradation.

  14. In vitro evaluation of carbohydrate-cysteamine thiazolidines as pro-drugs for the treatment of cystinosis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cystinosis is a genetic disorder caused by the malfunction of cystinosin characterized by accumulation of cystine. Cysteamine, the medication used in cystinosis, causes halitosis resulting in poor patient compliance. Halitosis is mainly caused by the formation of dimethylsulfide as the final product...

  15. Technical note: Examining ozone deposition over seawater

    EPA Science Inventory

    Surface layer resistance plays an important role in determining ozone deposition velocity over sea-water and can be influenced by chemical interactions at the air-water interface. Here, we examine the effect of chemical interactions of iodide, dimethylsulfide, dissolved organic c...

  16. Direct observations of Biogenic Volatile Organic Compound (BVOC) Air-Sea Exchange in the remote North Atlantic from the High-Wind Gas-Exchange Study (HiWinGS)

    NASA Astrophysics Data System (ADS)

    Kim, M.; Yang, M. X.; Blomquist, B.; Huebert, B. J.; Bertram, T. H.

    2014-12-01

    Biogenic Volatile Organic Compounds (BVOCs) are reactive trace gases that impact both chemistry and climate by regulating oxidant loadings, determining secondary organic aerosol production rates as well as altering particle hygroscopicity. While continental BVOC exchange rates are well studied, global marine flux estimates are poorly constrained. In Fall 2013, a chemical-ionization time-of-flight mass spectrometer (CI-ToF-MS) utilizing benzene cations was deployed as part of the High Wind Gas Exchange Study (HiWinGs) to quantify monoterpenes, isoprene and dimethylsulfide fluxes in the remote North Atlantic. Dimethylsulfide measurements are in strong agreement with those determined by the University of Hawaii's atmospheric pressure ionization mass-spectrometer. In the remote marine boundary layer, positive monoterpene fluxes (i.e. emissions) were observed while isoprene levels rarely exceeded the detection limit.

  17. Kirkwood-Buff integrals for ideal solutions

    NASA Astrophysics Data System (ADS)

    Ploetz, Elizabeth A.; Bentenitis, Nikolaos; Smith, Paul E.

    2010-04-01

    The Kirkwood-Buff (KB) theory of solutions is a rigorous theory of solution mixtures which relates the molecular distributions between the solution components to the thermodynamic properties of the mixture. Ideal solutions represent a useful reference for understanding the properties of real solutions. Here, we derive expressions for the KB integrals, the central components of KB theory, in ideal solutions of any number of components corresponding to the three main concentration scales. The results are illustrated by use of molecular dynamics simulations for two binary solutions mixtures, benzene with toluene, and methanethiol with dimethylsulfide, which closely approach ideal behavior, and a binary mixture of benzene and methanol which is nonideal. Simulations of a quaternary mixture containing benzene, toluene, methanethiol, and dimethylsulfide suggest this system displays ideal behavior and that ideal behavior is not limited to mixtures containing a small number of components.

  18. Factors controlling emissions of dimethylsulphide from salt marshes

    NASA Technical Reports Server (NTRS)

    Dacey, John W. H.; Wakeham, Stuart G.; King, Gary M.

    1987-01-01

    Salt marshes are presently identified as systems exhibiting high area-specific sulfur emission in the form of dimethylsulfide (DMS) and H2S, with the former predominating in vegetated areas of the marshes. Attention is presently given to the distribution of DMS in salt marshes; it is found that this compound primarily arises from physiological processes in the leaves of higher plants, especially the grass species Spartina alterniflora. Uncertainties associated with DMS emission measurements are considered.

  19. Selenium detoxification by volatilization and precipitation in aquatic plants

    SciTech Connect

    Fan, T.W.M.; Higashi, R.M.

    1995-12-31

    The narrow margin of requirement and toxicity for selenium makes it a difficult pollution problem to solve. Selenium bioaccumulation has been a major threat to wildlife in California and is becoming a major concern in the San Francisco Bay/Estuaries. Despite the past efforts in Se nutrition, chemistry, and remediation, its toxicity and detoxification mechanism(s) in wildlife, particularly primary producers, is still unclear, due to a lack of understanding in Se biochemistry. This is becoming a critical issue in assessing Se risk and remediation. To address this gap, the authors have been characterizing Se speciation and its linkage to detoxification mechanism(s) of two indigenous aquatic plants, duckweed (Lemna minor) and a microphyte (Chlorella). Using GT-MS analysis, they found that Chlorella monocultures transformed Se oxyanions into volatile dimethylselenide and dimethyidiselenide and into insoluble So at extremely high Se (up to 750 ppm) concentrations. This alga did not accumulate selenomethionine which is among the most toxic forms of Se to wildlife. Dimethylsulfide was also volatilized, consistent with the hypothesis that dimethylsulfide/dimethylselenide emissions share a similar biochemical pathway. Se-treated Chlorella biomass released dimethylsulfide/dimethylselenide upon alkaline hydrolysis, suggesting the presence of dimethylsulfonium and dimethylselenonium propionates. Dimethylsulfoniumpropionate is known as an osmoprotectant in marine phytoplankton and as a major contributor to global biogenic dimethylsulfide emissions. Dimethylselenoniumpropionate has not been identified previously and may be a byproduct of dimethylsulfoniumpropionate synthesis. The unusual Se tolerance of Chlorella may be due to its ability to volatilize and precipitate Se. Such activities may be utilized for in situ Se bioremediation. Similar investigations with duckweed is underway.

  20. Low level measurements of atmospheric DMS, H2S, and SO2 for GTE/CITE-3

    NASA Technical Reports Server (NTRS)

    Saltzman, Eric; Cooper, David

    1991-01-01

    This project involved the measurement of atmospheric dimethylsulfide (DMS) and hydrogen sulfide (H2S) as part of the GTE/CITE-3 instrument intercomparison program. The two instruments were adapted for use on the NASA Electra aircraft and participated in all phases of the mission. This included ground-based measurements of NIST-provided standard gases and a series of airborne missions over the Western Atlantic Ocean. Analytical techniques used are described and the results are summarized.

  1. Volatile organic sulfur compounds in anaerobic sludge and sediments: biodegradation and toxicity.

    PubMed

    van Leerdam, Robin C; de Bok, Frank A M; Lomans, Bart P; Stams, Alfons J M; Lens, Piet N L; Janssen, Albert J H

    2006-12-01

    A variety of environmental samples was screened for anaerobic degradation of methanethiol, ethanethiol, propanethiol, dimethylsulfide, and dimethyldisulfide. All sludge and sediment samples degraded methanethiol, dimethylsulfide, and dimethyldisulfide anaerobically. In contrast, ethanethiol and propanethiol were not degraded by the samples investigated under any of the conditions tested. Methanethiol, dimethylsulfide, and dimethyldisulfide were mainly degraded by methanogenic archaea. In the presence of sulfate and the methanogenic inhibitor bromoethane sulfonate, degradation of these compounds coupled to sulfate reduction occurred as well, but at much lower rates. Besides their biodegradability, also the toxicity of methanethiol, ethanethiol, and propanethiol to methanogenesis with methanol, acetate, and H2/CO2 as the substrates was assessed. The 50% inhibition concentration of methanethiol on the methane production from these substrates ranged between 7 and 10 mM. The 50% inhibition concentration values of ethanethiol and propanethiol for the degradation of methanol and acetate were between 6 and 8 mM, whereas hydrogen consumers were less affected by ethanethiol and propanethiol, as indicated by their higher 50% inhibition concentration (14 mM). Sulfide inhibited methanethiol degradation already at relatively low concentrations: methanethiol degradation was almost completely inhibited at an initial sulfide concentration of 8 mM. These results define the operational limits of anaerobic technologies for the treatment of volatile organic sulfur compounds in sulfide-containing wastewater streams.

  2. Technical note: Examining ozone deposition over seawater

    NASA Astrophysics Data System (ADS)

    Sarwar, Golam; Kang, Daiwen; Foley, Kristen; Schwede, Donna; Gantt, Brett; Mathur, Rohit

    2016-09-01

    Surface layer resistance plays an important role in determining ozone deposition velocity over sea-water and can be influenced by chemical interactions at the air-water interface. Here, we examine the effect of chemical interactions of iodide, dimethylsulfide, dissolved organic carbon, and bromide in seawater on ozone deposition. We perform a series of simulations using the hemispheric Community Multiscale Air Quality model for summer months in the Northern Hemisphere. Our results suggest that each chemical interaction enhances the ozone deposition velocity and decreases the atmospheric ozone mixing ratio over seawater. Iodide enhances the median deposition velocity over seawater by 0.023 cm s-1, dissolved organic carbon by 0.021 cm s-1, dimethylsulfide by 0.002 cm s-1, and bromide by ∼0.0006 cm s-1. Consequently, iodide decreases the median atmospheric ozone mixing ratio over seawater by 0.7 ppb, dissolved organic carbon by 0.8 ppb, dimethylsulfide by 0.1 ppb, and bromide by 0.02 ppb. In a separate model simulation, we account for the effect of dissolved salts in seawater on the Henry's law constant for ozone and find that it reduces the median deposition velocity by 0.007 cm s-1 and increases surface ozone mixing ratio by 0.2 ppb. The combined effect of these processes increases the median ozone deposition velocity over seawater by 0.040 cm s-1, lowers the atmospheric ozone mixing ratio by 5%, and slightly improves model performance relative to observations.

  3. Sulfur isotope measurements of submicrometer sulfate aerosol particles over the Pacific Ocean

    NASA Technical Reports Server (NTRS)

    Calhoun, Julie A.; Charlson, Robert J.; Bates, Timothy S.

    1991-01-01

    Stable isotopes were used to analyze the submicron-size sulfate aerosol particles in the atmosphere over the Pacific Ocean, together with the air-mass back trajectories, in order to test the hypothesis of Charlson et al. (1987) who suggested that, over the remote ocean areas, the primary source of atmospheric nonseasalt (NSS) sulfate is marine emissions of dimethylsulfide (DMS). The observed results of isotopic fractionation between the seawater sulfate and NSS sulfate fractions was found to be consistent with the isotopic fractionation predicted for the transformation of the seawater sulfate to the atmospheric NSS sulfate via a DMS path way, supporting the hypothesis of Charlson et al.

  4. Radical cations of sulfides and disulfides: An ESR study

    SciTech Connect

    Bonazzola, L.; Michaut, J.P.; Roncin, J.

    1985-09-15

    Exposure of dilute solutions of dimethylsulfide, methanethiol, tetrahydrothiophene, terbutyl and diterbutyl-sulfides, dimethyl-disulfide, and diterbutyldisulfide, in freon at 77 K to /sup 60/Co ..gamma.. rays gave the corresponding cations. From the reported ESR spectra, g tensors were obtained. It was found that both sulfide and disulfide cations exhibit the same g tensor: (g/sub max/ = 2.034 +- 0.002, g/sub int/ = 2.017 +- 0.001, g/sub min/ = 2.001 +- 0.005). From this result it has been shown that the disulfide cation is planar. This finding was supported by fully optimized geometry ab initio calculations.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  6. Physiology and biochemistry of human subjects during entrapment.

    PubMed

    Agapiou, A; Mikedi, K; Karma, S; Giotaki, Z K; Kolostoumbis, D; Papageorgiou, C; Zorba, E; Spiliopoulou, C; Amann, A; Statheropoulos, M

    2013-03-01

    A classification of various categories of entrapped people under the ruins of collapsed buildings after earthquakes, technical failures or explosions is proposed. Type and degree of injury at the moment of building collapse and duration of entrapment are the two basic parameters in this classification. The aim is to provide sources and types of volatile organic compounds (VOCs) that can be used for establishing a new method for locating entrapped victims based on human chemical signatures. Potential target compounds, among others, are ammonia, acetone, isoprene, dimethylsulfide, dimethyldisulfide and trimethylamine. In this context, the possible neuroendocrine, metabolic and physical responses of potential victims during the different types of entrapment are correlated with the sources of VOCs such as expired air, urine, blood and sweat. The proposed classification scheme was developed as part of an integrated research project which investigates the use of combined audio, video and chemical methods for the early location of entrapped people under the ruins of collapsed buildings.

  7. Methanohalophilus zhilinae sp. nov., an alkaliphilic, halophilic, methylotrophic methanogen

    NASA Technical Reports Server (NTRS)

    Mathrani, I. M.; Boone, D. R.; Mah, R. A.; Fox, G. E.; Lau, P. P.

    1988-01-01

    Methanohalophilus zhilinae, a new alkaliphilic, halophilic, methylotrophic species of methanogenic bacteria, is described. Strain WeN5T (T = type strain) from Bosa Lake of the Wadi el Natrun in Egypt was designated the type strain and was further characterized. This strain was nonmotile, able to catabolize dimethylsulfide, and able to grow in medium with a methyl group-containing substrate (such as methanol or trimethylamine) as the sole organic compound added. Sulfide (21 mM) inhibited cultures growing on trimethylamine. The antibiotic susceptibility pattern of strain WeN5T was typical of the pattern for archaeobacteria, and the guanine-plus-cytosine content of the deoxyribonucleic acid was 38 mol%. Characterization of the 16S ribosomal ribonucleic acid sequence indicated that strain WeN5T is phylogenetically distinct from members of previously described genera other than Methanohalophilus and supported the partition of halophilic methanogens into their own genus.

  8. Air chemistry over the tropical forest of Guyana

    NASA Astrophysics Data System (ADS)

    Gregory, G. L.; Harriss, R. C.; Talbot, R. W.; Browell, E. V.; Beck, S. M.; Sebacher, D. I.; Rasmussen, R. A.; Garstang, M.; Andreae, M. O.; Hinton, R. R.

    1986-07-01

    A comparison is made of the atmospheric chemistry within and above the atmospheric boundary layer over the tropical forest of Guyana. The data were gathered by NASA during the Global Tropospheric Experiment program in 1984, with an instrumented aircraft being used to collect data at altitudes of 3.5 km and between 150-450 m. The synoptic data covered concentrations of O3, CO, dimethylsulfide (DMS), halocarbons and isoprene and three different aerosol particulate measurements (DIAL system). The forest boundary layer proved to be a significant sink for O3, and a source for substantial emissions of DMS. Isoprene emitted by the forest was photochemically oxidized and became a source of CO.

  9. Release and Consumption of DMSP from Emiliania Huxleyi during grazing by Oxyrrhis Marina

    NASA Technical Reports Server (NTRS)

    Wolfe, Gordon V.; Sherr, Evelyn B.; Sherr, Barry F.

    1994-01-01

    Degradation and release to solution of intracellular dimethylsulfoniopropionate (DMSP) from Emiliania huxleyi 370 was observed during grazing by the heterotrophic dinoflagellate Oxyrrhis marina in 24 h bottle incubations. Between 30 and 70% of the lost algal DMSP was metabolized by the grazers without production of dimethylsulfide (DMS) when grazer densities were 150 to 450/ml. The rest was released to solution and about 30% was converted to DMS by bacteria associated with the grazer culture. These experiments demonstrate that grazing by herbivorous protists may be an important sink for DMSP in marine waters, removing a potential source of DMS. Microzooplankton grazing may also indirectly increase the production of DMS by transferring algal DMSP to the dissolved pool, making it available for bacterial metabolism.

  10. The Amazon Boundary Layer Experiment (ABLE 2A) - Dry season 1985

    NASA Technical Reports Server (NTRS)

    Harriss, R. C.; Browell, E. V.; Hoell, J. M., Jr.; Bendura, R. J.; Beck, S. M.; Wofsy, S. C.; Mcneal, R. J.; Navarro, R. L.; Riley, J. T.; Snell, R. L.

    1988-01-01

    The Amazon Boundary Layer Experiment (ABLE 2A) used data from aircraft, ground-based, and satellite platforms to characterize the chemistry and dynamics of the lower atmosphere over the Amazon Basin during the early-to-middle dry season, July and August 1985. This paper reports the conceptual framework and experimental approach used in ABLE 2A and serves as an introduction to the detailed papers which follow in this issue. The results of ABLE 2A demonstrate that isoprene, methane, carbon dioxide, nitric oxide, dimethylsulfide, and organic aerosol emissions from soils and vegetation play a major role in determining the chemical composition of the atmospheric mixed layer over undisturbed forest and wetland environments. As the dry season progresses, emissions from both local and distant biomass burning become an important source of carbon monoxide, nitric oxide and ozone in the atmosphere over the central Amazon Basin.

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

    SciTech Connect

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

    1996-12-31

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

  12. Subtle differences in the hydrogen bonding of alcohol to divalent oxygen and sulfur

    NASA Astrophysics Data System (ADS)

    Du, Lin; Tang, Shanshan; Hansen, Anne S.; Frandsen, Benjamin N.; Maroun, Zeina; Kjaergaard, Henrik G.

    2017-01-01

    The Osbnd H⋯O and Osbnd H⋯S hydrogen bonds were investigated by gas phase FTIR spectroscopy of alcohol-dimethylether and alcohol-dimethylsulfide complexes, with alcohols of increasing hydrogen bond donor strength; methanol (MeOH), ethanol (EtOH) and 2,2,2-trifluoroethanol (TFE). The TFE complexes are more stable and form stronger hydrogen bonds compared to complexes with MeOH and EtOH, which are comparable, and only for the stronger hydrogen bond donor (TFE) are the small differences in acceptor molecules highlighted. The equilibrium constant for complex formation was determined from the experimental and calculated intensity of the OH-stretching transition. The interactions are illustrated by theoretical calculations and topological analysis.

  13. Halitosis in cystinosis patients after administration of immediate-release cysteamine bitartrate compared to delayed-release cysteamine bitartrate.

    PubMed

    Besouw, Martine; Tangerman, Albert; Cornelissen, Elisabeth; Rioux, Patrice; Levtchenko, Elena

    2012-09-01

    Halitosis due to dimethylsulfide (DMS) generation is a major side effect of cysteamine in the treatment of cystinosis. Recently, an enteric coated formulation of cysteamine bitartrate (RP103) administered twice daily was demonstrated to be non-inferior for lowering WBC cystine levels compared to the non-enteric coated formulation (Cystagon®), administered 4 times per day. Since both formulations had different pharmacokinetic profiles, we compared DMS breath levels after administration of either RP103 or Cystagon® in four cystinosis patients. Although cysteamine areas under the curve (AUCs) were comparable, AUC of DMS was lower after the administration of RP103 compared to Cystagon®. This observation is of importance in cystinosis patients, since halitosis hampers compliance with cysteamine therapy.

  14. Microbial transformations in Alkali Lake, Oregon. Final report, 1 Aug 88-31 Jul 91

    SciTech Connect

    Boone, D.R.

    1991-01-01

    An examination was made of the terminal metabolic processes in subsurface sediments near West Alkali Lake, Oregon, by performing microbial counts of methanogenic bacteria and isolating the predominant methanogenic culture. This methanogen was characterized and found to be physiologically and phylogenetically different from other described strains, so it represents a previously undescribed species of bacterium, which was named 'Methanohalophilus oregonensis'. In contrast to published descriptions of many other methanogens which have been isolated from hypersaline environments, this one is halotolerant rather than halophilic. Another important characteristic of this organism is that it is capable of catabolizing dimethylsulfide or methanethiol. This ability is important because these methylated sulfur compounds are major conduits by which sulfur moves between the atmosphere and terrestrial and aquatic ecosystems. Phylogenetic comparisons to known methanogens showed that this strain is closely related to another methanogen, 'Methanolobus siciliae' T4/M which was named but not described.

  15. Dimethylsulfoniopropionate (DMSP) cell quota of key Southern North Sea spring diatoms and Phaeocystis globosa.

    NASA Astrophysics Data System (ADS)

    Speeckaert, Gaëlle; Gypens, Nathalie; Lancelot, Christiane; Borges, Alberto V.

    2015-04-01

    Dimethylsulfide (DMS) in the ocean results of complex transformations of dimethylsulfoniopropionate (DMSP) produced by phytoplankton under different controls, including microbial transformation pathways. The phytoplankton composition is an important factor of variability due to the species dependence of the DMSP production and conversion to DMS. To better appraise the link between phytoplankton diversity and the DMS(P) cycling in the Southern North Sea we present measurements of the DMSP cell quota of key spring phytoplankton species (Skeletonema costatum, Thalassiosira rotula, Rhizosolenia delicatula, Asterionella glacialis, Nitzschia closterium, Chaetoceros debilis, Chaetoceros socialis and Phaeocystis globosa) isolated from the North Sea and maintained in non-limiting and axenic laboratory culture conditions. Results are discussed with regards to literature data and hypothesis currently used in DMS(P) biogeochemical models.

  16. L-methionine degradation potentialities of cheese-ripening microorganisms.

    PubMed

    Bonnarme, P; Lapadatescu, C; Yvon, M; Spinnler, H E

    2001-11-01

    Volatile sulphur compounds are major flavouring compounds in many traditional fermented foods including cheeses. These compounds are products of the catabolism of L-methionine by cheese-ripening microorganisms. The diversity of L-methionine degradation by such microorganisms, however, remains to be characterized. The objective of this work was to compare the capacities to produce volatile sulphur compounds by five yeasts, Geotrichum candidum, Yarrowia lipolytica, Kluyveromyces lactis, Debaryomyces hansenii, Saccharomyces cerevisiae and five bacteria, Brevibacterium linens, Corynebacterium glutamicum, Arthrobacter sp., Micrococcus lutens and Staphylococcus equorum of technological interest for cheese-ripening. The ability of whole cells of these microorganisms to generate volatile sulphur compounds from L-methionine was compared. The microorganisms produced a wide spectrum of sulphur compounds including methanethiol, dimethylsulfide, dimethyldisulfide, dimethyltrisulfide and also S-methylthioesters, which varied in amount and type according to strain. Most of the yeasts produced methanethiol, dimethylsulfide, dimethyldisulfide and dimethyltrisulfide but did not produce S-methylthioesters, apart from G. candidum that produced S-methyl thioacetate. Bacteria, especially Arth. sp. and Brevi. linens, produced the highest amounts and the greatest variety of volatile sulphur compounds includling methanethiol, sulfides and S-methylthioesters, e.g. S-methyl thioacetate, S-methyl thiobutyrate, S-methyl thiopropionate and S-methyl thioisovalerate. Cell-free extracts of all the yeasts and bacteria were examined for the activity of enzymes possibly involved in L-methionine catabolism, i.e. L-methionine demethiolase, L-methionine aminotransferase and L-methionine deaminase. They all possessed L-methionine demethiolase activity, while some (K. lactis, Deb. hansenii, Arth. sp., Staph. equorum) were deficient in L-methionine aminotransferase, and none produced L-methionine deaminase

  17. Energy generation and the sulfur-carbon cycle. Progress report

    SciTech Connect

    Not Available

    1981-01-01

    Laboratory studies demonstrated that a variety of anaerobic bacterial species actively reduced dimethylsulfoxide as an electron acceptor while oxidizing organic substrates as electron donors during growth. The microbial decomposition of methionine in anaerobic Lake Mendota sediments, methanethiol and dimethylsulfide were detected as intermediates; whereas, methane, carbon dioxide, and hydrogen sulfide were the final end products of anaerobic decomposition. Dimethylsulfide and methylmercaptan were immediate methane precursors in Lake Mendota sediments. The oxidation of methane by anaerobic bacteria and characterization of an acetate fermenting methanogenic bacterium were studied. Cultures of methanogenic bacteria demonstrated that methanogens converted /sup 14/CH/sub 4/ to /sup 14/CO/sub 2/ by a pathway that involved different cellular intermediates than those involved in methane production. The general physiological properties of an acetate fermenting methanogen isolated from sewage sludge was characterized. Most notably, this species would not grow on H/sub 2/ + CO/sub 2/. Studies on the influence of sulfate metabolism on carbon turnover in Lake Mendota suggested that approximately 50% of the reduced endogenous carbon was mineralized via sulfate reduction and 50% via methanogenesis. Most of the endogenous carbon mineralized via sulfate reduction occurred in the surface sediments. Sulfate reduction was not limited by in situ sulfate concentration in surface sediments. Studies on biopolymer decomposition showed in situ turnover rate constants for /sup 14/C-pectin of 0.11 h/sup -1/ in Lake Mendota sediments and 0.004 h/sup -1/ in Knaack Lake. The number of anaerobic pectin degrading bacteria in the sediments of both lakes varied with seasons. (ERB)

  18. Gaseous (DMS, MSA, SO2, H2SO4 and DMSO) and particulate (sulfate and methanesulfonate) sulfur species over the northeastern coast of Crete

    NASA Astrophysics Data System (ADS)

    Bardouki, H.; Berresheim, H.; Vrekoussis, M.; Sciare, J.; Kouvarakis, G.; Oikonomou, K.; Schneider, J.; Mihalopoulos, N.

    2003-07-01

    A detailed study of the levels, the temporal and diurnal variability of the main compounds involved in the biogenic sulfur cycle was carried out in Crete (Eastern Mediterranean) during the Mediterranean Intensive Oxidant Study (MINOS) field experiment in July-August 2001. Intensive measurements of gaseous dimethylsulfide (DMS), dimethylsulfoxide (DMSO), sulfur dioxide (SO2), sulfuric (H2SO4) and methanesulfonic acids (MSA) and particulate sulfate (SO42-) and methanesulfonate (MS-) have been performed during the campaign. Dimethylsulfide (DMS) levels ranged from 2.9 to 136 pmol · mol-1 (mean value of 21.7 pmol · mol-1) and showed a clear diurnal variation with daytime maximum. During nighttime DMS levels fall close or below the detection limit of 2 pmol ·mol-1. Concurrent measurements of OH and NO3 radicals during the campaign indicate that NO3 levels can explain most of the observed diurnal variation of DMS. Dimethylsulfoxide (DMSO) ranged between 0.02 and 10.1 pmol · mol-1 (mean value of 1.7 pmol · mol-1) and presents a diurnal variation similar to that of DMS. SO2 levels ranged from 220 to 2970 pmol · mol-1 (mean value of 1030 pmol · mol-1), while nss-SO42- and MS- ranged from 330 to 7100 pmol · mol-1, (mean value of 1440 pmol · mol-1) and 1.1 to 37.5 pmol · mol- (mean value of 11.5 pmol · mol-1) respectively. Of particular interest are the measurements of gaseous MSA and H2SO4. MSA ranged from below the detection limit (3×104) to 3.7×107 molecules cm-3, whereas H2SO4 ranged between 1×105 and 9.0×107 molecules cm-3. The measured H2SO4 maxima are among the highest reported in literature and can be attributed to high insolation, absence of precipitation and increased SO2 levels in the area. From the concurrent SO2, OH, and H2SO4 measurements a sticking coefficient of 0.52±0.28 was calculated for H2SO4. From the concurrent MSA, OH, and DMS measurements the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to range between 0

  19. Gaseous (DMS, MSA, SO2, H2SO4 and DMSO) and particulate (sulfate and methanesulfonate) sulfur species over the northeastern coast of Crete

    NASA Astrophysics Data System (ADS)

    Bardouki, H.; Berresheim, H.; Vrekoussis, M.; Sciare, J.; Kouvarakis, G.; Oikonomou, K.; Schneider, J.; Mihalopoulos, N.

    2003-10-01

    A detailed study of the levels, the temporal and diurnal variability of the main compounds involved in the biogenic sulfur cycle was carried out in Crete (Eastern Mediterranean) during the Mediterranean Intensive Oxidant Study (MINOS) field experiment in July-August 2001. Intensive measurements of gaseous dimethylsulfide (DMS), dimethylsulfoxide (DMSO), sulfur dioxide (SO2), sulfuric (H2SO4) and methanesulfonic acids (MSA) and particulate sulfate (SO42-) and methanesulfonate (MS-) have been performed during the campaign. Dimethylsulfide (DMS) levels ranged from 2.9 to 136 pmol·mol-1 (mean value of 21.7 pmol·mol-1) and showed a clear diurnal variation with daytime maximum. During nighttime DMS levels fall close or below the detection limit of 2 pmol·mol-1. Concurrent measurements of OH and NO3 radicals during the campaign indicate that NO3 levels can explain most of the observed diurnal variation of DMS. Dimethylsulfoxide (DMSO) ranged between 0.02 and 10.1 pmol·mol-1 (mean value of 1.7 pmol·mol-1) and presents a diurnal variation similar to that of DMS. SO2 levels ranged from 220 to 2970 pmol·mol-1 (mean value of 1030 pmol·mol-1), while nss-SO42- and MS- ranged from 330 to 7100 pmol·mol-1, (mean value of 1440 pmol·mol-1) and 1.1 to 37.5 pmol·mol-1 (mean value of 11.5 pmol·mol-1) respectively. Of particular interest are the measurements of gaseous MSA and H2SO4. MSA ranged from below the detection limit (3x104) to 3.7x107 molecules cm-3, whereas H2SO4 ranged between 1x105 and 9.0x107 molecules cm-3. The measured H2SO4 maxima are among the highest reported in literature and can be attributed to high insolation, absence of precipitation and increased SO2 levels in the area. From the concurrent SO2, OH, and H2SO4 measurements a sticking coefficient of 0.52±0.28 was calculated for H2SO4. From the concurrent MSA, OH, and DMS measurements the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to range between 0.1-0.4%. This low MSA

  20. Metagenomic insights into strategies of carbon conservation and unusual sulfur biogeochemistry in a hypersaline Antarctic lake

    PubMed Central

    Yau, Sheree; Lauro, Federico M; Williams, Timothy J; DeMaere, Matthew Z; Brown, Mark V; Rich, John; Gibson, John AE; Cavicchioli, Ricardo

    2013-01-01

    Organic Lake is a shallow, marine-derived hypersaline lake in the Vestfold Hills, Antarctica that has the highest reported concentration of dimethylsulfide (DMS) in a natural body of water. To determine the composition and functional potential of the microbial community and learn about the unusual sulfur chemistry in Organic Lake, shotgun metagenomics was performed on size-fractionated samples collected along a depth profile. Eucaryal phytoflagellates were the main photosynthetic organisms. Bacteria were dominated by the globally distributed heterotrophic taxa Marinobacter, Roseovarius and Psychroflexus. The dominance of heterotrophic degradation, coupled with low fixation potential, indicates possible net carbon loss. However, abundant marker genes for aerobic anoxygenic phototrophy, sulfur oxidation, rhodopsins and CO oxidation were also linked to the dominant heterotrophic bacteria, and indicate the use of photo- and lithoheterotrophy as mechanisms for conserving organic carbon. Similarly, a high genetic potential for the recycling of nitrogen compounds likely functions to retain fixed nitrogen in the lake. Dimethylsulfoniopropionate (DMSP) lyase genes were abundant, indicating that DMSP is a significant carbon and energy source. Unlike marine environments, DMSP demethylases were less abundant, indicating that DMSP cleavage is the likely source of high DMS concentration. DMSP cleavage, carbon mixotrophy (photoheterotrophy and lithoheterotrophy) and nitrogen remineralization by dominant Organic Lake bacteria are potentially important adaptations to nutrient constraints. In particular, carbon mixotrophy relieves the extent of carbon oxidation for energy production, allowing more carbon to be used for biosynthetic processes. The study sheds light on how the microbial community has adapted to this unique Antarctic lake environment. PMID:23619305

  1. The genetic potential for key biogeochemical processes in Arctic frost flowers and young sea ice revealed by metagenomic analysis.

    PubMed

    Bowman, Jeff S; Berthiaume, Chris T; Armbrust, E Virginia; Deming, Jody W

    2014-08-01

    Newly formed sea ice is a vast and biogeochemically active environment. Recently, we reported an unusual microbial community dominated by members of the Rhizobiales in frost flowers at the surface of Arctic young sea ice based on the presence of 16S gene sequences related to these strains. Here, we use metagenomic analysis of two samples, from a field of frost flowers and the underlying young sea ice, to explore the metabolic potential of this surface ice community. The analysis links genes for key biogeochemical processes to the Rhizobiales, including dimethylsulfide uptake, betaine glycine turnover, and halocarbon production. Nodulation and nitrogen fixation genes characteristic of terrestrial root-nodulating Rhizobiales were generally lacking from these metagenomes. Non-Rhizobiales clades at the ice surface had genes that would enable additional biogeochemical processes, including mercury reduction and dimethylsulfoniopropionate catabolism. Although the ultimate source of the observed microbial community is not known, considerations of the possible role of eolian deposition or transport with particles entrained during ice formation favor a suspended particle source for this microbial community.

  2. PTR-MS measurements and analysis of models for the calculation of Henry's law constants of monosulfides and disulfides.

    PubMed

    Schuhfried, Erna; Biasioli, Franco; Aprea, Eugenio; Cappellin, Luca; Soukoulis, Christos; Ferrigno, Antonella; Märk, Tilmann D; Gasperi, Flavia

    2011-04-01

    Sulfides are known for their strong odor impact even at very low concentrations. Here, we report Henry's law constants (HLCs) measured at the nanomolar concentration range in water for monosulfides (dimethylsulfide, ethylmethylsulfide, diethylsulfide, allylmethylsulfide) and disulfides (dimethyldisulfide, diethylsulfide, dipropylsulfide) using a dynamic stripping technique coupled to Proton Transfer Reaction-Mass Spectrometry (PTR-MS). The experimental data were compared with literature values and to vapor/solubility calculations and their consistency was confirmed employing the extra-thermodynamic enthalpy-entropy compensation effect. Our experimental data are compatible with reported literature values, and they are typically lower than averaged experimental literature values by about 10%. Critical comparison with other freely available models (modeled vapor/solubility; group and bond additivity methods; Linear Solvation Energy Relationship; SPARC) was performed to validate their applicability to monosulfides and disulfides. Evaluation of theoretical models reveals a large deviation from our measured values by up to four times (in units of Matm(-1)). Two group contribution models were adjusted in view of the new data, and HLCs for a list of sulfur compounds were calculated. Based on our findings we recommend the evaluation and adaption of theoretical models for monosulfides and disulfides to lower values of solubility and higher values of fugacity.

  3. Degradation of methanethiol by methylotrophic methanogenic archaea in a lab-scale upflow anaerobic sludge blanket reactor.

    PubMed

    de Bok, F A M; van Leerdam, R C; Lomans, B P; Smidt, H; Lens, P N L; Janssen, A J H; Stams, A J M

    2006-12-01

    In a lab-scale upflow anaerobic sludge blanket reactor inoculated with granular sludge from a full-scale wastewater treatment plant treating paper mill wastewater, methanethiol (MT) was degraded at 30 degrees C to H2S, CO2, and CH4. At a hydraulic retention time of 9 h, a maximum influent concentration of 6 mM MT was applied, corresponding to a volumetric loading rate of 16.5 mmol liter-1 day-1. The archaeal community within the reactor was characterized by anaerobic culturing and denaturing gradient gel electrophoresis analysis, cloning, and sequencing of 16S rRNA genes and quantitative PCR. Initially, MT-fermenting methanogenic archaea related to members of the genus Methanolobus were enriched in the reactor. Later, they were outcompeted by Methanomethylovorans hollandica, which was detected in aggregates but not inside the granules that originated from the inoculum, the microbial composition of which remained fairly unchanged. Possibly other species within the Methanosarcinacaea also contributed to the fermentation of MT, but they were not enriched by serial dilution in liquid media. The archaeal community within the granules, which was dominated by Methanobacterium beijingense, did not change substantially during the reactor operation. Some of the species related to Methanomethylovorans hollandica were enriched by serial dilutions, but their growth rates were very low. Interestingly, the enrichments could be sustained only in the presence of MT and did not utilize any of the other typical substrates for methylotrophic methanogens, such as methanol, methyl amine, or dimethylsulfide.

  4. The distribution of dimethylsulfoniopropionate in tropical Pacific coral reef invertebrates

    NASA Astrophysics Data System (ADS)

    van Alstyne, Kathryn L.; Schupp, Peter; Slattery, Marc

    2006-08-01

    Dimethylsulfoniopropionate (DMSP) is an important component of the global sulfur cycle and may be involved, via its cleavage product dimethylsulfide, in climate regulation. Although it is common in many algae, reports of DMSP in animals, particularly tropical invertebrates, are limited. This study examined the distribution of DMSP in a diverse group of coral reef invertebrates. DMSP was present in all 22 species of cnidarians and ranged from 9 to 723 μmol g-1 of dry mass (DM) with a mean (± 1SD) of 110 ± 180 μmol g-1 DM. It was not detected in a flatworm and an ascidian or in two of five sponges. Concentrations in sponges ranged from undetectable to 16 μmol g-1 DM with a mean of 4 ± 7 μmol g-1 DM. Within the cnidarians, DMSP concentrations did not differ among orders. Among cnidarian species, DMSP concentrations were correlated with symbiotic zooxanthellae densities. Within cnidarian species, DMSP concentrations of individuals were positively correlated with zooxanthellae densities in three of the four species examined. We speculate that DMSP is dietarily derived in sponges and derived from zooxanthellae in the cnidarians. The functions of DMSP in coral reef invertebrates are not known.

  5. Development and testing of a high-resolution model for tropospheric sulfate driven by observation-derived meteorology

    SciTech Connect

    Benkovitz, C.M.

    1994-05-01

    A high-resolution three-dimensional Eulerian transport and transformation model has been developed to simulate concentrations of tropospheric sulfate for specific times and locations; it was applied over the North Atlantic and adjacent continental regions during October and November, 1986. The model represents emissions of anthropogenic SO{sub 2} and sulfate and of biogenic sulfur species, horizontal and vertical transport, gas-phase oxidation of SO{sub 2} and dimethylsulfide, aqueous-phase oxidation of SO{sub 2}, and wet and dry deposition of SO{sub 2}, sulfate, and methanesulfonic acid (MSA). The meteorological driver is the 6-hour output from the forecast model of the European Centre for Medium-Range Weather Forecasts. Calculated sulfate concentrations and column burdens, examined in detail for October 15 and October 22 at 6Z, are related to existing weather patterns. These results exhibit rich temporal and spatial structure; the characteristic (1/e) temporal autocorrelation time for the sulfate column burdens over the central North Atlantic averages 20 hours; 95% of the values were 25 hours or less. The characteristic distance of spatial autocorrelation over this region depends on direction and averages 1,600 km; with 10{sup th} percentile value of 400 km and 90{sup th} percentile value of 1,700 km. Daily average model sulfate concentrations at the lowest vertical accurately represent the spatial variability, temporal episodicity, and absolute magnitudes of surface concentrations measured by monitoring stations in Europe, Canada and Barbados.

  6. Measurement of gas/water uptake coefficients for trace gases active in the marine environment

    SciTech Connect

    Davidovits, P. . Dept. of Chemistry); Worsnop, D.W.; Zahniser, M.S.; Kolb, C.E. . Center for Chemical and Environmental Physics)

    1992-02-01

    Ocean produced reduced sulfur compounds including dimethylsulfide (DMS), hydrogen sulfide (H{sub 2}S), carbon disulfide (CS{sub 2}), methyl mercaptan (CH{sub 3}CH) and carbonyl sulfide (OCS) deliver a sulfur burden to the atmosphere which is roughly equal to sulfur oxides produced by fossil fuel combustion. These species and their oxidation products dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO{sub 2}) and methane sulfonic acid (MSA) dominate aerosol and CCN production in clean marine air. Furthermore, oxidation of reduced sulfur species will be strongly influenced by NO{sub x}/O{sub 3} chemistry in marine atmospheres. The multiphase chemical processes for these species must be understood in order to study the evolving role of combustion produced sulfur oxides over the oceans. We have measured the chemical and physical parameters affecting the uptake of reduced sulfur compounds, their oxidation products, ozone, and nitrogen oxides by the ocean's surface, and marine clouds, fogs, and aerosols. These parameters include: gas/surface mass accommodation coefficients; physical and chemically modified (effective) Henry's law constants; and surface and liquid phase reaction constants. These parameters are critical to understanding both the interaction of gaseous trace species with cloud and fog droplets and the deposition of trace gaseous species to dew covered, fresh water and marine surfaces.

  7. Measurement of gas/water uptake coefficients for trace gases active in the marine environment. [Annual report

    SciTech Connect

    Davidovits, P.; Worsnop, D.W.; Zahniser, M.S.; Kolb, C.E.

    1992-02-01

    Ocean produced reduced sulfur compounds including dimethylsulfide (DMS), hydrogen sulfide (H{sub 2}S), carbon disulfide (CS{sub 2}), methyl mercaptan (CH{sub 3}CH) and carbonyl sulfide (OCS) deliver a sulfur burden to the atmosphere which is roughly equal to sulfur oxides produced by fossil fuel combustion. These species and their oxidation products dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO{sub 2}) and methane sulfonic acid (MSA) dominate aerosol and CCN production in clean marine air. Furthermore, oxidation of reduced sulfur species will be strongly influenced by NO{sub x}/O{sub 3} chemistry in marine atmospheres. The multiphase chemical processes for these species must be understood in order to study the evolving role of combustion produced sulfur oxides over the oceans. We have measured the chemical and physical parameters affecting the uptake of reduced sulfur compounds, their oxidation products, ozone, and nitrogen oxides by the ocean`s surface, and marine clouds, fogs, and aerosols. These parameters include: gas/surface mass accommodation coefficients; physical and chemically modified (effective) Henry`s law constants; and surface and liquid phase reaction constants. These parameters are critical to understanding both the interaction of gaseous trace species with cloud and fog droplets and the deposition of trace gaseous species to dew covered, fresh water and marine surfaces.

  8. Use of 13C-Labeled Substrates to Determine Relative Methane Production Rates in Hypersaline Microbial Communities

    NASA Astrophysics Data System (ADS)

    Kelley, C. A.; Bebout, B.; Chanton, J.

    2015-12-01

    Rates and pathways of methane production were determined from photosynthetic soft microbial mats and gypsum-encrusted endoevaporites collected in hypersaline environments from California, Mexico and Chile, as well as an organic-rich mud from a pond in the El Tatio volcanic fields, Chile. Samples (mud, homogenized soft mats and endoevaporites) were incubated anaerobically with deoxygenated site water, and the increase in methane concentration through time in the headspaces of the incubation vials was used to determine methane production rates. To ascertain the substrates used by the methanogens, 13C-labeled methylamines, methanol, dimethylsulfide, acetate or bicarbonate were added to the incubations (one substrate per vial) and the stable isotopic composition of the resulting methane was measured. The vials amended with 13C-labeled methylamines produced the most 13C-enriched methane, generally followed by the 13C-labeled methanol-amended vials. The stable isotope data and the methane production rates were used to determine first order rate constants for each of the substrates at each of the sites. Estimates of individual substrate use revealed that the methylamines produced 55 to 92% of the methane generated, while methanol was responsible for another 8 to 40%.

  9. Dimethylsulfoniopropionate metabolism by Pfiesteria-associated Roseobacter spp.

    PubMed

    Miller, Todd R; Belas, Robert

    2004-06-01

    The Roseobacter clade of marine bacteria is often found associated with dinoflagellates, one of the major producers of dimethylsulfoniopropionate (DMSP). In this study, we tested the hypothesis that Roseobacter species have developed a physiological relationship with DMSP-producing dinoflagellates mediated by the metabolism of DMSP. DMSP was measured in Pfiesteria and Pfiesteria-like (Cryptoperidiniopsis) dinoflagellates, and the identities and metabolic potentials of the associated Roseobacter species to degrade DMSP were determined. Both Pfiesteria piscicida and Pfiesteria shumwayae produce DMSP with an average intracellular concentration of 3.8 microM. Cultures of P. piscicida or Cryptoperidiniopsis sp. that included both the dinoflagellates and their associated bacteria rapidly catabolized 200 microM DMSP (within 30 h), and the rate of catabolism was much higher for P. piscicida cultures than for P. shumwayae cultures. The community of bacteria from P. piscicida and Cryptoperidiniopsis cultures degraded DMSP with the production of dimethylsulfide (DMS) and acrylate, followed by 3-methylmercaptopropionate (MMPA) and methanethiol (MeSH). Four DMSP-degrading bacteria were isolated from the P. piscicida cultures and found to be taxonomically related to Roseobacter species. All four isolates produced MMPA from DMSP. Two of the strains also produced MeSH and DMS, indicating that they are capable of utilizing both the lyase and demethylation pathways. The diverse metabolism of DMSP by the dinoflagellate-associated Roseobacter spp. offers evidence consistent with a hypothesis that these bacteria benefit from association with DMSP-producing dinoflagellates.

  10. Odor-Sensing System to Support Social Participation of People Suffering from Incontinence.

    PubMed

    Ortiz Pérez, Alvaro; Kallfaß-de Frenes, Vera; Filbert, Alexander; Kneer, Janosch; Bierer, Benedikt; Held, Pirmin; Klein, Philipp; Wöllenstein, Jürgen; Benyoucef, Dirk; Kallfaß, Sigrid; Mescheder, Ulrich; Palzer, Stefan

    2016-12-29

    This manuscript describes the design considerations, implementation, and laboratory validation of an odor sensing module whose purpose is to support people that suffer from incontinence. Because of the requirements expressed by the affected end-users the odor sensing unit is realized as a portable accessory that may be connected to any pre-existing smart device. We have opted for a low-cost, low-power consuming metal oxide based gas detection approach to highlight the viability of developing an inexpensive yet helpful odor recognition technology. The system consists of a hotplate employing, inkjet-printed p-type semiconducting layers of copper(II) oxide, and chromium titanium oxide. Both functional layers are characterized with respect to their gas-sensitive behavior towards humidity, ammonia, methylmercaptan, and dimethylsulfide and we demonstrate detection limits in the parts-per-billion range for the two latter gases. Employing a temperature variation scheme that reads out the layer's resistivity in a steady-state, we use each sensor chip as a virtual array. With this setup, we demonstrate the feasibility of detecting odors associated with incontinence.

  11. Methanolobus zinderi sp. nov., a methylotrophic methanogen isolated from a deep subsurface coal seam.

    PubMed

    Doerfert, Sebastian N; Reichlen, Matthew; Iyer, Prabha; Wang, Mingyu; Ferry, James G

    2009-05-01

    A methanogenic organism from the domain Archaea (SD1(T)) was isolated from saline water released from a coal seam located 926 m below the surface via a methane-producing well near Monroe, Louisiana, USA. Growth and methanogenesis were supported with methanol, monomethylamine, dimethylamine or trimethylamine, but not with dimethylsulfide, formate, acetate or H(2)/CO(2). Cells grew in high-salt minimal medium but growth was stimulated with yeast extract or tryptone. Cells were single, non-motile, irregular coccoids 0.5-1.0 microm in diameter and the cell wall contained protein. Conditions for the maximum rate of growth were 40-50 degrees C, 0.2-0.6 M NaCl, 100->or=200 mM MgCl(2), and pH 7.0-8.0. The G+C content of the genomic DNA was 42+/-1mol %. A comparison of 16S rRNA gene sequences indicated that strain SD1(T) was most closely related to Methanolobus oregonensis DSM 5435(T) with 96 % gene sequence similarity. It is proposed that strain SD1(T) represents a novel species, Methanolobus zinderi sp. nov. The type strain is SD1(T) (=ATCC BAA-1601(T)=DSM 21339(T)).

  12. Methanosarcina horonobensis sp. nov., a methanogenic archaeon isolated from a deep subsurface Miocene formation.

    PubMed

    Shimizu, Satoru; Upadhye, Rahul; Ishijima, Yoji; Naganuma, Takeshi

    2011-10-01

    A methanogenic organism, designated strain HB-1(T), from the domain Archaea was isolated from groundwater sampled from a subsurface Miocene formation located in Horonobe, Hokkaido, Japan. The strain grew on methanol, dimethylamine, trimethylamine, dimethylsulfide and acetate but not on monomethylamine, H(2)/CO(2), formate, 2-propanol, 2-butanol or cyclopentanol. Cells were Gram-reaction-negative, non-motile, irregular cocci that were 1.4-2.9 µm in diameter and occurred singly or in pairs. The strain grew at 20-42 °C (optimum 37 °C), at pH 6.0-7.75 (optimum pH 7.0-7.25) and in 0-0.35 M NaCl (optimum 0.1 M). The G+C content of the genomic DNA was 41.4 mol%. 16S rRNA gene sequencing revealed that the strain was a member of the genus Methanosarcina but that it clearly differed from all recognized species of this genus (93.1-97.9 % sequence similarity). The phenotypic and phylogenetic features of strain HB-1(T) indicate that it represents a novel species of the genus Methanosarcina, for which the name Methanosarcina horonobensis sp. nov. is proposed. The type strain is HB-1(T) ( = DSM 21571(T)  = JCM 15518(T)  = NBRC 102577(T)).

  13. Back-Transport of Sulfur Species in the High-Southern Latitudes

    NASA Astrophysics Data System (ADS)

    Cosme, E.; Hourdin, F.; Legrand, M.; Genthon, C.; Martinerie, P.

    2002-05-01

    To interpret polar ice core records of sulfate and methanesulfonic acid (MSA), a good understanding of the processes involved in dimethylsulfide (DMS) oxidation is needed. In particular, the signification of changes in the MSA to non-sea-salt sulfate ratio remains unclear. In cold environment, DMS oxidation through the addition channel, partly leading to MSA, prevails over the abstraction channel that does not yield MSA. However, at several Antarctic stations, the MSA to non-sea-salt sulfate ratio is found higher in the summer (warmer) season than in winter. To improve the interpretation of the MSA to non-sea-salt sulfate ratio, we wish to locate the sources contributing to the sulfur species in Antarctica and to identify how they change with season. To do this, we use the Laboratoire de Météorologie Dynamique (CNRS, Paris, France) Atmospheric General Circulation Model with an imbedded sulfur chemistry module (Cosme et al., Sulfur cycle in the high southern latitudes in the LMD-ZT General Circulation Model, submitted to JGR). The climate / chemistry model is first run forward to archive climate and chemistry parameters which affect the sulfur species. These parameters are then used to run backward an adjoint of the model, thus providing an inverse history of transport and chemistry. We will first present the adjoint transport and chemistry equations. Then we will show and discuss preliminary results related to the interpretation of the MSA to non-sea-salt sulfate ratio in the Antarctic region.

  14. Volatile organic compound emissions from dairy cows and their waste as measured by proton-transfer-reaction mass spectrometry.

    PubMed

    Shaw, Stephanie L; Mitloehner, Frank M; Jackson, Wendi; Depeters, Edward J; Fadel, James G; Robinson, Peter H; Holzinger, Rupert; Goldstein, Allen H

    2007-02-15

    California dairies house approximately 1.8 million lactating and 1.5 million dry cows and heifers. State air regulatory agencies view these dairies as a major air pollutant source, but emissions data are sparse, particularly for volatile organic compounds (VOCs). The objective of this work was to determine VOC emissions from lactating and dry dairy cows and their waste using an environmental chamber. Carbon dioxide and methane were measured to provide context for the VOCs. VOCs were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The compounds with highest fluxes when cows plus waste were present were methanol, acetone + propanal, dimethylsulfide, and m/z 109 (likely 4-methyl-phenol). The compounds with highest fluxes from fresh waste (urine and feces) were methanol, m/z 109, and m/z 60 (likely trimethylamine). Ethanol fluxes are reported qualitatively, and several VOCs that were likely emitted (formaldehyde, methylamine, dimethylamine) were not detectable by PTR-MS. The sum of reactive VOC fluxes measured when cows were present was a factor of 6-10 less than estimates historically used for regulatory purposes. In addition, ozone formation potentials of the dominant VOCs were -10% those of typical combustion or biogenic VOCs. Thus dairy cattle have a comparatively small impact on ozone formation per VOC mass emitted.

  15. Modeled methanesulfonic acid (MSA) concentrations in Antarctica: the influence of meteorology in explaining modern versus LGM differences in ice cores

    NASA Astrophysics Data System (ADS)

    Hezel, P. J.; Alexander, B.; Bitz, C. M.; Steig, E. J.

    2011-12-01

    Methanesulfonic acid (MSA) concentrations measured in ice cores in Antarctica for the last glacial maximum (LGM) are higher than modern day concentrations on the East Antarctic Plateau (Vostok), but are lower than modern concentrations in West Antarctica (Siple Dome). MSA concentrations measured in ice cores have been interpreted as an indicator of both local sea ice extent (via modulation of dimethylsulfide (DMS) emissions) and regional circulation on decadal time scales, but there has been no assessment of the importance of these two processes in determining MSA concentrations on glacial-interglacial time scales. Explanations for the modern - LGM MSA differences at Vostok invoke increased DMS emissions caused by increased dust fertilization in the LGM (Legrand et al., 1991). Saltzman et al. (2006) show that the MSA measurements at Siple Dome do not corroborate stronger DMS emissions in the Pacific sector during the LGM. We use the GEOS-Chem chemical transport model forced with GISS-ModelE meteorology from modern and LGM boundary conditions to simulate Antarctic MSA concentrations. We estimate the contribution of transport and precipitation to the modern-LGM difference at each location. Changes in DMS emissions, sea ice extent, and oxidant concentrations are evaluated as additional important factors in explaining modern versus LGM MSA concentrations in Antarctic ice cores.

  16. Modeled methanesulfonic acid (MSA) deposition in Antarctica and its relationship to sea ice

    NASA Astrophysics Data System (ADS)

    Hezel, P. J.; Alexander, B.; Bitz, C. M.; Steig, E. J.; Holmes, C. D.; Yang, X.; Sciare, J.

    2011-12-01

    Methanesulfonic acid (MSA) has previously been measured in ice cores in Antarctica as a proxy for sea ice extent and Southern Hemisphere circulation. In a series of chemical transport model (GEOS-Chem) sensitivity experiments, we identify mechanisms that control the MSA concentrations recorded in ice cores. Sea ice is linked to MSA via dimethylsulfide (DMS), which is produced biologically in the surface ocean and known to be particularly concentrated in the sea ice zone. Given existing ocean surface DMS concentration data sets, the model does not demonstrate a strong relationship between sea ice and MSA deposition in Antarctica. The variability of DMS emissions associated with sea ice extent is small (11-30%) due to the small interannual variability of sea ice extent. Wind plays a role in the variability in DMS emissions, but its contribution relative to that of sea ice is strongly dependent on the assumed DMS concentrations in the sea ice zone. Atmospheric sulfur emitted as DMS from the sea ice undergoes net transport northward. Our model runs suggest that DMS emissions from the sea ice zone may account for 26-62% of MSA deposition at the Antarctic coast and 36-95% in inland Antarctica. Though our results are sensitive to model assumptions, it is clear that an improved understanding of both DMS concentrations and emissions from the sea ice zone are required to better assess the impact of sea ice variability on MSA deposition to Antarctica.

  17. Variations in the methanesulfonate to sulfate molar ratio in submicrometer marine aerosol particles over the south Pacific Ocean

    NASA Technical Reports Server (NTRS)

    Bates, Timothy S.; Calhoun, Julie A.; Quinn, Patricia K.

    1992-01-01

    Seawater concentrations of dimethylsulfide (DMS) and atmospheric concentrations of DMS, sulfur dioxide, methanesulfonate (MSA), and non-sea-salt (nss) sulfate were measured over the eastern Pacific Ocean between 105 deg and 110 deg W from 20 deg N to 60 deg S during February and March 1989. Although the samples collected in the Southern Hemisphere appear to be of marine origin, no significant correlation was found between the latitudinal distributions of DMS, SO2, MSA, and nss SO4(2-). However, an inverse correlation was found between atmospheric temperature and the MSA to nss SO4(2-) molar ratio in submicrometer aerosol particles with a decrease in temperature corresponding to an increase in the molar ratio. Although this trend is consistent with laboratory results indicating the favored production of MSA at lower temperatures, it is contrary to Southern Hemisphere baseline station data. This suggests either a decrease in the supply of DMS relative to nonmarine sources of nss SO4(2-) at the baseline stations in winter or additional mechanisms that affect the relative production of MSA and nss SO4(2-).

  18. Measurement of volatile organic compounds in exhaled breath as collected in evacuated electropolished canisters.

    PubMed

    Pleil, J D; Lindstrom, A B

    1995-03-24

    A set of three complementary analytical methods were developed specifically for exhaled breath as collected in evacuated stainless steel canisters using gas chromatographic-mass spectrometric detection. The first is a screening method to quantify the carbon dioxide component (generally at 4-5% concentration), the second method measures the very volatile high-level endogenous compounds [e.g. acetone and isoprene at 500-1000 parts per billion by volume (ppbv), methanol, ethanol, dimethylsulfide at 2-10 ppbv], and the third method is designed to measure trace-level environmental contaminants and other endogenous volatile organic compounds (VOCs) (sub-ppbv) in breath. The canister-based sample format allows all three methods to be applied to each individual sample for complete constituent characterization. Application of these methods is shown to be useful in the following ways: analysis of CO2 levels indicates the approximate quantity of alveolar breath collected (as opposed to whole breath) in a sample; levels of major endogenous compounds are shown to be influenced by physical activities and subsequent recovery periods; and environmental exposures to xenobiotic VOCs can be characterized by assessment of post-exposure breath elimination curves. The instrumentation and methodology are described and example chromatograms and quantitative data plots demonstrating the utility of the methods are presented.

  19. Microaerobic steroid biosynthesis and the molecular fossil record of Archean life.

    PubMed

    Waldbauer, Jacob R; Newman, Dianne K; Summons, Roger E

    2011-08-16

    The power of molecular oxygen to drive many crucial biogeochemical processes, from cellular respiration to rock weathering, makes reconstructing the history of its production and accumulation a first-order question for understanding Earth's evolution. Among the various geochemical proxies for the presence of O(2) in the environment, molecular fossils offer a unique record of O(2) where it was first produced and consumed by biology: in sunlit aquatic habitats. As steroid biosynthesis requires molecular oxygen, fossil steranes have been used to draw inferences about aerobiosis in the early Precambrian. However, better quantitative constraints on the O(2) requirement of this biochemistry would clarify the implications of these molecular fossils for environmental conditions at the time of their production. Here we demonstrate that steroid biosynthesis is a microaerobic process, enabled by dissolved O(2) concentrations in the nanomolar range. We present evidence that microaerobic marine environments (where steroid biosynthesis was possible) could have been widespread and persistent for long periods of time prior to the earliest geologic and isotopic evidence for atmospheric O(2). In the late Archean, molecular oxygen likely cycled as a biogenic trace gas, much as compounds such as dimethylsulfide do today.

  20. Interaction between nitrogen and sulfur cycles in the polluted marine boundary layer

    NASA Astrophysics Data System (ADS)

    Yvon, S. A.; Plane, J. M. C.; Nien, C.-F.; Cooper, D. J.; Saltzman, E. S.

    1996-01-01

    Simultaneous measurements are reported of the nitrate radical (NO3), nitrogen dioxide (NO2), ozone (O3), and dimethylsulfide (DMS) in the nighttime marine boundary layer over Biscayne Bay in South Florida. These field observations are analyzed and used to initialize a boundary layer box model which examines the relative importance of the various sinks for NOx in the marine boundary layer. The results show that the observed lifetime of NO3 (≤6 min.) is probably controlled both by the loss of nitrogen pentoxide (N2O5) to reaction with water vapor and aerosols and by the reaction between NO3 and DMS. The model is then extended to investigate the loss of nitrogen oxides from an air parcel that remains in the boundary layer with a constant sea-to-air DMS flux for several days. The principal conclusions are (1) that DMS is a much more important sink for NO3 at lower NO2 levels and (2) that the reaction between NO3 and DMS is an important sink for DMS in the marine boundary layer and could exceed that of the daytime removal by OH.

  1. Diversity of bacterial dimethylsulfoniopropionate degradation genes in surface seawater of Arctic Kongsfjorden

    PubMed Central

    Zeng, Yin-Xin; Qiao, Zong-Yun; Yu, Yong; Li, Hui-Rong; Luo, Wei

    2016-01-01

    Dimethylsulfoniopropionate (DMSP), which is the major source of organic sulfur in the world’s oceans, plays a significant role in the global sulfur cycle. This compound is rapidly degraded by marine bacteria either by cleavage to dimethylsulfide (DMS) or demethylation to 3-methylmercaptopropionate (MMPA). The diversity of genes encoding bacterial demethylation (dmdA) and DMS production (dddL and dddP) were measured in Arctic Kongsfjorden. Both dmdA and dddL genes were detected in all stations along a transect from the outer to the inner fjord, while dddP gene was only found in the outer and middle parts of the fjord. The dmdA gene was completely confined to the Roseobacter clade, while the dddL gene was confined to the genus Sulfitobacter. Although the dddP gene pool was also dominated by homologs from the Roseobacter clade, there were a few dddP genes showing close relationships to both Alphaproteobacter and Gammaproteobacter. The results of this study suggest that the Roseobacter clade may play an important role in DMSP catabolism via both demethylation and cleavage pathways in surface waters of Kongsfjorden during summer. PMID:27604458

  2. Production and fate of methylated sulfur compounds from methionine and dimethylsulfoniopropionate in anoxic salt marsh sediments

    SciTech Connect

    Kiene, R.P.; Visscher, P.T.

    1987-10-01

    Anoxic salt marsh sediments were amended with DL-methionine and dimethylsulfoniopropionate (DMSP). Microbial metabolism of methionine yielded methane thiol (MSH) as the major volatile organosulfur product, with the formation of lesser amounts of dimethylsulfide (DMS). Biological transformation of DMSP resulted in the rapid release of DMS and only small amounts of MSH. Experiments with microbial inhibitors indicated that production of MSH from methionine was carried out by procaryotic organisms, probably sulfate-reducing bacteria. Methane-producing bacteria did not metabolize methionine. The involvement of specific groups of organisms in DMSP hydrolysis could not be determined with the inhibitors used, because DMSP was hydrolyzed in all samples except those which were autoclaved. Unamended sediment slurries, prepared from Spartina alterniflora sediments, contained significant concentrations of DMS. Endogenous methylated sulfur compounds and those produced from added methionine and DMSP were consumed by sediment microbes. Both sulfate-reducing and methane-producing bacteria were involved in DMS and MSH consumption. Methanogenesis was stimulated by the volatile organosulfur compounds released from methionine and DMSP. However, apparent competition for these compounds exists between methanogens and sulfate reducers. At low (1 ..mu..M) concentrations of methionine, the terminal S-methyl group was metabolized almost exclusively to CO/sub 2/ and only small amounts of CH/sub 4/. At higher concentrations of methionine, the proportion of the methyl-sulfur groups converted to CH/sub 4/ increased.

  3. Sulfur: The plankton/climate connection

    SciTech Connect

    Malin, G.; Turner, S.M.; Liss, P.S. )

    1992-10-01

    A key process in the global sulfur cycle is the transfer of volatile forms of the element from sea to land via the atmosphere. Early budgets calculated the amount of sulfur required to balance the cycle and generally assumed that this flux was achieved by formation of hydrogen sulfide (H[sub 2]S) in coastal waters, mud flats, etc. However, Lovelock et al. (1972) made the first field measurements of dimethylsulfide (DMS) in seawater and suggested that it represented the missing link in the S cycle. Other sulfur gases, such as carbonylsulfide (COS), carbon disulfide (CS[sub 2]), methylmercaptan (CH[sub 3]SH), and dimethyldisulfide (CH[sub 3]SSCH[sub 3]), are also often observed, but DMS is usually dominant (Andreae et al. 1983, Cline and Bates 1983, Turner and Liss 1985). Over the past decade or so thousands of analyses have been made covering coastal, shelf, and open ocean environments, which show that DMS is ubiquitous in seawater but that considerable spatial and temporal variability occurs (see Cooper and Matrai 1989). In this review the authors consider processes leading to the formation of DMS in seawater, its emission to the atmosphere, and transformations therein, the possible role of DMS oxidation products in climate regulation as proposed by Charlson et al. (1987), and how global changes might affect DMS production. 80 refs., 2 figs.

  4. Link Between Enhanced Arctic Tropospheric BrO Observed By Aura OMI and Meteorological Conditions

    NASA Astrophysics Data System (ADS)

    Choi, S.; Joiner, J.; Salawitch, R. J.; Canty, T. P.; Theys, N.; da Silva, A.; Chance, K.; Suleiman, R. M.; Kurosu, T. P.

    2014-12-01

    Bromine radicals (Br + BrO) are important species owing to the ability to destroy ozone catalytically. They may also impact oxidative pathways of many trace gases including dimethylsulfide (DMS) and mercury. Bromine monoxide (BrO) is the most commonly observed bromine radical species. Since it absorbs ultraviolet (UV) radiation, it can be observed using remote sensing technique including Differential Optical Absorption Spectroscopy (DOAS). Previous studies have reported rapid enhancements tropospheric BrO (so called "BrO explosion") connected to near-surface ozone depletion events during springtime in the Arctic. Space-based observation of BrO through Ozone Monitoring Instrument (OMI) is an excellent tool for studying bromine chemistry particularly for the Arctic due to its frequent observations at high latitudes. We derive tropospheric columns BrO by subtracting estimates of stratospheric column BrO from OMI total column BrO and air mass factor (AMF) correction, and analyze the tropospheric columns BrO in conjunction with Modern-Era Retrospective analysis for Research and Application (MERRA) meteorological fields provided by NASA Global Modeling and Assimilation Office (GMAO) in order to investigate a link between BrO explosion and near-surface meteorological factors.

  5. Link between Enhanced Arctic tropospheric BrO observed by Aura OMI and meteorological conditions

    NASA Astrophysics Data System (ADS)

    Choi, S.; Joiner, J.; Theys, N.; Salawitch, R. J.; Wales, P.; Canty, T. P.; Chance, K.; Suleiman, R. M.; Palm, S. P.; Cullather, R. I.; Darmenov, A.; da Silva, A.; Kurosu, T. P.

    2015-12-01

    Bromine radicals (Br + BrO) are important species owing to the ability to destroy ozone catalytically. They may also impact oxidative pathways of many trace gases including dimethylsulfide (DMS) and mercury. Bromine monoxide (BrO) is the most commonly observed bromine radical species. Since it absorbs ultraviolet (UV) radiation, it can be observed using remote sensing technique including Differential Optical Absorption Spectroscopy (DOAS). Previous studies have reported rapid enhancements tropospheric BrO (so called "bromine explosion") connected to near-surface ozone depletion events during springtime in the Arctic. Space-based observation of BrO through Ozone Monitoring Instrument (OMI) is an excellent tool for studying bromine chemistry particularly for the Arctic due to its frequent observations at high latitudes. We derive tropospheric columns BrO by subtracting estimates of stratospheric column BrO from OMI total column BrO and air mass factor (AMF) correction, and analyze the tropospheric columns BrO in conjunction with Modern-Era Retrospective analysis for Research and Application (MERRA) meteorological fields provided by NASA Global Modeling and Assimilation Office (GMAO) in order to investigate a link between bromine explosion and near-surface meteorological factors.

  6. Diversity of bacterial dimethylsulfoniopropionate degradation genes in surface seawater of Arctic Kongsfjorden

    NASA Astrophysics Data System (ADS)

    Zeng, Yin-Xin; Qiao, Zong-Yun; Yu, Yong; Li, Hui-Rong; Luo, Wei

    2016-09-01

    Dimethylsulfoniopropionate (DMSP), which is the major source of organic sulfur in the world’s oceans, plays a significant role in the global sulfur cycle. This compound is rapidly degraded by marine bacteria either by cleavage to dimethylsulfide (DMS) or demethylation to 3-methylmercaptopropionate (MMPA). The diversity of genes encoding bacterial demethylation (dmdA) and DMS production (dddL and dddP) were measured in Arctic Kongsfjorden. Both dmdA and dddL genes were detected in all stations along a transect from the outer to the inner fjord, while dddP gene was only found in the outer and middle parts of the fjord. The dmdA gene was completely confined to the Roseobacter clade, while the dddL gene was confined to the genus Sulfitobacter. Although the dddP gene pool was also dominated by homologs from the Roseobacter clade, there were a few dddP genes showing close relationships to both Alphaproteobacter and Gammaproteobacter. The results of this study suggest that the Roseobacter clade may play an important role in DMSP catabolism via both demethylation and cleavage pathways in surface waters of Kongsfjorden during summer.

  7. Characterization of Light Non-Methane Hydrocarbons, Surface Water DOC, and Aerosols over the Nordic Seas

    NASA Astrophysics Data System (ADS)

    Hudson, E. D.; Ariya, P. A.

    2006-12-01

    Whole air, size-fractionated marine aerosols, and surface ocean water DOC were sampled together during June-July 2004 on the Nordic seas, in order to explore factors leading to the formation of volatile organic compounds (VOCs) at the sea surface and their transfer to the atmosphere. High site-to-site variability in 19 non-methane hydrocarbon concentrations suggests highly variable, local sources for these compounds. Acetone, C5 and C6 hydrocarbons, and dimethylsulfide were identified in the seawater samples using solid-phase microextraction/GC-MS. The aerosols were analysed by SEM-EDX and contained primarily inorganic material (sea salt, marine sulfates, and carbonates) and little organic matter. However, a culturable bacterium was isolated from the large (9.9 - 18 μ m) fraction at one site, and identified as Micrococcus luteus. We will discuss the implication of these results on potential exchange processes at the ocean-atmosphere interface and the impact of bioaerosols in transferring marine organic carbon to atmospheric organic carbon.

  8. Ocean acidification and marine trace gas emissions.

    PubMed

    Hopkins, Frances E; Turner, Suzanne M; Nightingale, Philip D; Steinke, Michael; Bakker, Dorothee; Liss, Peter S

    2010-01-12

    The oceanic uptake of man-made CO(2) emissions is resulting in a measureable decrease in the pH of the surface oceans, a process which is predicted to have severe consequences for marine biological and biogeochemical processes [Caldeira K, Wickett ME (2003) Nature 425:365; The Royal Society (2005) Policy Document 12/05 (Royal Society, London)]. Here, we describe results showing how a doubling of current atmospheric CO(2) affects the production of a suite of atmospherically important marine trace gases. Two CO(2) treatments were used during a mesocosm CO(2) perturbation experiment in a Norwegian fjord (present day: approximately 380 ppmv and year 2100: approximately 750 ppmv), and phytoplankton blooms were stimulated by the addition of nutrients. Seawater trace gas concentrations were monitored over the growth and decline of the blooms, revealing that concentrations of methyl iodide and dimethylsulfide were significantly reduced under high CO(2.) Additionally, large reductions in concentrations of other iodocarbons were observed. The response of bromocarbons to high CO(2) was less clear cut. Further research is now required to understand how ocean acidification might impact on global marine trace gas fluxes and how these impacts might feed through to changes in the earth's future climate and atmospheric chemistry.

  9. Environmental biology of the marine Roseobacter lineage.

    PubMed

    Wagner-Döbler, Irene; Biebl, Hanno

    2006-01-01

    The Roseobacter lineage is a phylogenetically coherent, physiologically heterogeneous group of alpha-Proteobacteria comprising up to 25% of marine microbial communities, especially in coastal and polar oceans, and it is the only lineage in which cultivated bacteria are closely related to environmental clones. Currently 41 subclusters are described, covering all major marine ecological niches (seawater, algal blooms, microbial mats, sediments, sea ice, marine invertebrates). Members of the Roseobacter lineage play an important role for the global carbon and sulfur cycle and the climate, since they have the trait of aerobic anoxygenic photosynthesis, oxidize the greenhouse gas carbon monoxide, and produce the climate-relevant gas dimethylsulfide through the degradation of algal osmolytes. Production of bioactive metabolites and quorum-sensing-regulated control of gene expression mediate their success in complex communities. Studies of representative isolates in culture, whole-genome sequencing, e.g., of Silicibacter pomeroyi, and the analysis of marine metagenome libraries have started to reveal the environmental biology of this important marine group.

  10. Sensitivity of modelled sulfate aerosol and its radiative effect on climate to ocean DMS concentration and air-sea flux

    NASA Astrophysics Data System (ADS)

    Tesdal, Jan-Erik; Christian, James R.; Monahan, Adam H.; von Salzen, Knut

    2016-09-01

    Dimethylsulfide (DMS) is a well-known marine trace gas that is emitted from the ocean and subsequently oxidizes to sulfate in the atmosphere. Sulfate aerosols in the atmosphere have direct and indirect effects on the amount of solar radiation reaching the Earth's surface. Thus, as a potential source of sulfate, ocean efflux of DMS needs to be accounted for in climate studies. Seawater concentration of DMS is highly variable in space and time, which in turn leads to high spatial and temporal variability in ocean DMS emissions. Because of sparse sampling (in both space and time), large uncertainties remain regarding ocean DMS concentration. In this study, we use an atmospheric general circulation model with explicit aerosol chemistry (CanAM4.1) and several climatologies of surface ocean DMS concentration to assess uncertainties about the climate impact of ocean DMS efflux. Despite substantial variation in the spatial pattern and seasonal evolution of simulated DMS fluxes, the global-mean radiative effect of sulfate is approximately linearly proportional to the global-mean surface flux of DMS; the spatial and temporal distribution of ocean DMS efflux has only a minor effect on the global radiation budget. The effect of the spatial structure, however, generates statistically significant changes in the global-mean concentrations of some aerosol species. The effect of seasonality on the net radiative effect is larger than that of spatial distribution and is significant at global scale.

  11. Microaerobic steroid biosynthesis and the molecular fossil record of Archean life

    PubMed Central

    Waldbauer, Jacob R.; Newman, Dianne K.; Summons, Roger E.

    2011-01-01

    The power of molecular oxygen to drive many crucial biogeochemical processes, from cellular respiration to rock weathering, makes reconstructing the history of its production and accumulation a first-order question for understanding Earth’s evolution. Among the various geochemical proxies for the presence of O2 in the environment, molecular fossils offer a unique record of O2 where it was first produced and consumed by biology: in sunlit aquatic habitats. As steroid biosynthesis requires molecular oxygen, fossil steranes have been used to draw inferences about aerobiosis in the early Precambrian. However, better quantitative constraints on the O2 requirement of this biochemistry would clarify the implications of these molecular fossils for environmental conditions at the time of their production. Here we demonstrate that steroid biosynthesis is a microaerobic process, enabled by dissolved O2 concentrations in the nanomolar range. We present evidence that microaerobic marine environments (where steroid biosynthesis was possible) could have been widespread and persistent for long periods of time prior to the earliest geologic and isotopic evidence for atmospheric O2. In the late Archean, molecular oxygen likely cycled as a biogenic trace gas, much as compounds such as dimethylsulfide do today. PMID:21825157

  12. Henry's law solubilities and Śetchenow coefficients for biogenic reduced sulfur species obtained from gas-liquid uptake measurements

    NASA Astrophysics Data System (ADS)

    de Bruyn, W. J.; Swartz, E.; Hu, J. H.; Shorter, Jeffrey A.; Davidovits, P.; Worsnop, D. R.; Zahniser, M. S.; Kolb, C. E.

    1995-04-01

    Biogenically produced reduced sulfur compounds, including dimethylsulfide (DMS, CH3SCH3), hydrogen sulfide (H2S), carbon disulfide (CS2), methyl mercaptan (CH3SH), and carbonyl sulfide (OCS), are a major source of sulfur in the marine atmosphere. This source is estimated to contribute 25-40% of global sulfur emissions. These species and their oxidation products, dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), and methane sulfonic acid (MSA), dominate the production of aerosol and cloud condensation nuclei (CCN) in the clean marine atmosphere. The multiphase chemical processes for these species must be understood in order to study the evolving role of combustion-produced sulfur oxides over the oceans. Using a newly developed bubble column apparatus, a series of aqueous phase uptake studies have been completed for the reduced sulfur species DMS, H2S, CS2, CH3SH, and OCS. Aqueous phase uptake has been studied as a function of temperature (278-298 K), pH (1-14), H2O2 concentration (0-1 M), NaCl concentration (0-5 M), and (NH4)2SO4 concentration (0-4 M). The Henry's law coefficients for CH3SH and CS2 were determined for the first time, as were the Setchenow coefficients for all the species studied.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  14. Production of Molecular Iodine and Tri-iodide in the Frozen Solution of Iodide: Implication for Polar Atmosphere.

    PubMed

    Kim, Kitae; Yabushita, Akihiro; Okumura, Masanori; Saiz-Lopez, Alfonso; Cuevas, Carlos A; Blaszczak-Boxe, Christopher S; Min, Dae Wi; Yoon, Ho-Il; Choi, Wonyong

    2016-02-02

    The chemistry of reactive halogens in the polar atmosphere plays important roles in ozone and mercury depletion events, oxidizing capacity, and dimethylsulfide oxidation to form cloud-condensation nuclei. Among halogen species, the sources and emission mechanisms of inorganic iodine compounds in the polar boundary layer remain unknown. Here, we demonstrate that the production of tri-iodide (I3(-)) via iodide oxidation, which is negligible in aqueous solution, is significantly accelerated in frozen solution, both in the presence and the absence of solar irradiation. Field experiments carried out in the Antarctic region (King George Island, 62°13'S, 58°47'W) also showed that the generation of tri-iodide via solar photo-oxidation was enhanced when iodide was added to various ice media. The emission of gaseous I2 from the irradiated frozen solution of iodide to the gas phase was detected by using cavity ring-down spectroscopy, which was observed both in the frozen state at 253 K and after thawing the ice at 298 K. The accelerated (photo-)oxidation of iodide and the subsequent formation of tri-iodide and I2 in ice appear to be related with the freeze concentration of iodide and dissolved O2 trapped in the ice crystal grain boundaries. We propose that an accelerated abiotic transformation of iodide to gaseous I2 in ice media provides a previously unrecognized formation pathway of active iodine species in the polar atmosphere.

  15. Back-Transport of Sulfur Species in the High-Southern Latitude

    NASA Astrophysics Data System (ADS)

    Cosme, E.; Hourdin, F.; Legrand, M.; Genthon, C.; Martinerie, P.

    2003-04-01

    To interpret polar ice core records of sulfate and methanesulfonic acid (MSA), a good understanding of the processes involved in dimethylsulfide (DMS) oxidation is needed. In particular, the signification of changes in the MSA to non-sea-salt sulfate ratio remains unclear. In cold environment, DMS oxidation through the addition channel, partly leading to MSA, prevails over the abstraction channel that does not yield MSA. However, at several Antarctic stations, the MSA to non-sea-salt sulfate ratio is found higher in the summer (warmer) season than in winter. To improve the interpretation of the MSA to non-sea-salt sulfate ratio, we wish to locate the sources contributing to the sulfur species in Antarctica and to identify how they change with season. To do this, we use the Laboratoire de Météorologie Dynamique (CNRS, Paris, France) Atmospheric General Circulation Model with an imbedded sulfur chemistry module (Cosme et al., Sulfur cycle in the high southern latitudes in the LMD-ZT General Circulation Model, JGR 107). The climate /chemistry model is first run forward to archive climate and chemistry parameters which affect the sulfur species. These parameters are then used to run backward an adjoint of the model, thus providing an inverse history of transport and chemistry. We will first present the adjoint transport and chemistry equations. Then we will show and discuss preliminary results related to the interpretation of the MSA to non-sea-salt sulfate ratio in the Antarctic region.

  16. Quadruple sulfur isotope constraints on the origin and cycling of volatile organic sulfur compounds in a stratified sulfidic lake

    NASA Astrophysics Data System (ADS)

    Oduro, Harry; Kamyshny, Alexey; Zerkle, Aubrey L.; Li, Yue; Farquhar, James

    2013-11-01

    We have quantified the major forms of volatile organic sulfur compounds (VOSCs) distributed in the water column of stratified freshwater Fayetteville Green Lake (FGL), to evaluate the biogeochemical pathways involved in their production. The lake's anoxic deep waters contain high concentrations of sulfate (12-16 mmol L-1) and sulfide (0.12 μmol L-1 to 1.5 mmol L-1) with relatively low VOSC concentrations, ranging from 0.1 nmol L-1 to 2.8 μmol L-1. Sulfur isotope measurements of combined volatile organic sulfur compounds demonstrate that VOSC species are formed primarily from reduced sulfur (H2S/HS-) and zero-valent sulfur (ZVS), with little input from sulfate. Thedata support a role of a combination of biological and abiotic processes in formation of carbon-sulfur bonds between reactive sulfur species and methyl groups of lignin components. These processes are responsible for very fast turnover of VOSC species, maintaining their low levels in FGL. No dimethylsulfoniopropionate (DMSP) was detected by Electrospray Ionization Mass Spectrometry (ESI-MS) in the lake water column or in planktonic extracts. These observations indicate a pathway distinct from oceanic and coastal marine environments, where dimethylsulfide (DMS) and other VOSC species are principally produced via the breakdown of DMSP by plankton species.

  17. Direct oceanic emissions unlikely to account for the missing source of atmospheric carbonyl sulfide

    NASA Astrophysics Data System (ADS)

    Lennartz, Sinikka T.; Marandino, Christa A.; von Hobe, Marc; Cortes, Pau; Quack, Birgit; Simo, Rafel; Booge, Dennis; Pozzer, Andrea; Steinhoff, Tobias; Arevalo-Martinez, Damian L.; Kloss, Corinna; Bracher, Astrid; Röttgers, Rüdiger; Atlas, Elliot; Krüger, Kirstin

    2017-01-01

    The climate active trace-gas carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere. A missing source in its atmospheric budget is currently suggested, resulting from an upward revision of the vegetation sink. Tropical oceanic emissions have been proposed to close the resulting gap in the atmospheric budget. We present a bottom-up approach including (i) new observations of OCS in surface waters of the tropical Atlantic, Pacific and Indian oceans and (ii) a further improved global box model to show that direct OCS emissions are unlikely to account for the missing source. The box model suggests an undersaturation of the surface water with respect to OCS integrated over the entire tropical ocean area and, further, global annual direct emissions of OCS well below that suggested by top-down estimates. In addition, we discuss the potential of indirect emission from CS2 and dimethylsulfide (DMS) to account for the gap in the atmospheric budget. This bottom-up estimate of oceanic emissions has implications for using OCS as a proxy for global terrestrial CO2 uptake, which is currently impeded by the inadequate quantification of atmospheric OCS sources and sinks.

  18. Climate regulation by marine phytoplankton. : A test by anthropogenic SO/sub 2/ emissions

    SciTech Connect

    Schwartz, S.E.

    1989-05-01

    The potential sensitivity of global mean albedo and temperature to N prompted a novel suggestion consistent with the Gaia hypothesis for regulation of global climate by marine phytoplankton. Certain species of coccolithophores excrete dimethylsulfide (DMS), and this DMS is arguably the principal source of reduced sulfur gases in the global atmosphere and, in the absence of anthropogenic SO/sub 2/, the principal source of atmospheric gaseous sulfur species. Such gaseous sulfur species are oxidized in the atmosphere to form sulfuric acid, which rapidly forms an aerosol. Since sulfate-containing AP are highly efficient CCN, it is argued that an increase in DMS production by marine phytoplankton would yield increased concentrations of CCN, resulting in increased cloud albedo, decreased surface insolation, and decreased planetary temperature. It is further hypothesized that such decreased insolation or temperature might result in decreased production of DMS by marine phytoplankton, i.e., that the process might constitute a negative feedback loop for regulation of planetary climate by marine microorganisms. 18 refs., 3 figs., 1 tab.

  19. Global alteration of ocean ecosystem functioning due to increasing human CO2 emissions.

    PubMed

    Nagelkerken, Ivan; Connell, Sean D

    2015-10-27

    Rising anthropogenic CO2 emissions are anticipated to drive change to ocean ecosystems, but a conceptualization of biological change derived from quantitative analyses is lacking. Derived from multiple ecosystems and latitudes, our metaanalysis of 632 published experiments quantified the direction and magnitude of ecological change resulting from ocean acidification and warming to conceptualize broadly based change. Primary production by temperate noncalcifying plankton increases with elevated temperature and CO2, whereas tropical plankton decreases productivity because of acidification. Temperature increases consumption by and metabolic rates of herbivores, but this response does not translate into greater secondary production, which instead decreases with acidification in calcifying and noncalcifying species. This effect creates a mismatch with carnivores whose metabolic and foraging costs increase with temperature. Species diversity and abundances of tropical as well as temperate species decline with acidification, with shifts favoring novel community compositions dominated by noncalcifiers and microorganisms. Both warming and acidification instigate reduced calcification in tropical and temperate reef-building species. Acidification leads to a decline in dimethylsulfide production by ocean plankton, which as a climate gas, contributes to cloud formation and maintenance of the Earth's heat budget. Analysis of responses in short- and long-term experiments and of studies at natural CO2 vents reveals little evidence of acclimation to acidification or temperature changes, except for microbes. This conceptualization of change across whole communities and their trophic linkages forecast a reduction in diversity and abundances of various key species that underpin current functioning of marine ecosystems.

  20. Competitive fitness of a predominant pelagic calcifier impaired by ocean acidification

    NASA Astrophysics Data System (ADS)

    Riebesell, Ulf; Bach, Lennart T.; Bellerby, Richard G. J.; Monsalve, J. Rafael Bermúdez; Boxhammer, Tim; Czerny, Jan; Larsen, Aud; Ludwig, Andrea; Schulz, Kai G.

    2017-01-01

    Coccolithophores--single-celled calcifying phytoplankton--are an important group of marine primary producers and the dominant builders of calcium carbonate globally. Coccolithophores form extensive blooms and increase the density and sinking speed of organic matter via calcium carbonate ballasting. Thereby, they play a key role in the marine carbon cycle. Coccolithophore physiological responses to experimental ocean acidification have ranged from moderate stimulation to substantial decline in growth and calcification rates, combined with enhanced malformation of their calcite platelets. Here we report on a mesocosm experiment conducted in a Norwegian fjord in which we exposed a natural plankton community to a wide range of CO2-induced ocean acidification, to test whether these physiological responses affect the ecological success of coccolithophore populations. Under high-CO2 treatments, Emiliania huxleyi, the most abundant and productive coccolithophore species, declined in population size during the pre-bloom period and lost the ability to form blooms. As a result, particle sinking velocities declined by up to 30% and sedimented organic matter was reduced by up to 25% relative to controls. There were also strong reductions in seawater concentrations of the climate-active compound dimethylsulfide in CO2-enriched mesocosms. We conclude that ocean acidification can lower calcifying phytoplankton productivity, potentially creating a positive feedback to the climate system.

  1. Odor-Sensing System to Support Social Participation of People Suffering from Incontinence

    PubMed Central

    Ortiz Pérez, Alvaro; Kallfaß-de Frenes, Vera; Filbert, Alexander; Kneer, Janosch; Bierer, Benedikt; Held, Pirmin; Klein, Philipp; Wöllenstein, Jürgen; Benyoucef, Dirk; Kallfaß, Sigrid; Mescheder, Ulrich; Palzer, Stefan

    2016-01-01

    This manuscript describes the design considerations, implementation, and laboratory validation of an odor sensing module whose purpose is to support people that suffer from incontinence. Because of the requirements expressed by the affected end-users the odor sensing unit is realized as a portable accessory that may be connected to any pre-existing smart device. We have opted for a low-cost, low-power consuming metal oxide based gas detection approach to highlight the viability of developing an inexpensive yet helpful odor recognition technology. The system consists of a hotplate employing, inkjet-printed p-type semiconducting layers of copper(II) oxide, and chromium titanium oxide. Both functional layers are characterized with respect to their gas-sensitive behavior towards humidity, ammonia, methylmercaptan, and dimethylsulfide and we demonstrate detection limits in the parts-per-billion range for the two latter gases. Employing a temperature variation scheme that reads out the layer’s resistivity in a steady-state, we use each sensor chip as a virtual array. With this setup, we demonstrate the feasibility of detecting odors associated with incontinence. PMID:28036081

  2. Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

    NASA Technical Reports Server (NTRS)

    Wine, Paul H.; Nicovich, J. M.; Hynes, Anthony J.; Stickel, Robert E.; Thorn, R. P.; Chin, Mian; Cronkhite, Jeffrey A.; Shackelford, Christie J.; Zhao, Zhizhong; Daykin, Edward P.

    1993-01-01

    Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

  3. Bacterial ethane formation from reduced, ethylated sulfur compounds in anoxic sediments

    USGS Publications Warehouse

    Oremland, R.S.; Whiticar, Michael J.; Strohmaier, F.E.; Kiene, R.P.

    1988-01-01

    Trace levels of ethane were produced biologically in anoxic sediment slurries from five chemically different aquatic environments. Gases from these locations displayed biogenic characteristics, having 12C-enriched values of ??13CH4 (-62 to -86%.), ??13C2H6 (-35 to -55%.) and high ratios (720 to 140,000) of CH4 [C2H6 + C3H8]. Endogenous production of ethane by slurries was inhibited by autoclaving or by addition of the inhibitor of methanogenic bacteria, 2-bromoethanesulfonic acid (BES). Ethane formation was stimulated markedly by ethanethiol (ESH), and, to a lesser extent, by diethylsulfide (DES). Formation of methane and ethane in ESH- or DES-amended slurries was blocked by BES. Experiments showed that ethionine (or an analogous compound) could be a precursor of ESH. Ethylamine or ethanol additions to slurries caused only a minor stimulation of ethane formation. Similarly, propanethiol additions resulted in only a minor enhancement of propane formation. Cell suspensions of a methyltrophic methanogen produced traces of ethane when incubated in the presence of DES, although the organism did not grow on this compound. These results indicate that methanogenic bacteria produce ethane from the traces of ethylated sulfur compounds present in recent sediments. Preliminary estimates of stable carbon isotope fractionation associated with sediment methane formation from dimethylsulfide was about 40%., while ethane formation from DES and ESH was only 4. 6 and 6.5%., respectively. ?? 1988.

  4. Aerosol production and growth in the marine boundary layer

    NASA Astrophysics Data System (ADS)

    Russell, Lynn M.; Pandis, Spyros N.; Seinfeld, John H.

    1994-10-01

    The dependence of cloud condensation nuclei (CCN) production on the marine dimethylsulfide (DMS) flux is modeled with a dynamic description of the gas, aerosol, and aqueous phase processes in a closed air parcel. The results support the conclusion reached in previous work with a steady state model that an approximately linear dependence exists between CCN concentration and DMS flux under typical remote marine conditions. This linearity does not hold for low DMS fluxes (the threshold is typically near 2.5 micromol/sq m/day) because the sea-salt particles heterogeneously convert the available SO2 to sulfate inhibiting the creation of new particles. The conditions under which this linear relationship holds are investigated by a series of sensitivity studies, focusing particular attention on the impact of the timing and frequency of cloud events. We consider the regimes of the model's semiempirical parameters, showing that the uncertainty associated with two such parameters, namely, the nucleation rate scaling factor and the sulfuric acid accommodation coefficient, is sufficient to change the predicted CCN production due to DMS from over 300/cu cm/day to none. This sensitivity accounts for most of the range of results predicted by previous models of the DMS-CCN system.

  5. Net effect of wort osmotic pressure on fermentation course, yeast vitality, beer flavor, and haze.

    PubMed

    Sigler, K; Matoulková, D; Dienstbier, M; Gabriel, P

    2009-04-01

    The net effect of increased wort osmolarity on fermentation time, bottom yeast vitality and sedimentation, beer flavor compounds, and haze was determined in fermentations with 12 degrees all-malt wort supplemented with sorbitol to reach osmolarity equal to 16 degrees and 20 degrees. Three pitchings were performed in 12 degrees/12 degrees/12 degrees, 16 degrees/16 degrees/12 degrees, and 20 degrees/20 degrees/12 degrees worts. Fermentations in 16 degrees and 20 degrees worts decreased yeast vitality measured as acidification power (AP) by a maximum of 10%, lowered yeast proliferation, and increased fermentation time. Repitching aggravated these effects. The 3rd "back to normal" pitching into 12 degrees wort restored the yeast AP and reproductive abilities while the extended fermentation time remained. Yeast sedimentation in 16 degrees and 20 degrees worts was delayed but increased about two times at fermentation end relative to that in 12 degrees wort. Third "back-to-normal" pitching abolished the delay in sedimentation and reduced its extent, which became nearly equal in all variants. Beer brewed at increased osmolarity was characterized by increased levels of diacetyl and pentanedione and lower levels of dimethylsulfide and acetaldehyde. Esters and higher alcohols displayed small variations irrespective of wort osmolarity or repitching. Increased wort osmolarity had no appreciable effect on the haze of green beer and accelerated beer clarification during maturation. In all variants, chill haze increased with repitching.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  7. Associative and dissociative mechanisms in the formation of phthalazine bridged organodiplatinum(II) complexes.

    PubMed

    Rashidi, Mehdi; Nabavizadeh, S Masoud; Zare, Ahad; Jamali, Sirous; Puddephatt, Richard J

    2010-09-20

    The reaction of phthalazine with the binuclear organoplatinum complexes [Me(2)Pt(μ-SMe(2))(μ-dppm)PtR(2)], R = Me, Ph, 4-tolyl or R(2) = (CH(2))(4), dppm = bis(diphenylphosphino)methane, gives the corresponding complexes [Me(2)Pt(μ-phthalazine)(μ-dppm)PtR(2)] by displacement of the bridging dimethylsulfide ligand. The structures of [Me(2)Pt(μ-SMe(2))(μ-dppm)PtMe(2)] and [Me(2)Pt(μ-phthalazine)(μ-dppm)PtMe(2)] have been determined. Kinetic studies show that the reactions occur mostly by a second order reaction when R = Me or R(2) = (CH(2))(4) but entirely by a first order reaction when R = Ph or 4-tolyl. Evidence is presented that the reactions when R = Me or R(2) = (CH(2))(4) can occur by either associative or dissociative mechanisms but that the reactions when R = Ph or 4-tolyl occur only by an unusual dissociative mechanism involving formation of an intermediate with a donor-acceptor Pt-Pt bond.

  8. Formation of methane and carbon dioxide from dimethylselenide in anoxic sediments and by a methanogenic bacterium

    USGS Publications Warehouse

    Oremland, Ronald S.; Zehr, Jon P.

    1986-01-01

    Anaerobic San Francisco Bay salt marsh sediments rapidly metabolized [14C]dimethylselenide (DMSe) to 14CH4 and 14CO2. Addition of selective inhibitors (2-bromoethanesulfonic acid or molybdate) to these sediments indicated that both methanogenic and sulfate-respiring bacteria could degrade DMSe to gaseous products. However, sediments taken from the selenium-contaminated Kesterson Wildlife Refuge produced only 14CO2 from [14C]DMSe, implying that methanogens were not important in the Kesterson samples. A pure culture of a dimethylsulfide (DMS)-grown methylotrophic methanogen converted [14C]DMSe to 14CH4 and14CO2. However, the organism could not grow on DMSe. Addition of DMS to either sediments or the pure culture retarded the metabolism of DMSe. This effect appeared to be caused by competitive inhibition, thereby indicating a common enzyme system for DMS and DMSe metabolism. DMSe appears to be degraded as part of the DMS pool present in anoxic environments. These results suggest that methylotrophic methanogens may demethylate methylated forms of other metals and metalloids found in nature.

  9. Marine microgels as a source of cloud condensation nuclei in the high Arctic.

    PubMed

    Orellana, Mónica V; Matrai, Patricia A; Leck, Caroline; Rauschenberg, Carlton D; Lee, Allison M; Coz, Esther

    2011-08-16

    Marine microgels play an important role in regulating ocean basin-scale biogeochemical dynamics. In this paper, we demonstrate that, in the high Arctic, marine gels with unique physicochemical characteristics originate in the organic material produced by ice algae and/or phytoplankton in the surface water. The polymers in this dissolved organic pool assembled faster and with higher microgel yields than at other latitudes. The reversible phase transitions shown by these Arctic marine gels, as a function of pH, dimethylsulfide, and dimethylsulfoniopropionate concentrations, stimulate the gels to attain sizes below 1 μm in diameter. These marine gels were identified with an antibody probe specific toward material from the surface waters, sized, and quantified in airborne aerosol, fog, and cloud water, strongly suggesting that they dominate the available cloud condensation nuclei number population in the high Arctic (north of 80°N) during the summer season. Knowledge about emergent properties of marine gels provides important new insights into the processes controlling cloud formation and radiative forcing, and links the biology at the ocean surface with cloud properties and climate over the central Arctic Ocean and, probably, all oceans.

  10. Evaluation of carbohydrate-cysteamine thiazolidines as pro-drugs for the treatment of cystinosis.

    PubMed

    Ramazani, Yasaman; Levtchenko, Elena N; Van Den Heuvel, Lambertus; Van Schepdael, Ann; Paul, Prasanta; Ivanova, Ekaterina A; Pastore, Anna; Hartman, Trina M; Price, Neil P J

    2017-02-01

    Cystinosis is a genetic disorder caused by malfunction of cystinosin and is characterized by accumulation of cystine. Cysteamine, the medication used in cystinosis, causes halitosis resulting in poor patient compliance. Halitosis is mainly caused by the formation of dimethylsulfide as the final product in the cysteamine metabolism pathway. We have synthesized carbohydrate-cysteamine thiazolidines, and hypothesized that the hydrolytic breakdown of cysteamine-thiazolidines can result in free cysteamine being released in target organs. To examine our hypothesis, we tested these analogs in vitro in patient-derived fibroblasts. Cystinotic fibroblasts were treated with different concentrations of arabinose-cysteamine, glucose-cysteamine and maltose-cysteamine. We demonstrated that the analogs break down into cysteamine extracellularly and might therefore not be fully taken up by the cells under the form of the pro-drug. Potential modifications of the analogs that enable their intracellular rather than extracellular breakdown, is necessary to pursue the potential of these analogs as pro-drugs.

  11. Simultaneous determination of eight common odors in natural water body using automatic purge and trap coupled to gas chromatography with mass spectrometry.

    PubMed

    Deng, Xuwei; Liang, Gaodao; Chen, Jun; Qi, Min; Xie, Ping

    2011-06-17

    Production and fate of taste and odor (T&O) compounds in natural waters are a pressing environmental issue. Simultaneous determination of these complex compounds (covering a wide range of boiling points) has been difficult. A simple and sensitive method for the determination of eight malodors products of cyanobacterial blooms was developed using automatic purge and trap (P&T) coupled with gas chromatography-mass spectrometry (GC-MS). This extraction and concentration technique is solvent-free. Dimethylsulfide (DMS), dimethyltrisulfide (DMTS), 2-isopropyl-3-methoxypyrazine (IPMP), 2-isobutyl-3-methoxypyrazine (IBMP), 2-methylisoborneol (MIB), β-cyclocitral, geosmin (GSM) and β-ionone were separated within 15.3 min. P&T uses trap #07 and high-purity nitrogen purge gas. The calibration curves of the eight odors show good linearity in the range of 1-500 ng/L with a correlation coefficient above 0.999 (levels=8) and with residuals ranging from approximately 83% to 124%. The limits of detection (LOD) (S/N=3) are all below 1.5 ng/L that of GSM is even lower at 0.08 ng/L. The relative standard deviations (RSD) are between 3.38% and 8.59% (n=5) and recoveries of the analytes from water samples of a eutrophic lake are between 80.54% and 114.91%. This method could be widely employed for monitoring these eight odors in natural waters.

  12. Environmental, biochemical and genetic drivers of DMSP degradation and DMS production in the Sargasso Sea.

    PubMed

    Levine, Naomi Marcil; Varaljay, Vanessa A; Toole, Dierdre A; Dacey, John W H; Doney, Scott C; Moran, Mary Ann

    2012-05-01

    Dimethylsulfide (DMS) is a climatically relevant trace gas produced and cycled by the surface ocean food web. Mechanisms driving intraannual variability in DMS production and dimethylsulfoniopropionate (DMSP) degradation in open-ocean, oligotrophic regions were investigated during a 10-month time-series at the Bermuda Atlantic Time-series Study site in the Sargasso Sea. Abundance and transcription of bacterial DMSP degradation genes, DMSP lyase enzyme activity, and DMS and DMSP concentrations, consumption rates and production rates were quantified over time and depth. This interdisciplinary data set was used to test current hypotheses of the role of light and carbon supply in regulating upper-ocean sulfur cycling. Findings supported UV-A-dependent phytoplankton DMS production. Bacterial DMSP degraders may also contribute significantly to DMS production when temperatures are elevated and UV-A dose is moderate, but may favour DMSP demethylation under low UV-A doses. Three groups of bacterial DMSP degraders with distinct intraannual variability were identified and niche differentiation was indicated. The combination of genetic and biochemical data suggest a modified 'bacterial switch' hypothesis where the prevalence of different bacterial DMSP degradation pathways is regulated by a complex set of factors including carbon supply, temperature and UV-A dose.

  13. Evidence of methanesulfonate utilizers in the Sargasso Sea metagenome.

    PubMed

    Leitão, Elsa; Moradas-Ferreira, Pedro; De Marco, Paolo

    2009-09-01

    Methanesulfonate (MSA) is one of the products of the photo-oxidation of dimethylsulfide in the atmosphere. The genes responsible for the import of MSA into the cell (msm EFGH) and for its oxidation to formaldehyde (msm ABCD) have been previously sequenced from the soil bacterium Methylosulfonomonas methylovora str. M2 while genes for an MSA monooxygenase have been sequenced from marine bacterium Marinosulfonomonas methylotropha str. TR3. We performed a sequence-based screening of the Sargasso Sea metagenome for homologues of the MSA monooxygenase (MSAMO) and MSA import genes. Our search retrieved one scaffold bearing genes with high identity to the msm ABCD cluster plus two scaffolds bearing genes highly identical to the msm EFGH operon. We increased the available data by sequencing two metagenome plasmids, which revealed more msm genes. In these three cases synteny with the original msm operons was revealed. We also retrieved several singletons showing high identity to shorter segments of the msm clusters or individual msm genes. Furthermore, a characteristic 26-aa internal spacer of the MsmA Rieske-type motif was conserved. Our findings support the case for a significant role of MSA degraders in the marine sulfur cycle and seem to suggest that they may be prominent members of the methylotrophic community in surface ocean waters.

  14. Climate Change and Aerosol Feedbacks

    NASA Astrophysics Data System (ADS)

    Norman, Ann-Lise

    2008-05-01

    Climate instability is expected as mixing ratios of greenhouse gases in the Earth's atmosphere increase. The current trend in rising temperature can be related to anthropogenic greenhouse gas emissions. However, this trend may change as feedback mechanisms amplify; one of the least-understood aspects of climate change. Formation of cloud condensation nuclei from rising sulfate concentrations in the atmosphere may counteract the current warming trend. A key point is where the sulfate, and cloud condensation nuclei are formed. Is cloud formation widespread or localized near sulfate emission sources? A major source of atmospheric sulfate is dimethylsulfide, a compound related to biotic turnover in the surface ocean that constitutes a widespread natural source of aerosols over the remote ocean. A second major source contributing a significant proportion of atmospheric sulfate in the northern hemisphere is produced over continents from industrial activities and fossil fuel combustion. Distinguishing the source of sulfate in well-mixed air is important so that relationships with cloud formation, sea-ice in polar regions, and albedo can be explored. This distinction in sulfate sources can be achieved using isotope apportionment techniques. Recent measurements show an increase in biogenic sulfate coincident with rising temperatures in the Arctic and large amounts sulfur from DMS oxidation over the Atlantic, potentially indicating a widespread biotic feedback to warming over northern oceans.

  15. The averaging effect of odorant mixing as determined by air dilution sensory tests: a case study on reduced sulfur compounds.

    PubMed

    Kim, Ki-Hyun

    2011-01-01

    To learn more about the effects of mixing different odorants, a series of air dilution sensory (ADS) tests were conducted using four reduced sulfur compounds [RSC: hydrogen sulfide (H(2)S), methanethiol (CH(3)SH), dimethylsulfide (DMS), and dimethyldisulfide (DMDS)] at varying concentration levels. The tests were initially conducted by analyzing samples containing single individual RSCs at a wide range of concentrations. The resulting data were then evaluated to define the empirical relationship for each RSC between the dilution-to-threshold (D/T) ratio and odor intensity (OI) scaling. Based on the relationships defined for each individual RSC, the D/T ratios were estimated for a synthetic mixture of four RSCs. The effect of mixing was then examined by assessing the relative contribution of each RSC to those estimates with the aid of the actually measured D/T values. This stepwise test confirmed that the odor intensity of the synthetic mixture is not governed by the common theoretical basis (e.g., rule of additivity, synergism, or a stronger component model) but is best represented by the averaged contribution of all RSC components. The overall results of this study thus suggest that the mixing phenomenon between odorants with similar chemical properties (like RSC family) can be characterized by the averaging effect of all participants.

  16. Detoxification of hydrogen sulfide and methanethiol in the cecal mucosa.

    PubMed

    Levitt, M D; Furne, J; Springfield, J; Suarez, F; DeMaster, E

    1999-10-01

    Colonic bacteria liberate large quantities of the highly toxic gases hydrogen sulfide (H(2)S) and methanethiol (CH(3)SH). The colonic mucosa presumably has an efficient means of detoxifying these compounds, which is thought to occur through methylation of H(2)S to CH(3)SH and CH(3)SH to dimethylsulfide (CH(3)SCH(3)). We investigated this detoxification pathway by incubating rat cecal mucosal homogenates with gas containing H(2)S, CH(3)SH, or CH(3)SCH(3). Neither CH(3)SH nor CH(3)SCH(3) was produced during H(2)S catabolism, whereas catabolism of CH(3)SH liberated H(2)S but not CH(3)SCH(3). Thus, H(2)S and CH(3)SH are not detoxified by methylation to CH(3)SCH(3). Rather, CH(3)SH is demethylated to H(2)S, and H(2)S is converted to nonvolatile metabolites. HPLC analysis of the homogenate showed the metabolite to be primarily thiosulfate. Analysis of cecal venous blood obtained after intracecal instillation of H(2)(35)S revealed that virtually all absorbed H(2)S had been oxidized to thiosulfate. The oxidation rate of H(2)S by colonic mucosa was 10,000 times greater than the reported methylation rate. Conversion to thiosulfate appears to be the mechanism whereby the cecal mucosa protects itself from the injurious effects of H(2)S and CH(3)SH, and defects in this detoxification possibly could play a role in colonic diseases such as ulcerative colitis.

  17. Volatile metabolites of higher plant crops as a photosynthesizing life support system component under temperature stress at different light intensities.

    PubMed

    Gitelson, I I; Tikhomirov, A A; Parshina, O V; Ushakova, S A; Kalacheva, G S

    2003-01-01

    The effect of elevated temperatures of 35 and 45 degrees C (at the intensities of photosynthetically active radiation 322, 690 and 1104 micromoles m-2 s-1) on the photosynthesis, respiration, and qualitative and quantitative composition of the volatiles emitted by wheat (Triticum aestuvi L., cultivar 232) crops was investigated in growth chambers. Identification and quantification of more than 20 volatile compounds (terpenoids--alpha-pinene, delta 3 carene, limonene, benzene, alpha- and trans-caryophyllene, alpha- and gamma-terpinene, their derivatives, aromatic hydrocarbons, etc.) were conducted by gas chromatograph/mass spectrometry. Under light intensity of 1104 micromoles m-2 s-1 heat resistance of photosynthesis and respiration increased at 35 degrees C and decreased at 45 degrees C. The action of elevated temperatures brought about variations in the rate and direction of the synthesis of volatile metabolites. The emission of volatile compounds was the greatest under a reduced irradiation of 322 micromoles m-2 s-1 and the smallest under 1104 micromoles m-2 s-1 at 35 degrees C. During the repair period, the contents and proportions of volatile compounds were different from their initial values, too. The degree of disruption and the following recovery of the functional state depended on the light intensity during the exposure to elevated temperatures. The investigation of the atmosphere of the growth chamber without plants has revealed the substances that were definitely technogenic in origin: tetramethylurea, dimethylsulfide, dibutylsulfide, dibutylphthalate, and a number of components of furan and silane nature.

  18. How phosphorus limitation can control climatic gas emission

    NASA Astrophysics Data System (ADS)

    Gypens, Nathalie; Borges, Alberto V.; Speeckaert, Gaelle; Ghyoot, Caroline

    2015-04-01

    Anthropogenic activities severely increased river nutrient [nitrogen (N) and phosphorus (P)] loads to European coastal areas. However, specific nutrient reduction policies implemented since the late 1990's have considerably reduced P loads, while N is maintained. In the Southern North Sea, the resulting N: P: Si imbalance (compared to phytoplankton requirements) stimulated the growth of Phaeocystis colonies modifying the functioning of the ecosystem and, therefore, the carbon cycle but also the biogenic sulphur cycle, Phaeocystis being a significant producer of DMSP (dimethylsulphide propionate), the precursor of dimethylsulfide (DMS). In this application, the mechanistic MIRO-BIOGAS model is used to investigate the effects of changing N and P loads on ecosystem structure and their impact on DMS and CO2 emissions. In particular, competition for P between phytoplankton groups (diatoms vs Phaeocystis colonies) but also between phytoplankton and bacteria is explored. The ability of autotroph and heterotroph organism to use dissolved organic phosphorus (DOP) as P nutrient source is also explored and its effect on climatic gas emission estimated. Simulations were done from 1950 to 2010 and different nutrient limiting conditions are analyzed.

  19. Isolation and molecular detection of methylotrophic bacteria occurring in the human mouth.

    PubMed

    Anesti, Vasiliki; McDonald, Ian R; Ramaswamy, Meghna; Wade, William G; Kelly, Donovan P; Wood, Ann P

    2005-08-01

    Diverse methylotrophic bacteria were isolated from the tongue, and supra- and subgingival plaque in the mouths of volunteers and patients with periodontitis. One-carbon compounds such as dimethylsulfide in the mouth are likely to be used as growth substrates for these organisms. Methylotrophic strains of Bacillus, Brevibacterium casei, Hyphomicrobium sulfonivorans, Methylobacterium, Micrococcus luteus and Variovorax paradoxus were characterized physiologically and by their 16S rRNA gene sequences. The type strain of B. casei was shown to be methylotrophic. Enzymes of methylotrophic metabolism were characterized in some strains, and activities consistent with growth using known pathways of C1-compound metabolism demonstrated. Genomic DNA from 18 tongue and dental plaque samples from nine volunteers was amplified by the polymerase chain reaction using primers for the 16S rRNA gene of Methylobacterium and the mxaF gene of methanol dehydrogenase. MxaF was detected in all nine volunteers, and Methylobacterium was detected in seven. Methylotrophic activity is thus a feature of the oral bacterial community.

  20. CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis.

    PubMed

    Galí, Martí; Kieber, David J; Romera-Castillo, Cristina; Kinsey, Joanna D; Devred, Emmanuel; Pérez, Gonzalo L; Westby, George R; Marrasé, Cèlia; Babin, Marcel; Levasseur, Maurice; Duarte, Carlos M; Agustí, Susana; Simó, Rafel

    2016-12-20

    Photolysis is a major removal pathway for the biogenic gas dimethylsulfide (DMS) in the surface ocean. Here we tested the hypothesis that apparent quantum yields (AQY) for DMS photolysis varied according to the quantity and quality of its photosensitizers, chiefly chromophoric dissolved organic matter (CDOM) and nitrate. AQY compiled from the literature and unpublished studies ranged across 3 orders of magnitude at the 330 nm reference wavelength. The smallest AQY(330) were observed in coastal waters receiving major riverine inputs of terrestrial CDOM (0.06-0.5 m(3) (mol quanta)(-1)). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m(3) (mol quanta)(-1). The largest AQY(330), up to 34 m(3) (mol quanta)(-1)), were seen in the Southern Ocean potentially associated with upwelling. Despite the large AQY variability, daily photolysis rate constants at the sea surface spanned a smaller range (0.04-3.7 d(-1)), mainly because of the inverse relationship between CDOM absorption and AQY. Comparison of AQY(330) with CDOM spectral signatures suggests there is an interplay between CDOM origin (terrestrial versus marine) and photobleaching that controls variations in AQYs, with a secondary role for nitrate. Our results can be used for regional or large-scale assessment of DMS photolysis rates in future studies.

  1. Marine microgels as a source of cloud condensation nuclei in the high Arctic

    PubMed Central

    Orellana, Mónica V.; Matrai, Patricia A.; Leck, Caroline; Rauschenberg, Carlton D.; Lee, Allison M.; Coz, Esther

    2011-01-01

    Marine microgels play an important role in regulating ocean basin-scale biogeochemical dynamics. In this paper, we demonstrate that, in the high Arctic, marine gels with unique physicochemical characteristics originate in the organic material produced by ice algae and/or phytoplankton in the surface water. The polymers in this dissolved organic pool assembled faster and with higher microgel yields than at other latitudes. The reversible phase transitions shown by these Arctic marine gels, as a function of pH, dimethylsulfide, and dimethylsulfoniopropionate concentrations, stimulate the gels to attain sizes below 1 μm in diameter. These marine gels were identified with an antibody probe specific toward material from the surface waters, sized, and quantified in airborne aerosol, fog, and cloud water, strongly suggesting that they dominate the available cloud condensation nuclei number population in the high Arctic (north of 80°N) during the summer season. Knowledge about emergent properties of marine gels provides important new insights into the processes controlling cloud formation and radiative forcing, and links the biology at the ocean surface with cloud properties and climate over the central Arctic Ocean and, probably, all oceans. PMID:21825118

  2. Global alteration of ocean ecosystem functioning due to increasing human CO2 emissions

    PubMed Central

    Nagelkerken, Ivan; Connell, Sean D.

    2015-01-01

    Rising anthropogenic CO2 emissions are anticipated to drive change to ocean ecosystems, but a conceptualization of biological change derived from quantitative analyses is lacking. Derived from multiple ecosystems and latitudes, our metaanalysis of 632 published experiments quantified the direction and magnitude of ecological change resulting from ocean acidification and warming to conceptualize broadly based change. Primary production by temperate noncalcifying plankton increases with elevated temperature and CO2, whereas tropical plankton decreases productivity because of acidification. Temperature increases consumption by and metabolic rates of herbivores, but this response does not translate into greater secondary production, which instead decreases with acidification in calcifying and noncalcifying species. This effect creates a mismatch with carnivores whose metabolic and foraging costs increase with temperature. Species diversity and abundances of tropical as well as temperate species decline with acidification, with shifts favoring novel community compositions dominated by noncalcifiers and microorganisms. Both warming and acidification instigate reduced calcification in tropical and temperate reef-building species. Acidification leads to a decline in dimethylsulfide production by ocean plankton, which as a climate gas, contributes to cloud formation and maintenance of the Earth’s heat budget. Analysis of responses in short- and long-term experiments and of studies at natural CO2 vents reveals little evidence of acclimation to acidification or temperature changes, except for microbes. This conceptualization of change across whole communities and their trophic linkages forecast a reduction in diversity and abundances of various key species that underpin current functioning of marine ecosystems. PMID:26460052

  3. Role of sea ice and hemispheric circulation mode on sulphur oxidised compounds (Methanesulfonate and Sulfate) in the Artic aerosol

    NASA Astrophysics Data System (ADS)

    Becagli, Silvia; Calzolai, Giulia; Dayan, Uri; Di Biagio, Claudia; di Sarra, Alcide; Frosini, Daniele; Mazzola, Mauro; Rugi, Francesco; Severi, Mirko; Traversi, Rita; Vitale, Vito; Udisti, Roberto

    2013-04-01

    The recent decline in sea ice cover in the Arctic Ocean is expected to affect the regional radiation budget and to influence the ocean-atmosphere exchange of dimethylsulfide (DMS), thus the amount of biogenic aerosols formed from its atmospheric oxidation, such as methanesulfonate (MS-) and non-sea salt sulphate (nssSO42-). This study examines the temporal evolution of atmospheric MS- and nssSO42-, as measured in atmospheric aerosols, at Ny-Ålesund, (78.9°N, 11.9°E, Svalbard islands) and Thule (76.5°N, 68.8°W, Greenland) during three years (2010-12). Aerosol sampling was carried out using a PM10 sampler with Teflon filters, and a 12-stage impactor (SDI, Small Deposit-area Impactor) with polycarbonate filters. Analyses were performed by ion chromatography, for ion composition, and ICP-SFMS, for selected metals; both techniques are sufficiently sensitive, accurate, and reproducible to be applied to very low atmospheric load of aerosol particles, typical of remote polar regions. The evolution of MS- and nssSO4 concentrations was analysed as a function of speciation (as acidic species or ammonium salt), size distribution, and airmass pathways. This study reveals that nssSO4 is meanly associated with long range transport from anthropic sources, and presents a relative maximum in spring. Conversely, MS- arises from natural local sources and shows a peak in mid-summer. A large interannual variability is observed in MS- concentration with values in spring-summer 2010 in both the stations higher than in the other summers. In the previous winter a larger sea ice extent and larger sea ice melting surface in the following spring were observed. Arrigo et al. (2008) have observed a 22% increase in the annual primary productivity, that has been attributed to a longer phytoplankton growing season connected with the progressive decline in sea ice coverage in the Arctic over the past decade. Modeling results (Gabric et al., 2005) suggest that an increase in DMS production would

  4. Influence of Sea Ice on Arctic Marine Sulfur Biogeochemistry in the Community Climate System Model

    SciTech Connect

    Deal, Clara; Jin, Meibing

    2013-06-30

    Global climate models (GCMs) have not effectively considered how responses of arctic marine ecosystems to a warming climate will influence the global climate system. A key response of arctic marine ecosystems that may substantially influence energy exchange in the Arctic is a change in dimethylsulfide (DMS) emissions, because DMS emissions influence cloud albedo. This response is closely tied to sea ice through its impacts on marine ecosystem carbon and sulfur cycling, and the ice-albedo feedback implicated in accelerated arctic warming. To reduce the uncertainty in predictions from coupled climate simulations, important model components of the climate system, such as feedbacks between arctic marine biogeochemistry and climate, need to be reasonably and realistically modeled. This research first involved model development to improve the representation of marine sulfur biogeochemistry simulations to understand/diagnose the control of sea-ice-related processes on the variability of DMS dynamics. This study will help build GCM predictions that quantify the relative current and possible future influences of arctic marine ecosystems on the global climate system. Our overall research objective was to improve arctic marine biogeochemistry in the Community Climate System Model (CCSM, now CESM). Working closely with the Climate Ocean Sea Ice Model (COSIM) team at Los Alamos National Laboratory (LANL), we added 1 sea-ice algae and arctic DMS production and related biogeochemistry to the global Parallel Ocean Program model (POP) coupled to the LANL sea ice model (CICE). Both CICE and POP are core components of CESM. Our specific research objectives were: 1) Develop a state-of-the-art ice-ocean DMS model for application in climate models, using observations to constrain the most crucial parameters; 2) Improve the global marine sulfur model used in CESM by including DMS biogeochemistry in the Arctic; and 3) Assess how sea ice influences DMS dynamics in the arctic marine

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

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

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

  6. Real-time analysis of sulfur-containing volatiles in Brassica plants infested with root-feeding Delia radicum larvae using proton-transfer reaction mass spectrometry

    PubMed Central

    van Dam, Nicole M.; Samudrala, Devasena; Harren, Frans J. M.; Cristescu, Simona M

    2012-01-01

    Background and aims Plants damaged by herbivores emit a variety of volatile organic compounds (VOCs). Here we used proton-transfer reaction mass spectrometry (PTR-MS) as a sensitive detection method for online analysis of herbivore-induced VOCs. Previously, it was found that Brassica nigra plants emit several sulfur-containing VOCs when attacked by cabbage root fly (Delia radicum) larvae with m/z 60 as a marker for the formation of allylisothiocyanate from the glucosinolate sinigrin. We tested the hypothesis that m/z 60 emission occurs only in plants with sinigrin in their roots. Additionally, we tested the hypothesis that methanethiol, dimethylsulfide and dimethyldisulfide are only emitted after larval infestation. Methodology Proton-transfer reaction mass spectrometry was used to track sulfur-containing VOCs from six different species of Brassica over time. The roots were either artificially damaged or infested with cabbage root fly larvae. Glucosinolate profiles of the roots were analysed using high-pressure liquid chromatography and compared with VOC emissions. Principal results Brassica nigra, B. juncea and B. napus primarily emitted m/z 60 directly after artificial damage or root fly infestation. Sulfide and methanethiol emissions from B. nigra and B. juncea also increased after larval damage but much later (6–12 h after damage). Brassica rapa, B. oleracea and B. carinata principally emitted methanethiol after artificial and after larval damage. Brassica oleracea and B. carinata showed some increase in m/z 60 emission after larval damage. Comparison with root glucosinolate profiles revealed that sinigrin cannot be the only precursor for m/z 60. Conclusions The principal compound emitted after root damage is determined by the plant species, and not by damage type or root glucosinolate composition. Once determined, the principal compounds may be used as markers for identifying damaged or infested plants. Further analyses of plant enzymes involved in the

  7. Characterization of odor released during handling of swine slurry: Part I. Relationship between odorants and perceived odor concentrations

    NASA Astrophysics Data System (ADS)

    Blanes-Vidal, V.; Hansen, M. N.; Adamsen, A. P. S.; Feilberg, A.; Petersen, S. O.; Jensen, B. B.

    Odor emission from livestock production systems is a major nuisance in many rural areas. This study aimed at determining the major airborne chemical compounds responsible for the unpleasant odor perceived in swine facilities during slurry handling, and at proposing predictive models of odor concentration (OC) based on the concentrations of specific odorants in the air. A multivariate data analysis strategy involving principal components analysis and multiple linear regressions was implemented to analyze the relationships between concentration of 35 gases (measured by GC/MS or gas detection tubes), and the overall OC perceived by sensory analysis. The study compiled data on the concentration of odor and odorants, measured in the headspace of 24 unstored and stored slurry samples collected from three different types of production units on 8 commercial swine farms. Among all the measured constituents, OC was found to have the highest correlation with the sulfur containing compounds (i.e. hydrogen sulfide, dimethylsulfide, dimethyldisulfide, dimethyltrisulfide). The concentration of hydrogen sulfide accounted for 68% of the variation in OC above the stirred slurry samples. The highest concentrations of volatile organic compounds were observed for phenols and indoles, which made a significant contribution to the overall OC when the slurry was fresh. The contribution of ammonia to the OC was only significant in the absence of hydrogen sulfide. The precision of predictive models of OC based on the concentration of specific odorants in the air was satisfactory ( R2 between 0.66 and 0.89). Hence, this study suggests that monitoring of specific odor compounds released from agitated swine slurry can be used to predict the concentration of odor perceived close to the source (e.g. at storage units), allowing the assessment of odor nuisance potentials.

  8. DMS cycle in the marine ocean-atmosphere system a global model study

    NASA Astrophysics Data System (ADS)

    Kloster, S.; Feichter, J.; Maier-Reimer, E.; Six, K. D.; Stier, P.; Wetzel, P.

    2005-08-01

    A global coupled ocean-atmosphere modeling system is established to study the production of Dimethylsulfide (DMS) in the ocean, the DMS flux to the atmosphere, and the resulting sulfur concentrations in the atmosphere. The DMS production and consumption processes in the ocean are simulated in the marine biogeochemistry model HAMOCC5, embedded in a ocean general circulation model (MPI-OM). The atmospheric model ECHAM5 is extended by the microphysical aerosol model HAM, treating the sulfur chemistry in the atmosphere and the evolution of the microphysically interacting internally- and externally mixed aerosol populations.

    We simulate a global annual mean DMS sea surface concentration of 1.8 nmol/l, a DMS emission of 28 Tg(S)/yr, a DMS burden in the atmosphere of 0.077 Tg(S), and a DMS lifetime of 1.0 days. To quantify the role of DMS in the atmospheric sulfur cycle we simulate the relative contribution of DMS-derived SO2 and SO4-2 to the total atmospheric sulfur concentrations. DMS contributes 25% to the global annually averaged SO2 column burden. For SO4-2 the contribution is 27%.

    The coupled model setup allows the evaluation of the simulated DMS quantities with measurements taken in the ocean and in the atmosphere. The simulated global distribution of DMS sea surface concentrations compares reasonably well with measurements. The comparison to SO4-2 surface concentration measurements in regions with a high DMS contribution to SO4-2 shows an overestimation by the model. This overestimation is most pronounced in the biologically active season with high DMS emissions and most likely caused by a too high simulated SO4-2 yield from DMS oxidation.

  9. Single-particle characterization of summertime Antarctic aerosols collected at King George Island using quantitative energy-dispersive electron probe X-ray microanalysis and attenuated total reflection Fourier transform-infrared imaging techniques.

    PubMed

    Maskey, Shila; Geng, Hong; Song, Young-Chul; Hwang, Heejin; Yoon, Young-Jun; Ahn, Kang-Ho; Ro, Chul-Un

    2011-08-01

    Single-particle characterization of Antarctic aerosols was performed to investigate the impact of marine biogenic sulfur species on the chemical compositions of sea-salt aerosols in the polar atmosphere. Quantitative energy-dispersive electron probe X-ray microanalysis was used to characterize 2900 individual particles in 10 sets of aerosol samples collected between March 12 and 16, 2009 at King Sejong Station, a Korean scientific research station located at King George Island in the Antarctic. Two size modes of particles, i.e., PM(2.5-10) and PM(1.0-2.5), were analyzed, and four types of particles were identified, with sulfur-containing sea-salt particles being the most abundant, followed by genuine sea-salt particles without sulfur species, iron-containing particles, and other species including CaCO(3)/CaMg(CO(3))(2), organic carbon, and aluminosilicates. When a sulfur-containing sea-salt particle showed an atomic concentration ratio of sulfur to sodium of >0.083 (seawater ratio), it is regarded as containing nonsea-salt sulfate (nss-SO(4)(2-)) and/or methanesulfonate (CH(3)SO(3)(-)), which was supported by attenuated total reflection Fourier transform-infrared imaging measurements. These internal mixture particles of sea-salt/CH(3)SO(3)(-)/SO(4)(2-) were very frequently encountered. As nitrate-containing particles were not encountered, and the air-masses for all of the samples originated from the Pacific Ocean (based on 5-day backward trajectories), the oxidation of dimethylsulfide (DMS) emitted from phytoplanktons in the ocean is most likely to be responsible for the formation of the mixed sea-salt/CH(3)SO(3)(-)/SO(4)(2-) particles.

  10. Emissions of Monoterpenes and DMS from Corn and their Influence on Nighttime Chemical Processing of Nitrogen Oxides

    NASA Astrophysics Data System (ADS)

    Graus, M.; De Gouw, J. A.; Brown, S. S.; Williams, E. J.; Eller, A. S.; Gilman, J. B.; Lerner, B. M.; Fall, R.; Warneke, C.

    2012-12-01

    In the United States large amounts of corn are grown for the use as animal feed, for the food industry and for the production of fuel ethanol. In 2012 the acreage of corn planted was 390,000 km2 covering over 4.2% of the US land surface. The BioCORN 2011 field experiment took place in summer 2011 to look at ecosystem fluxes of volatile organic compounds (VOCs) from a cornfield in Colorado during the period of rapid biomass increase and the development of flowers and ears. Eddy covariance, soil and leaf cuvette measurements using various instruments including PTR-MS, NI-PT-CIMS and GC-MS were used to determine fluxes of VOCs, CO2 and NOx. Corn plants emit significant amounts of VOCs with methanol being the largest emission and smaller emissions of other VOCs such acetone, acetaldehyde, monoterpene and dimethylsulfide (DMS). During the day VOCs mainly react with hydroxyl radicals and during the night with nitrate radicals (NO3), where emissions from corn may act as a sink for reactive nitrogen. DMS, mainly emitted from oceans and to a lesser extent from terrestrial vegetation, had a diurnal cycle: mixing ratios high during the night, but fluxes high during the day. DMS was found to dominate the reactivity of NO3 followed by monoterpenes and the heterogeneous loss of N2O5, which has implications for the nighttime chemistry. Other results of BioCORN 2011 on VOC emissions from corn and their impact on atmospheric chemistry will be presented and discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2002-05-01

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

  12. Clustered Genes Encoding the Methyltransferases of Methanogenesis from Monomethylamine

    PubMed Central

    Burke, Stephen A.; Lo, Sam L.; Krzycki, Joseph A.

    1998-01-01

    Coenzyme M (CoM) is methylated during methanogenesis from monomethyamine in a reaction catalyzed by three proteins. Using monomethylamine, a 52-kDa polypeptide termed monomethylamine methyltransferase (MMAMT) methylates the corrinoid cofactor bound to a second polypeptide, monomethylamine corrinoid protein (MMCP). Methylated MMCP then serves as a substrate for MT2-A, which methylates CoM. The genes for these proteins are clustered on 6.8 kb of DNA in Methanosarcina barkeri MS. The gene encoding MMCP (mtmC) is located directly upstream of the gene encoding MMAMT (mtmB). The gene encoding MT2-A (mtbA) was found 1.1 kb upstream of mtmC, but no obvious open reading frame was found in the intergenic region between mtbA and mtmC. A single monocistronic transcript was found for mtbA that initiated 76 bp from the translational start. Separate transcripts of 2.4 and 4.7 kb were detected, both of which carried mtmCB. The larger transcript also encoded mtmP, which is homologous to the APC family of cationic amine permeases and may therefore encode a methylamine permease. A single transcriptional start site was found 447 bp upstream of the translational start of mtmC. MtmC possesses the corrinoid binding motif found in corrinoid proteins involved in dimethylsulfide- and methanol-dependent methanogenesis, as well as in methionine synthase. The open reading frame of mtmB was interrupted by a single in-frame, midframe, UAG codon which was also found in mtmB from M. barkeri NIH. A mechanism that circumvents UAG-directed termination of translation must operate during expression of mtmB in this methanogen. PMID:9642198

  13. Clustered genes encoding the methyltransferases of methanogenesis from monomethylamine.

    PubMed

    Burke, S A; Lo, S L; Krzycki, J A

    1998-07-01

    Coenzyme M (CoM) is methylated during methanogenesis from monomethyamine in a reaction catalyzed by three proteins. Using monomethylamine, a 52-kDa polypeptide termed monomethylamine methyltransferase (MMAMT) methylates the corrinoid cofactor bound to a second polypeptide, monomethylamine corrinoid protein (MMCP). Methylated MMCP then serves as a substrate for MT2-A, which methylates CoM. The genes for these proteins are clustered on 6.8 kb of DNA in Methanosarcina barkeri MS. The gene encoding MMCP (mtmC) is located directly upstream of the gene encoding MMAMT (mtmB). The gene encoding MT2-A (mtbA) was found 1.1 kb upstream of mtmC, but no obvious open reading frame was found in the intergenic region between mtbA and mtmC. A single monocistronic transcript was found for mtbA that initiated 76 bp from the translational start. Separate transcripts of 2.4 and 4.7 kb were detected, both of which carried mtmCB. The larger transcript also encoded mtmP, which is homologous to the APC family of cationic amine permeases and may therefore encode a methylamine permease. A single transcriptional start site was found 447 bp upstream of the translational start of mtmC. MtmC possesses the corrinoid binding motif found in corrinoid proteins involved in dimethylsulfide- and methanol-dependent methanogenesis, as well as in methionine synthase. The open reading frame of mtmB was interrupted by a single in-frame, midframe, UAG codon which was also found in mtmB from M. barkeri NIH. A mechanism that circumvents UAG-directed termination of translation must operate during expression of mtmB in this methanogen.

  14. Climatic context of the First Aerosol Characterization Experiment (ACE 1): A meteorological and chemical overview

    NASA Astrophysics Data System (ADS)

    Hainsworth, A. H. W.; Dick, A. L.; Gras, J. L.

    1998-01-01

    During the intensive field operations period (November 15 to December 14, 1995) of the First Aerosol Characterization Experiment (ACE 1) cold front activity was generally above average, resulting in below average temperatures, pressures, and rainfall. The principal cause was the presence for much of the experiment of a long wave trough. This trough was mobile, traversing the ACE area during the project, with some warm anomalies evident in the areas under the influence of the long wave ridges. There is evidence of greater convective activity than normal possibly leading to a slightly deeper than average mixing layer. A greater west to northwesterly component to the air flow than average during November appears to have led to higher than average concentrations of radon and particles in the clean, marine or "baseline" sector at Cape Grim (190° to 280°). This is likely to have resulted from inclusion of continental air from western parts of the Australian mainland in the baseline sector winds. Although aerosol-bound sulfur species were generally near their normal concentrations across the ACE 1 area, the overall pattern including atmospheric dimethylsulfide suggests slightly higher than usual sulfur species levels in the southern part of the region and lower concentrations in the northern part during November. This could be related to changes in marine biogenie productivity, air-sea exchange, or atmospheric removal. In December, the changing long wave pattern brought an increase in south and southwesterly flow over the entire region. The baseline sector became less affected by continental species, but it appears that the colder conditions brought by this pattern have led to lower than usual atmospheric concentrations of biogenie species, as the region went into one of the coldest summers on record.

  15. The Effects of Trimethylamine and Organic Matter Additions on the Stable Carbon Isotopic Composition of Methane Produced in Hypersaline Microbial Mat Environments

    NASA Astrophysics Data System (ADS)

    Kelley, C. A.; Nicholson, B. E.; Beaudoin, C. S.; Detweiler, A. M.; Bebout, B.

    2014-12-01

    Methane production has been observed in a number of hypersaline environments, and it is generally thought that this methane is produced through the use of non-competitive substrates, such as the methylamines, methanol and dimethylsulfide. The stable carbon isotopic composition of the produced methane has suggested that the methanogens are operating under conditions of substrate limitation. We investigated substrate limitation in gypsum-hosted endoevaporite and soft mat hypersaline environments by the additions of trimethylamine, a non-competitive substrate for methanogenesis, and dried microbial mat, a source of natural organic matter. The δ13C values of the methane produced after amendments were compared to those in unamended control vials. At all hypersaline sites investigated, the δ13C values of the methane produced in the amended vials were statistically lower (by 10 to 71 ‰) than the unamended controls, supporting the hypothesis of substrate limitation at these sites. When substrates were added to the incubation vials, the methanogens within the vials fractionated carbon isotopes to a greater degree, resulting in the production of more 13C-depleted methane. Trimethylamine-amended samples produced lower methane δ13C values than the mat-amended samples. This difference in the δ13C values between the two types of amendments could be due to differences in isotope fractionation associated with the dominant methane production pathway (or substrate used) within the vials, with trimethylamine being the main substrate used in the trimethylamine-amended vials. We hypothesize that increased natural organic matter in the mat-amended vials would increase fermentation rates, leading to higher H2 concentrations and increased CO2/H2 methanogenesis.

  16. Effects of dust additions on phytoplankton growth and DMS production in high CO2 northeast Pacific HNLC waters

    NASA Astrophysics Data System (ADS)

    Mélançon, J.; Levasseur, M.; Lizotte, M.; Scarratt, M.; Tremblay, J.-É.; Tortell, P.; Yang, G.-P.; Shi, G.-Y.; Gao, H.-W.; Semeniuk, D. M.; Robert, M.; Arychuk, M.; Johnson, K.; Sutherland, N.; Davelaar, M.; Nemcek, N.; Peña, A.; Richardson, W.

    2015-08-01

    Ocean acidification (OA) is likely to have an effect on the fertilizing potential of desert dust in high-nutrient, low-chlorophyll oceanic regions, either by modifying Fe speciation and bioavailability, or by altering phytoplankton Fe requirements and acquisition. To address this issue, short incubations (4 days) of northeast subarctic Pacific waters enriched with either FeSO4 or dust, and set at pH 8.0 (in situ) and 7.8 were conducted in August 2010. We assessed the impact of a decrease in pH on dissolved Fe concentration, phytoplankton biomass, taxonomy and productivity, and the production of dimethylsulfide (DMS) and its algal precursor dimethylsulfoniopropionate (DMSP). Chlorophyll a (chl a) remained unchanged in the controls and doubled in both the FeSO4-enriched and dust-enriched incubations, confirming the Fe-limited status of the plankton assemblage during the experiment. In the acidified treatments, a significant reduction (by 16-38 %) of the final concentration of chl a was measured compared to their non-acidified counterparts, and a 15 % reduction in particulate organic carbon (POC) concentration was measured in the dust-enriched acidified treatment compared to the dust-enriched non-acidified treatment. FeSO4 and dust additions had a fertilizing effect mainly on diatoms and cyanobacteria. Lowering the pH affected mostly the haptophytes, but pelagophyte concentrations were also reduced in some acidified treatments. Acidification did not significantly alter DMSP and DMS concentrations. These results show that dust deposition events in a low-pH iron-limited Northeast subarctic Pacific are likely to stimulate phytoplankton growth to a lesser extent than in today's ocean during the few days following fertilization and point to a low initial sensitivity of the DMSP and DMS dynamics to OA.

  17. Dust in an acidified ocean: iron bioavailability, phytoplankton growth and DMS

    NASA Astrophysics Data System (ADS)

    Mélançon, J.; Levasseur, M.; Lizotte, M.; Scarratt, M. G.; Tremblay, J. E.; Tortell, P. D.; Yang, G.; Shi, G. Y.; Gao, H.; Semeniuk, D.; Robert, M.; Arychuk, M.; Johnson, K.; Sutherland, N.; Davelaar, M.; Nemcek, N.; Pena, A.; Richardson, W.

    2015-12-01

    Ocean acidification (OA) is likely to have an effect on the fertilizing potential of desert dust in high-nutrient, low-chlorophyll oceanic regions, either by modifying Fe speciation and bioavailability, or by altering phytoplankton Fe requirements and acquisition. To address this issue, short incubations (4 days) of northeast subarctic Pacific waters enriched with either FeSO4 or dust, and maintained at pH 8.0 (in situ) and 7.8 were conducted in August 2010. We assessed the impact of a decrease in pH on dissolved Fe concentration, phytoplankton biomass, taxonomy and productivity, and the production of dimethylsulfide (DMS) and its algal precursor dimethylsulfoniopropionate (DMSP). Chlorophyll a (chl a) remained unchanged in the controls and doubled in both the FeSO4-enriched and dust-enriched incubations, confirming the Fe-limited status of the plankton assemblage during the experiment. In the acidified treatments, a significant reduction (by 16-38%) of the final concentration of chl a was measured compared to their non-acidified counterparts, and a 15% reduction in particulate organic carbon (POC) concentration was measured in the dust-enriched acidified treatment compared to the dust-enriched non-acidified treatment. FeSO4 and dust additions had a fertilizing effect mainly on diatoms and cyanobacteria. Lowering the pH affected mostly the haptophytes, but pelagophyte concentrations were also reduced in some acidified treatments. Acidification did not significantly alter DMSP and DMS concentrations. These results show that dust deposition events in a low-pH iron-limited Northeast subarctic Pacific are likely to stimulate phytoplankton growth to a lesser extent than in today's ocean during the few days following fertilization and point to a low initial sensitivity of the DMSP and DMS dynamics to OA.

  18. Impact of ocean acidification on phytoplankton assemblage, growth, and DMS production following Fe-dust additions in the NE Pacific high-nutrient, low-chlorophyll waters

    NASA Astrophysics Data System (ADS)

    Mélançon, Josiane; Levasseur, Maurice; Lizotte, Martine; Scarratt, Michael; Tremblay, Jean-Éric; Tortell, Philippe; Yang, Gui-Peng; Shi, Guang-Yu; Gao, Huiwang; Semeniuk, David; Robert, Marie; Arychuk, Michael; Johnson, Keith; Sutherland, Nes; Davelaar, Marty; Nemcek, Nina; Peña, Angelica; Richardson, Wendy

    2016-03-01

    Ocean acidification (OA) is likely to have an effect on the fertilizing potential of desert dust in high-nutrient, low-chlorophyll oceanic regions, either by modifying iron (Fe) speciation and bioavailability or by altering phytoplankton Fe requirements and acquisition. To address this issue, short incubations (4 days) of northeast subarctic Pacific waters enriched with either FeSO4 or dust and set at pH 8.0 (in situ) and 7.8 were conducted in August 2010. We assessed the impact of a decrease in pH on dissolved Fe concentration, phytoplankton biomass, taxonomy and productivity, and the production of dimethylsulfide (DMS) and its algal precursor dimethylsulfoniopropionate (DMSP). Chlorophyll a (chl a) remained unchanged in the controls and doubled in both the FeSO4-enriched and dust-enriched incubations, confirming the Fe-limited status of the plankton assemblage during the experiment. In the acidified treatments, a significant reduction (by 16-38 %) in the final concentration of chl a was measured compared to their nonacidified counterparts, and a 15 % reduction in particulate organic carbon (POC) concentration was measured in the dust-enriched acidified treatment compared to the dust-enriched nonacidified treatment. FeSO4 and dust additions had a fertilizing effect mainly on diatoms and cyanobacteria as estimated from algal pigment signatures. Lowering the pH affected mostly the haptophytes, but pelagophyte concentrations were also reduced in some acidified treatments. Acidification did not significantly alter DMSP and DMS concentrations. These results show that dust deposition events in a low-pH iron-limited northeast subarctic Pacific are likely to stimulate phytoplankton growth to a lesser extent than in today's ocean during the few days following fertilization and point to a low initial sensitivity of the DMSP and DMS dynamics to OA.

  19. Metabolism of reduced methylated sulfur compounds in anaerobic sediments and by a pure culture of an estuarine methanogen

    USGS Publications Warehouse

    Kiene, R.P.; Oremland, Ronald S.; Catena, Anthony; Miller, Laurence G.; Capone, D.G.

    1986-01-01

    Addition of dimethylsulfide (DMS), dimethyldisulfide (DMDS), or methane thiol (MSH) to a diversity of anoxic aquatic sediments (e.g., fresh water, estuarine, alkaline/hypersaline) stimulated methane production. The yield of methane recovered from DMS was often 52 to 63%, although high concentrations of DMS (as well as MSH and DMDS) inhibited methanogenesis in some types of sediments. Production of methane from these reduced methylated sulfur compounds was blocked by 2-bromoethanesulfonic acid. Sulfate did not influence the metabolism of millimolar levels of DMS, DMDS, or MSH added to sediments. However, when DMS was added at ∼2-μM levels as [14C]DMS, metabolism by sediments resulted in a 14CH4/14CO2 ratio of only 0.06. Addition of molybdate increased the ratio to 1.8, while 2-bromoethanesulfonic acid decreased it to 0, but did not block 14CO2 production. These results indicate the methanogens and sulfate reducers compete for DMS when it is present at low concentrations; however, at high concentrations, DMS is a “noncompetitive” substrate for methanogens. Metabolism of DMS by sediments resulted in the appearance of MSH as a transient intermediate. A pure culture of an obligately methylotrophic estuarine methanogen was isolated which was capable of growth on DMS. Metabolism of DMS by the culture also resulted in the transient appearance of MSH, but the organism could grow on neither MSH nor DMDS. The culture metabolized [14C]-DMS to yield a 14CH4/14CO2 ratio of ∼2.8. Reduced methylated sulfur compounds represent a new class of substrates for methanogens and may be potential precursors of methane in a variety of aquatic habitats.

  20. Metabolism of reduced methylated sulfur compounds in anaerobic sediments and by a pure culture of an estuarine methanogen

    SciTech Connect

    Kiene, R.P.; Oremland, R.S.; Catena, A.; Miller, L.G.; Capone, A.G.

    1986-11-01

    Addition of dimethylsulfide (DMS), dimethyldisulfide (DMDS), or methane thiol (MSH) to a diversity of anoxic aquatic sediments (e.g., fresh water, estuarine, alkaline/hypersaline) stimulated methane production. The yield of methane recovered from DMS was often 52 to 63%, although high concentrations of DMS (as well as MSH and DMDS) inhibited methanogenesis in some types of sediments. Production of methane from these reduced methylated sulfur compounds was blocked by 2-bromoethanesulfonic acid. Sulfate did not influence the metabolism of millimolar levels of DMS, DMDs, or MSH added to sediments. However, when DMS was added at approx.2-3=M levels as (/sup 14/C)DMS, metabolism by sediments resulted in a /sup 14/CH/sub 4///sup 14/CO/sub 2/ ratio of only 0.06. Addition of molybdate increased the ratio of 1.8, while 2-bromoethanesulfonic acid decreased it to 0, but did not block /sup 14/CO/sub 2/ production. These results indicate the methanogens and sulfate reducers compete for DMS when it is present at low concentrations; however, at high concentrations, DMS is a noncompetitive substrate for methanogens. Metabolism of DMS by sediments resulted in the appearance of MSH as a transient intermediate. A pure culture of an obligately methylotrophic estuarine methanogen was isolated which was capable of growth on DMS. Metabolism of DMS by the culture also resulted in the transient appearance of MSH, but the organism could grow on neither MSH nor DMDS. The culture metabolized (/sup 14/C)-DMS to yield a /sup 14/CH/sub 4///sup 14/CO/sub 2/ ratio of approx. 2.8.

  1. Metabolism of acrylate to {beta}-hydroxypropionate and its role in dimethylsulfoniopropionate lyase induction by a salt marsh sediment bacterium, Alcaligenes faecalis M3A

    SciTech Connect

    Ansede, J.H.; Pellechia, P.J.; Yoch, D.C.

    1999-11-01

    Dimethylsulfoniopropionate (DMSP) is degraded to dimethylsulfide (DMS) and acrylate by the enzyme DMSP lyase. DMS or acrylate can serve as a carbon source for both free-living and endophytic bacteria in the marine environment. In this study, the authors report on the mechanism of DMSP-acrylate metabolism by Alcaligenes faecalis M3A. Suspensions of citrate-grown cells expressed a low level of DMSP lyase activity that could be induced to much higher levels in the presence of DMSP, acrylate, and its metabolic product, {beta}-hydroxypropionate. DMSP was degraded outside the cell, resulting in an extracellular accumulation of acrylate, which in suspensions of citrate-grown cells was then metabolized at a low endogenous rate. The inducible nature of acrylate metabolism was evidenced by both an increase in the rate of its degradation over time and the ability of acrylate-grown cells to metabolize this molecule at about an eight times higher rate than citrate-grown cells. Therefore, acrylate induces both its production (from DMSP) and its degradation by an acrylase enzyme. {sup 1}H and {sup 13}C nuclear magnetic resonance analyses were used to identify the products resulting from [1-{sup 13}C]acrylate metabolism. The results indicated that A.faecalis first metabolized acrylate to {beta}-hydroxypropionate outside the cell, which was followed by its intracellular accumulation and subsequent induction of DMSP lyase activity. In summary, the mechanism of DMSP degradation to acrylate and the subsequent degradation of acrylate to {beta}-hydroxypropionate in the aerobic {beta}-Proteobacterium A.faecalis has been described.

  2. Measurements of ocean derived aerosol off the coast of California

    NASA Astrophysics Data System (ADS)

    Bates, T. S.; Quinn, P. K.; Frossard, A. A.; Russell, L. M.; Hakala, J.; PetäJä, T.; Kulmala, M.; Covert, D. S.; Cappa, C. D.; Li, S.-M.; Hayden, K. L.; Nuaaman, I.; McLaren, R.; Massoli, P.; Canagaratna, M. R.; Onasch, T. B.; Sueper, D.; Worsnop, D. R.; Keene, W. C.

    2012-06-01

    Reliable characterization of particles freshly emitted from the ocean surface requires a sampling method that is able to isolate those particles and prevent them from interacting with ambient gases and particles. Here we report measurements of particles directly emitted from the ocean using a newly developed in situ particle generator (Sea Sweep). The Sea Sweep was deployed alongside R/V Atlantis off the coast of California during May of 2010. Bubbles were generated 0.75 m below the ocean surface with stainless steel frits and swept into a hood/vacuum hose to feed a suite of aerosol instrumentation on board the ship. The number size distribution of the directly emitted, nascent particles had a dominant mode at 55-60 nm (dry diameter) and secondary modes at 30-40 nm and 200-300 nm. The nascent aerosol was not volatile at 230°C and was not enriched in SO4=, Ca++, K+, or Mg++above that found in surface seawater. The organic component of the nascent aerosol (7% of the dry submicrometer mass) volatilized at a temperature between 230 and 600°C. The submicrometer organic aerosol characterized by mass spectrometry was dominated by non-oxygenated hydrocarbons. The nascent aerosol at 50, 100, and 145 nm dry diameter behaved hygroscopically like an internal mixture of sea salt with a small organic component. The CCN/CN activation ratio for 60 nm Sea Sweep particles was near 1 for all supersaturations of 0.3 and higher indicating that all of the particles took up water and grew to cloud drop size. The nascent organic aerosol mass fraction did not increase in regions of higher surface seawater chlorophyll but did show a positive correlation with seawater dimethylsulfide (DMS).

  3. Measurements of ocean derived aerosol off the coast of California

    NASA Astrophysics Data System (ADS)

    Bates, T. S.; Quinn, P. K.; Frossard, A. A.; Russell, L. M.; Hakala, J.; PetäJä, T.; Kulmala, M.; Covert, D. S.; Cappa, C. D.; Li, S.-M.; Hayden, K. L.; Nuaaman, I.; McLaren, R.; Massoli, P.; Canagaratna, M. R.; Onasch, T. B.; Sueper, D.; Worsnop, D. R.; Keene, W. C.

    2011-11-01

    Reliable characterization of particles freshly emitted from the ocean surface requires a sampling method that is able to isolate those particles and prevent them from interacting with ambient gases and particles. Here we report measurements of particles directly emitted from the ocean using a newly developed in situ particle generator (Sea Sweep). The Sea Sweep was deployed alongside R/V Atlantis off the coast of California during May of 2010. Bubbles were generated 0.75 m below the ocean surface with stainless steel frits and swept into a hood/vacuum hose to feed a suite of aerosol instrumentation on board the ship. The number size distribution of the directly emitted, nascent particles had a dominant mode at 55-60 nm (dry diameter) and secondary modes at 30-40 nm and 200-300 nm. The nascent aerosol was not volatile at 230°C and was not enriched in SO4=, Ca++, K+, or Mg++above that found in surface seawater. The organic component of the nascent aerosol (7% of the dry submicrometer mass) volatilized at a temperature between 230 and 600°C. The submicrometer organic aerosol characterized by mass spectrometry was dominated by non-oxygenated hydrocarbons. The nascent aerosol at 50, 100, and 145 nm dry diameter behaved hygroscopically like an internal mixture of sea salt with a small organic component. The CCN/CN activation ratio for 60 nm Sea Sweep particles was near 1 for all supersaturations of 0.3 and higher indicating that all of the particles took up water and grew to cloud drop size. The nascent organic aerosol mass fraction did not increase in regions of higher surface seawater chlorophyll but did show a positive correlation with seawater dimethylsulfide (DMS).

  4. Metabolomics and the Legacy of Previous Ecosystems: a Case Study from the Brine of Lake Vida (Antarctica)

    NASA Astrophysics Data System (ADS)

    Chou, L.; Kenig, F. P. H.; Murray, A. E.; Doran, P. T.; Fritsen, C. H.

    2015-12-01

    The McMurdo Dry Valleys of Antarctica are regarded as one of the best Earth analogs for astrobiological investigations of icy worlds. In the dry valleys, Lake Vida contains an anoxic and aphotic ice-sealed brine that has been isolated for millennia and yet is hosting a population of active microbes at -13˚ C. The biogeochemical processes used by these slow-growing microbes are still unclear. We attempt to elucidate the microbial processes responsible for the survivability of these organisms using metabolomics. Preliminary investigations of organic compounds of Lake Vida Brine (LVBr) was performed using gas chromatography-mass spectrometry (GC-MS) and solid-phase micro-extraction (SPME) GC-MS. LVBr contains a vast variety of lipids and is dominated by low molecular weight compounds. Many of these compounds are biomarkers of processes that took place in Lake Vida prior to evaporation and its cryo-encapsulation. These compounds include dimethylsulfide that is derived from the photosynthate dimethylsulfoniopropionate, dihydroactinidiolide that is derived from a diatom pigment, and 2-methyl-3-ethyl-maleimide that is derived from chlorophyll. These compounds, which dominate the lipid reservoir, represent a legacy from an ecosystem that is different from the current bacterial ecosystem of the brine. The abundance of the legacy compounds in the brine is most likely a reflection of the very slow metabolism of the bacterial community in the cold brine. It is important, thus, to be able to distinguish the legacy metabolites and their diagenetic products from the metabolites of the current ecosystem. This legacy issue is specific to a slow growing microbial ecosystem that cannot process the legacy carbon completely. It applies not only to Lake Vida brine, but other slow growing ecosystems such as other subglacial Antarctic lakes, the Arctic regions, and the deep biosphere.

  5. Effect of a variety of Chinese herbs and an herb-containing dentifrice on volatile sulfur compounds associated with halitosis: An in vitro analysis

    PubMed Central

    Li, Ming-yu; Wang, Jun; Xu, Zhu-ting

    2010-01-01

    Background: The principal components of halitosis are volatile sulfur compounds (VSCs) such as hydrogen sulfide, methyl mercaptan, and dimethylsulfide or compounds such as butyric acid, propionic acid, putrescine, and cadaverine. Objective: The aim of this study was to evaluate the effect of Chinese herbs on VSCs in vitro. Methods: Saliva samples from volunteers were used as the source for the evaluation of bacterial activity and VSC inhibition. Extracted substances from Chinese herbs were identified by VSC inhibition tests with a Halimeter and microbial sensitivity testing. The effectiveness on halitosis was compared between a dentifrice containing one of the effective Chinese herbs (ie, chrysanthemum flower [Chrysanthemum morifolium flos]), 4 commercially available antihalitosis dentifrices, and a positive control that received no treatment. Results: Ten volunteers provided saliva samples for VSC testing. Of the 40 herbs tested, 14 extracts had percent inhibition rates of VSCs >50%. Ten herbs showed greatest effect against all culturable microorganisms with bacterial inhibition >70%. There was a weak positive correlation between bacteriostasis and the anti-VSC activity of the herbs with a correlation coefficient of 0.2579 (Pearson). The mean (SD) values of the VSC testing were as follows: dentifrice containing chrysanthemum flower, 55.91 (8.16) ppb; Crest Tea Refreshing Dentifrice®, 48.39 (7.48) ppb (P = NS); Cortex Phellodendri Dentifrice®, 139.90 (14.70) ppb (P < 0.01); Colgate Total Plus Whitening®, 120.94 (15.58) ppb (P < 0.01); Zhong Hua Chinese Herbs Dentifrice®, 136.96 (13.06) ppb (P < 0.01); and positive control, 312.38 (28.58) ppb (P < 0.01). Conclusions: Of 40 herbs tested, 14 Chinese herbs were found to be effective for VSC inhibition. A dentifrice containing chrysanthemum flower reduced the formation of VSC in vitro, showing a significantly greater effect than the control group and 3 of 4 dentifrices already on the market. PMID:24683259

  6. 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%.

  7. Toxicological investigation of liquid petroleum gas explosion: human model for propane/ethyl mercaptan exposures.

    PubMed

    Lowry, W T; Gamse, B; Armstrong, A T; Corn, J M; Juarez, L; McDowell, J L; Owens, R

    1991-03-01

    Four individuals died as the result of a propane explosion. As with many propane explosions, the question was raised as to the adequacy of the product's odorization after the autopsy studies had been conducted. In most cases, this question leads to litigation. Ethyl mercaptan is a widely used odorant for propane and was used in this instance. Three of the four victims had blood available at autopsy for study. Quantitative analyses of the victims' blood, obtained during autopsy, were performed using gas chromatography/mass spectrometry, without subjecting the samples to hydrolysis. These analyses determined the relative amounts of propane and ethyl mercaptan in the blood to be 90, 63, and 175 mL/m3 headspace, and 0.36, 0.34, and 0.77 microgram/L blood, respectively. Since mercaptans have been reported in human blood as products of metabolism, modeling studies were conducted to establish the validity of the autopsy data and to develop an autopsy toxicology protocol for investigating explosion deaths. When subjects were not exposed to an atmosphere containing ethyl mercaptan, dimethylsulfide was the only mercaptan detectable in their blood without severe hydrolysis prior to analysis. Metabolic ethyl mercaptan is sufficiently bound to be undetectable by the methods used without hydrolysis. Human subjects were exposed to a flammable mixture of air and propane odorized with ethyl mercaptan. The analyses of the blood from these subjects produced results which were comparable with those for the explosion victims, establishing that the question of odorant adequacy can be addressed at the autopsy of propane explosion victims. It is extremely important that the pathologist and toxicologist investigating gas explosion deaths recognize the valuable evidence existing in the victim's blood.

  8. Henry`s law solubilities and Setchenow coefficients for biogenic reduced sulfur species obtained from gas-liquid uptake measurements

    SciTech Connect

    De Bruyn, W.J.; Swartz, E.; Hu, J.H.

    1995-04-20

    Biogenically produced reduced sulfur compounds, including dimethylsulfide (DMS, CH{sub 3}SCH{sub 3}), hydrogen sulfide (H{sub 2}S), carbon disulfide (CS{sub 2}), methyl mercaptan (CH{sub 3}SH), and carbonyl sulfide (OCS), are a major source of sulfur in the marine atmosphere. This source is estimated to contribute 25-40% of global sulfur emissions. These species and their oxidation products, dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO{sub 2}), and methane sulfonic acid (MSA), dominate the production of aerosol and cloud condensation nuclei (CCN) in the clean marine atmosphere. The multiphase chemical processes for these species must be understood in order to study the evolving role of combustion-produced sulfur oxides over the oceans. Using a newly developed bubble column apparatus, a series of aqueous phase uptake studies have been completed for the reduced sulfur species DMS, H{sub 2}S, CS{sub 2}, CH{sub 3}SH, and OCS. Aqueous phase uptake has been studied as a function of temperature (278-298 K), pH (1-14), H{sub 2}O{sub 2} concentration (0-1 M), NaCl concentration (0-5 M), and (NH{sub 4}){sub 2}SO{sub 4} concentration (0-4 M). The Henry`s law coefficients for CH{sub 3}SH and CS{sub 2} were determined for the first time, as were the Setchenow coefficients for all the species studied. 33 refs., 8 figs., 2 tabs.

  9. The sulfur cycle at high-southern latitudes in the LMD-ZT General Circulation Model

    NASA Astrophysics Data System (ADS)

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

    2002-12-01

    This modeling study was motivated by the recent publication of year-round records of dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) in Antarctica, completing the available series of sulfate and methanesulfonic acid (MSA). Sulfur chemistry has been incorporated in the Laboratoire de Météorologie Dynamique-Zoom Tracers (LMD-ZT) Atmospheric General Circulation Model (AGCM), with high-resolution and improved physics at high-southern latitudes. The model predicts the concentration of six major sulfur species through emissions, transport, wet and dry deposition, and chemistry in both gas and aqueous phases. Model results are broadly realistic when compared with measurements in air and snow or ice, as well as to results of other modeling studies, at high- and middle-southern latitudes. Atmospheric MSA concentrations are underestimated and DMSO concentrations are overestimated in summer, reflecting the lack of a DMSO heterogeneous sink leading to MSA. Experiments with various recently published estimates of the rate of this sink are reported. Although not corrected in this work, other defects are identified and discussed: DMS concentrations are underestimated in winter, MSA and non-sea-salt (nss) sulfate concentrations may be underestimated at the South Pole, the deposition scheme used in the model may not be adapted to polar regions, and the model does not adequately reproduces interannual variability. Oceanic DMS sources have a major contribution to the variability of sulfur in these regions. The model results suggest that in a large part of central Antarctica ground-level atmospheric DMS concentrations are larger in winter than in summer. At high-southern latitudes, high loads of DMS and DMSO are found and the main chemical sink of sulfur dioxide (SO2) is aqueous oxidation by ozone (O3), whereas oxidation by hydrogen peroxide (H2O2) dominates at the global scale. A comprehensive modeled sulfur budget of Antarctica is provided.

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

    NASA Astrophysics Data System (ADS)

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

    2002-12-01

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

  11. A meta-analysis of oceanic DMS and DMSP cycling processes: Disentangling the summer paradox

    NASA Astrophysics Data System (ADS)

    Galí, Martí; Simó, Rafel

    2015-04-01

    The biogenic volatile compound dimethylsulfide (DMS) is produced in the ocean mainly from the ubiquitous phytoplankton osmolyte dimethylsulfoniopropionate (DMSP). In the upper mixed layer, DMS concentration and the daily averaged solar irradiance are roughly proportional across latitudes and seasons. This translates into a seasonal mismatch between DMS and phytoplankton biomass at low latitudes, termed the "DMS summer paradox," which remains difficult to reproduce with biogeochemical models. Here we report on a global meta-analysis of DMSP and DMS cycling processes and their relationship to environmental factors. We show that DMS seasonality reflects progressive changes in a short-term dynamic equilibrium, set by the quotient between gross DMS production rates and the sum of biotic and abiotic DMS consumption rate constants. Gross DMS production is the principal driver of DMS seasonality, due to the synergistic increases toward summer in two of its underlying factors: phytoplankton DMSP content (linked to species succession) and short-term community DMSP-to-DMS conversion yields (linked to physiological stress). We also show that particulate DMSP transformations (linked to grazing-induced phytoplankton mortality) generally contribute a larger share of gross DMS production than dissolved-phase DMSP metabolism. The summer paradox is amplified by a decrease in microbial DMS consumption rate constants toward summer. However, this effect is partially compensated by a concomitant increase in abiotic DMS loss rate constants. Besides seasonality, we identify consistent covariation between key sulfur cycling variables and trophic status. These findings should improve the modeling projections of the main natural source of climatically active atmospheric sulfur.

  12. Aboveground and Belowground Herbivores Synergistically Induce Volatile Organic Sulfur Compound Emissions from Shoots but Not from Roots.

    PubMed

    Danner, Holger; Brown, Phil; Cator, Eric A; Harren, Frans J M; van Dam, Nicole M; Cristescu, Simona M

    2015-07-01

    Studies on aboveground (AG) plant organs have shown that volatile organic compound (VOC) emissions differ between simultaneous attack by herbivores and single herbivore attack. There is growing evidence that interactive effects of simultaneous herbivory also occur across the root-shoot interface. In our study, Brassica rapa roots were infested with root fly larvae (Delia radicum) and the shoots infested with Pieris brassicae, either singly or simultaneously, to study these root-shoot interactions. As an analytical platform, we used Proton Transfer Reaction Mass Spectrometry (PTR-MS) to investigate VOCs over a 3 day time period. Our set-up allowed us to monitor root and shoot emissions concurrently on the same plant. Focus was placed on the sulfur-containing compounds; methanethiol, dimethylsulfide (DMS), and dimethyldisulfide (DMDS), because these compounds previously have been shown to be biologically active in the interactions of Brassica plants, herbivores, parasitoids, and predators, yet have received relatively little attention. The shoots of plants simultaneously infested with AG and belowground (BG) herbivores emitted higher levels of sulfur-containing compounds than plants with a single herbivore species present. In contrast, the emission of sulfur VOCs from the plant roots increased as a consequence of root herbivory, independent of the presence of an AG herbivore. The onset of root emissions was more rapid after damage than the onset of shoot emissions. The shoots of double infested plants also emitted higher levels of methanol. Thus, interactive effects of root and shoot herbivores exhibit more strongly in the VOC emissions from the shoots than from the roots, implying the involvement of specific signaling interactions.

  13. Studies of sulfur biogeochemistry, microbiology and paleontology in three anoxic environments: The Black Sea, a salt marsh mat, and an Ordovician black shale

    SciTech Connect

    Muramoto, J.A.

    1992-01-01

    The author studied the biogeochemistry, microbial ecology and paleontology of three anoxic environments. In the Black Sea, three studies dealt with the role of particle fluxes in sulfur cycling and microbial ecology. In the water column, iron sulfides form at the oxic-anoxic interface from dissolved sulfide left after chemical oxidation, based on sulfur isotopes; formation in deep water is minimal and iron-limited. Sinking organic aggregates transport iron sulfides to the bottom. Sedimentary sulfides may originate from sulfide fluxes and record intensity of chemical vs. microbial oxidation at the oxic-anoxic interface. Sulfate reduction rates from modelled diagenesis of organic carbon fluxes agree with other measured rates. A box model summarizes sulfur cycling between water column and sediments. An algal sulfur compound, dimethylsulfoniopropionate (DMSP), precursor to dimethylsulfide (DMS), was measured in deep-sea particle fluxes. DMSP levels in particle fluxes vary seasonally and between oceans. Though DMSP is only 0.005% of organic carbon fluxes, its removal to the deep sea by fluxes may lessen sea-air DMS fluxes. A DMSP-DMS cycle for ocean and sediments is proposed. A third study compared bacteria biomass and morphology in particle fluxes and water column, using TEM and epifluorescence microscopy. Some bacteria had intracellular structures indicating autotrophy. Concentrations in particle fluxes were high compared to sediment bacteria populations elsewhere, but bacterial carbon is a tiny fraction of total organic carbon. In contrast, phototrophic bacteria dominated a microbial mat in a salt marsh where sulfate reduction is important. Cyanobacteria, purple and green sulfur bacteria species were strongly depth-zoned, and cell sizes decreased as depth increased. Also investigated was spatiotemporal change in a fossil lingulid brachiopod from a suboxic facies, using gradient analyses of benthic invertebrate and planktonic graptolite assemblages.

  14. Trimethylamine and Organic Matter Additions Reverse Substrate Limitation Effects on the δ13C Values of Methane Produced in Hypersaline Microbial Mats

    PubMed Central

    Nicholson, Brooke E.; Beaudoin, Claire S.; Detweiler, Angela M.; Bebout, Brad M.

    2014-01-01

    Methane production has been observed in a number of hypersaline environments, and it is generally thought that this methane is produced through the use of noncompetitive substrates, such as the methylamines, dimethylsulfide and methanol. Stable isotope measurements of the produced methane have also suggested that the methanogens are operating under conditions of substrate limitation. Here, substrate limitation in gypsum-hosted endoevaporite and soft-mat hypersaline environments was investigated by the addition of trimethylamine, a noncompetitive substrate for methanogenesis, and dried microbial mat, a source of natural organic matter. The δ13C values of the methane produced after amendments were compared to those in unamended control vials. At all hypersaline sites investigated, the δ13C values of the methane produced in the amended vials were statistically lower (by 10 to 71‰) than the unamended controls, supporting the hypothesis of substrate limitation at these sites. When substrates were added to the incubation vials, the methanogens within the vials fractionated carbon isotopes to a greater degree, resulting in the production of more 13C-depleted methane. Trimethylamine-amended samples produced lower methane δ13C values than the mat-amended samples. This difference in the δ13C values between the two types of amendments could be due to differences in isotope fractionation associated with the dominant methane production pathway (or substrate used) within the vials, with trimethylamine being the main substrate used in the trimethylamine-amended vials. It is hypothesized that increased natural organic matter in the mat-amended vials would increase fermentation rates, leading to higher H2 concentrations and increased CO2/H2 methanogenesis. PMID:25239903

  15. Transsulfuration in an adult with hepatic methionine adenosyltransferase deficiency.

    PubMed Central

    Gahl, W A; Bernardini, I; Finkelstein, J D; Tangerman, A; Martin, J J; Blom, H J; Mullen, K D; Mudd, S H

    1988-01-01

    We investigated sulfur and methyl group metabolism in a 31-yr-old man with partial hepatic methionine adenosyltransferase (MAT) deficiency. The patient's cultured fibroblasts and erythrocytes had normal MAT activity. Hepatic S-adenosylmethionine (SAM) was slightly decreased. This clinically normal individual lives with a 20-30-fold elevation of plasma methionine (0.72 mM). He excretes in his urine methionine and L-methionine-d-sulfoxide (2.7 mmol/d), a mixed disulfide of methanethiol and a thiol bound to an unidentified group X, which we abbreviate CH3S-SX (2.1 mmol/d), and smaller quantities of 4-methylthio-2-oxobutyrate and 3-methylthiopropionate. His breath contains 17-fold normal concentrations of dimethylsulfide. He converts only 6-7 mmol/d of methionine sulfur to inorganic sulfate. This abnormally low rate is due not to a decreased flux through the primarily defective enzyme, MAT, since SAM is produced at an essentially normal rate of 18 mmol/d, but rather to a rate of homocysteine methylation which is abnormally high in the face of the very elevated methionine concentrations demonstrated in this patient. These findings support the view that SAM (which is marginally low in this patient) is an important regulator that helps to determine the partitioning of homocysteine between degradation via cystathionine and conservation by reformation of methionine. In addition, these studies demonstrate that the methionine transamination pathway operates in the presence of an elevated body load of that amino acid in human beings, but is not sufficient to maintain methionine levels in a normal range. PMID:3339126

  16. Dimethyl sulfoxide modulation of diabetes onset in NOD mice.

    PubMed

    Klandorf, H; Chirra, A R; DeGruccio, A; Girman, D J

    1989-02-01

    Dimethyl sulfoxide (DMSO), a hydroxyl radical scavenger, is known as an immunosuppressive agent and can reduce autoantibody levels in experimental autoimmune diseases. Because classic diabetogens damage the DNA and membrane of the beta-cell by the generation of free radicals, the purpose of these investigations was to determine whether the intake of DMSO or its derivatives methylsulfonylmethane (MSM) and dimethylsulfide (DMS) could prevent the expression of autoimmune diabetes in the spontaneously diabetic NOD mouse. DMSO (2.5%), MSM (2.5%), and DMS (0.25%) were added to the drinking water of female NOD mice immediately after weaning. Control animals were maintained on regular drinking water. The presence of overt diabetes was monitored from the age of 2 mo by weekly urinary glucose testing until the animals either became overtly glucosuric or were greater than 240 days of age. In contrast to what we expected, DMSO (2.5%) markedly increased the rate at which the animals expressed overt diabetes (P less than .0004, log-rank test). MSM had no effect, whereas DMS reduced the incidence and rate of diabetes onset. When DMSO (2.5%) was administered to male NOD mice and control strains of mice (BALB/c and ICR), the control group did not develop glucosuria or insipidus, whereas DMSO increased the incidence of diabetes in the male NOD mice from 21 to 79%. In contrast, when DMSO was fed to female NOD mice on a purified AIN-76 diet, diabetes onset was reduced to 36%. We conclude that DMSO accelerates the uptake of dietary diabetogens into the beta-cell of genetically susceptible animals (NOD mice). The protective effect of the purified diet in such animals may be due to a lack of putative diabetogens in purified diet, or alternatively, the diet itself contains factor(s) that protect the beta-cell from autoimmune attack and/or destruction.

  17. Aerosol fine fraction in the Venice Lagoon: Particle composition and sources

    NASA Astrophysics Data System (ADS)

    Prodi, F.; Belosi, F.; Contini, D.; Santachiara, G.; Di Matteo, L.; Gambaro, A.; Donateo, A.; Cesari, D.

    2009-04-01

    The work presents a characterisation of aerosol sampled during three campaigns conducted in the Venice Lagoon from 30 June to 21 July 2004, from 15 February to 10 March 2005 and from 8 May to 25 May 2006. The results yield information about the physical-chemical characteristics of fine aerosol, the possible sources and its fate. Sulphate (SO 42-), nitrate (NO 3-) and ammonium (NH 4+) are identified as the main water soluble components. The sum of these ions in the spring campaign 2006 varies from 51% to nearly 100% of PM2.5 fraction aerosol. NH 4+ is found to be significantly correlated to non-sea-salt sulphate (nss-SO 42-) and NO 3-, thus indicating the prevalent presence of ammonium nitrate and sulphate. The overall lack of a clear diurnal and seasonal cycle of sulphate suggests a transport from the Po Valley, while the diurnal and seasonal profile of nitrate concentrations suggests a prevalence of local generation. Sulphates from sea water through oxidation of dimethylsulfide (DMS) are not negligible (about 10% of the anthropogenic sulphate). The marine aerosol contribution to PM1 and PM2.5 fractions, calculated using Na + as a tracer of sea-salts, is low (range 1-6%). In some cases chlorine depletion is observed. The content of chlorine in the aerosol particle is mostly higher than expected for marine environments (considered on the basis of Cl -/Na + ratio). Therefore, specific sources for the element have been suggested. Oxalic acid anion, which accounts for 55% of the organic compounds examined, presents mean values 180 ng m - 3 and 161 ng m - 3 in the winter and spring campaigns, comparable with reported values in low polluted urban areas. In the winter campaign there is a high correlation between formate and acetate ( R2 = 0.93), suggesting that a common source makes a high contribution to the measured concentrations.

  18. Explicit solvent simulations of the aqueous oxidation potential and reorganization energy for neutral molecules: gas phase, linear solvent response, and non-linear response contributions.

    PubMed

    Guerard, Jennifer J; Tentscher, Peter R; Seijo, Marianne; Samuel Arey, J

    2015-06-14

    First principles simulations were used to predict aqueous one-electron oxidation potentials (Eox) and associated half-cell reorganization energies (λaq) for aniline, phenol, methoxybenzene, imidazole, and dimethylsulfide. We employed quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations of the oxidized and reduced species in an explicit aqueous solvent, followed by EOM-IP-CCSD computations with effective fragment potentials for diabatic energy gaps of solvated clusters, and finally thermodynamic integration of the non-linear solvent response contribution using classical MD. A priori predicted Eox and λaq values exhibit mean absolute errors of 0.17 V and 0.06 eV, respectively, compared to experiment. We also disaggregate Eox into several well-defined free energy properties, including the gas phase adiabatic free energy of ionization (7.73 to 8.82 eV), the solvent-induced shift in the free energy of ionization due to linear solvent response (-2.01 to -2.73 eV), and the contribution from non-linear solvent response (-0.07 to -0.14 eV). The linear solvent response component is further apportioned into contributions from the solvent-induced shift in vertical ionization energy of the reduced species (ΔVIEaq) and the solvent-induced shift in negative vertical electron affinity of the ionized species (ΔNVEAaq). The simulated ΔVIEaq and ΔNVEAaq are found to contribute the principal sources of uncertainty in computational estimates of Eox and λaq. Trends in the magnitudes of disaggregated solvation properties are found to correlate with trends in structural and electronic features of the solute. Finally, conflicting approaches for evaluating the aqueous reorganization energy are contrasted and discussed, and concluding recommendations are given.

  19. Trimethylamine and Organic Matter Additions Reverse Substrate Limitation Effects on the δ13C Values of Methane Produced in Hypersaline Microbial Mats.

    PubMed

    Kelley, Cheryl A; Nicholson, Brooke E; Beaudoin, Claire S; Detweiler, Angela M; Bebout, Brad M

    2014-12-01

    Methane production has been observed in a number of hypersaline environments, and it is generally thought that this methane is produced through the use of noncompetitive substrates, such as the methylamines, dimethylsulfide and methanol. Stable isotope measurements of the produced methane have also suggested that the methanogens are operating under conditions of substrate limitation. Here, substrate limitation in gypsum-hosted endoevaporite and soft-mat hypersaline environments was investigated by the addition of trimethylamine, a noncompetitive substrate for methanogenesis, and dried microbial mat, a source of natural organic matter. The δ(13)C values of the methane produced after amendments were compared to those in unamended control vials. At all hypersaline sites investigated, the δ(13)C values of the methane produced in the amended vials were statistically lower (by 10 to 71‰) than the unamended controls, supporting the hypothesis of substrate limitation at these sites. When substrates were added to the incubation vials, the methanogens within the vials fractionated carbon isotopes to a greater degree, resulting in the production of more (13)C-depleted methane. Trimethylamine-amended samples produced lower methane δ(13)C values than the mat-amended samples. This difference in the δ(13)C values between the two types of amendments could be due to differences in isotope fractionation associated with the dominant methane production pathway (or substrate used) within the vials, with trimethylamine being the main substrate used in the trimethylamine-amended vials. It is hypothesized that increased natural organic matter in the mat-amended vials would increase fermentation rates, leading to higher H2 concentrations and increased CO2/H2 methanogenesis.

  20. Investigating the 'Iron Hypothesis' in the North Pacific: Trans-Pacific Dust and Methanesulfonate (MSA) in the Denali Ice Core, Alaska

    NASA Astrophysics Data System (ADS)

    Saylor, P. L.; Osterberg, E. C.; Winski, D.; Ferris, D. G.; Koffman, B. G.; Kreutz, K. J.; Wake, C. P.; Campbell, S. W.

    2015-12-01

    Oceanic deposition of Asian-sourced, Iron-rich dust particulate has been linked to enhanced phytoplankton productivity in regions of the Pacific Ocean. High Nutrient Low Chlorophyll (HNLC) ocean regions, such as the North Pacific, are hypothesized to play a significant role in changing atmospheric CO­2 concentrations on glacial-interglacial timescales. Phytoplankton blooms generate methanesulfonate (MSA), an atmospheric oxidation product of dimethylsulfide (DMS) that is readily aerosolized and deposited in nearby glacial ice. In the summer of 2013, an NSF-funded team from Dartmouth College and the Universities of Maine and New Hampshire collected two 1000 year-long parallel ice cores to bedrock from the summit plateau of Mount Hunter in Denali National Park, Alaska (62.940° N, 151.088° W, 3912 m elevation). The Mt. Hunter ice core site is well situated to record changes in trans-Pacific dust flux and MSA emissions in the North Pacific. Here we investigate the history of dust flux to Denali over the last millennium using major and trace element chemistry and microparticle concentration and size distribution data from the Mt. Hunter cores. We evaluate potential controlling mechanisms on Denali dust flux including conditions at Asian dust sources (storminess, wind speed, precipitation), the strength of the Aleutian Low, and large-scale climate modes such as the El Niño-Southern Oscillation and the Pacific Decadal Oscillation. We also evaluate the Mt. Hunter record for relationships between dust flux and MSA concentrations to investigate whether dust fertilization enhanced North Pacific phytoplankton production over the past 1000 years. Future work will create a composite North Pacific dust record using new and existing Mt. Logan ice core records to evaluate these relationships over the entire Holocene.

  1. Structures of dimethylsulfoniopropionate-dependent demethylase from the marine organism Pelagabacter ubique

    SciTech Connect

    Schuller, David J.; Reisch, Chris R.; Moran, Mary Ann; Whitman, William B.; Lanzilotta, William N.

    2012-01-20

    Dimethylsulfoniopropionate (DMSP) is a ubiquitous algal metabolite and common carbon and sulfur source for marine bacteria. DMSP is a precursor for the climatically active gas dimethylsulfide that is readily oxidized to sulfate, sulfur dioxide, methanesulfonic acid, and other products that act as cloud condensation nuclei. Although the environmental importance of DMSP metabolism has been known for some time, the enzyme responsible for DMSP demethylation by marine bacterioplankton, dimethylsufoniopropionate-dependent demethylase A (DmdA, EC 2.1.1.B5), has only recently been identified and biochemically characterized. In this work, we report the structure for the apoenzyme DmdA from Pelagibacter ubique (2.1 {angstrom}), as well as for DmdA co-crystals soaked with substrate DMSP (1.6 {angstrom}) or the cofactor tetrahydrofolate (THF) (1.6 {angstrom}). Surprisingly, the overall fold of the DmdA is not similar to other enzymes that typically utilize the reduced form of THF and in fact is a triple domain structure similar to what has been observed for the glycine cleavage T protein or sarcosine oxidase. Specifically, while the THF binding fold appears conserved, previous biochemical studies have shown that all enzymes with a similar fold produce 5,10-methylene-THF, while DmdA catalyzes a redox-neutral methyl transfer reaction to produce 5-methyl-THF. On the basis of the findings presented herein and the available biochemical data, we outline a mechanism for a redox-neutral methyl transfer reaction that is novel to this conserved THF binding domain.

  2. Salinity as a regulator of DMSP degradation in Ruegeria pomeroyi DSS-3.

    PubMed

    Salgado, Paula; Kiene, Ronald; Wiebe, William; Magalhães, Catarina

    2014-11-01

    Dimethylsulfoniopropionate (DMSP) is an important carbon and sulfur source to marine bacterial communities and the main precursor of dimethylsulfide (DMS), a gas that influences atmospheric chemistry and potentially the global climate. In nature, bacterial DMSP catabolism can yield different proportions of DMS and methanethiol (MeSH), but relatively little is known about the factors controlling the pathways of bacterial degradation that select between their formation (cleavage vs. demethiolation). In this study, we carried out experiments to evaluate the influence of salinity on the routes of DMSP catabolism in Ruegeria pomeroyi DSS-3. We monitored DMS and MeSH accumulation in cell suspensions grown in a range of salinities (10, 20, 30 ppt) and with different DMSP amendments (0, 50, 500 µM). Significantly higher concentrations of DMS accumulated in low salinity treatments (10 ppt; P < 0.001), in both Marine Basal Medium (MBM) and half-strength Yeast Tryptone Sea Salts (1/2 YTSS) media. Results showed a 47.1% and 87.5% decrease of DMS accumulation, from salinity 10 to 20 ppt, in MBM and 1/2 YTSS media, respectively. On the other hand, MeSH showed enhanced accumulations at higher salinities (20, 30 ppt), with a 90.6% increase of MeSH accumulation from the 20 ppt to the 30 ppt salinity treatments. Our results with R. pomeroyi DSS-3 in culture are in agreement with previous results from estuarine sediments and demonstrate that salinity can modulate selection of the DMSP enzymatic degradation routes, with a consequent potential impact on DMS and MeSH liberation into the atmosphere.

  3. Methanethiol metabolism and its role in the pathogenesis of hepatic encephalopathy in rats and dogs.

    PubMed

    Blom, H J; Chamuleau, R A; Rothuizen, J; Deutz, N E; Tangerman, A

    1990-04-01

    The metabolism of methanethiol was studied in rats. Administration of a noncomatogenic dose of methanethiol through inspired air or injection into the upper colon resulted in an elevation of the concentrations of methanethiol mixed disulfides in serum (protein--S--S--CH3 and X--S--S--CH3, X yet unknown) and in urine (X--S--S--CH3). The concentrations of methanethiol mixed disulfides proved to be a relative measure of exposure to methanethiol. The levels of volatile sulfur compounds methanethiol, dimethylsulfide and dimethyldisulfide in the air expired by rats exposed to a noncomatogenic dose of methanethiol through the colon were also elevated. Rats with acute hepatic encephalopathy caused by liver ischemia also showed elevation of methanethiol mixed disulfide levels on challenge of methanethiol through the colon or inspired air, but to a significantly smaller extent than did the corresponding sham-operated rats. This suggests that the liver is at least partly responsible for formation of methanethiol mixed disulfides. No additional toxic effects were observed in the rats with ischemic livers on methanethiol exposition when compared with normal rats, suggesting that the liver does not play an essential role in methanethiol detoxification. Metabolism of methanethiol by blood to sulfate, for example, might be more important. In rats with acute hepatic encephalopathy caused by liver ischemia and in dogs suffering from hepatic encephalopathy resulting from chronic liver disease, large and significant increases in ammonia levels were measured. However, the mean levels of methanethiol mixed disulfides in rats and dogs with hepatic encephalopathy were not different from the mean normal levels in these animals.(ABSTRACT TRUNCATED AT 250 WORDS)

  4. Quantification of dimethylsulfoniopropionate (DMSP) in Acropora spp. of reef-building coral using mass spectrometry with deuterated internal standard.

    PubMed

    Swan, Hilton B; Deschaseaux, Elisabeth S M; Jones, Graham B; Eyre, Bradley D

    2017-03-01

    Dimethylsulfoniopropionate (DMSP) in scleractinian coral is usually analysed indirectly as dimethylsulfide (DMS) using gas chromatography (GC) with a sulfur-specific detector. We developed a headspace GC method for mass spectral analysis of DMSP in branching coral where hexa-deuterated DMSP (d 6 -DMSP) was added to samples and standards to optimise the analytical precision and quantitative accuracy. Using this indirect HS-GC-MS method, we show that common coral sample handling techniques did not alter DMSP concentrations in Acropora aspera and that endogenous DMS was insignificant compared to the store of DMSP in A. aspera. Field application of the indirect HS-GC-MS method in all seasons over a 5-year period at Heron Island in the southern Great Barrier Reef indicated that healthy colonies of A. aspera ordinarily seasonally conserve their branch tip store of DMSP; however, this store increased to a higher concentration under extended thermal stress conditions driven by a strong El Niño Southern Oscillation event. A liquid chromatography mass spectral method (LC-MS) was subsequently developed for direct analysis of DMSP in branching coral, also utilising the d 6 -DMSP internal standard. The quantitative comparison of DMSP in four species of Acropora coral by indirect HS-GC-MS and direct LC-MS analyses gave equivalent concentrations in A. aspera only; in the other three species, HS-GC-MS gave consistently higher concentrations, indicating that indirect analysis of DMSP may lead to artificially high values for some coral species. Graphical Abstract Dimethylsulfoniopropionate (DMSP) was quantified in Acropora spp. of branching coral using deuterated stable isotope dilution mass spectrometry.

  5. A first appraisal of prognostic ocean DMS models and prospects for their use in climate models

    NASA Astrophysics Data System (ADS)

    Le Clainche, Yvonnick; VéZina, Alain; Levasseur, Maurice; Cropp, Roger A.; Gunson, Jim R.; Vallina, Sergio M.; Vogt, Meike; Lancelot, Christiane; Allen, J. Icarus; Archer, Stephen D.; Bopp, Laurent; Deal, Clara; Elliott, Scott; Jin, Meibing; Malin, Gill; Schoemann, VéRonique; Simó, Rafel; Six, Katharina D.; Stefels, Jacqueline

    2010-09-01

    Ocean dimethylsulfide (DMS) produced by marine biota is the largest natural source of atmospheric sulfur, playing a major role in the formation and evolution of aerosols, and consequently affecting climate. Several dynamic process-based DMS models have been developed over the last decade, and work is progressing integrating them into climate models. Here we report on the first international comparison exercise of both 1D and 3D prognostic ocean DMS models. Four global 3D models were compared to global sea surface chlorophyll and DMS concentrations. Three local 1D models were compared to three different oceanic stations (BATS, DYFAMED, OSP) where available time series data offer seasonal coverage of chlorophyll and DMS variability. Two other 1D models were run at one site only. The major point of divergence among models, both within 3D and 1D models, relates to their ability to reproduce the summer peak in surface DMS concentrations usually observed at low to mid- latitudes. This significantly affects estimates of global DMS emissions predicted by the models. The inability of most models to capture this summer DMS maximum appears to be constrained by the basic structure of prognostic DMS models: dynamics of DMS and dimethylsulfoniopropionate (DMSP), the precursor of DMS, are slaved to the parent ecosystem models. Only the models which include environmental effects on DMS fluxes independently of ecological dynamics can reproduce this summer mismatch between chlorophyll and DMS. A major conclusion of this exercise is that prognostic DMS models need to give more weight to the direct impact of environmental forcing (e.g., irradiance) on DMS dynamics to decouple them from ecological processes.

  6. Emission of volatile sulfur compounds from spruce trees

    SciTech Connect

    Rennenberg, H.; Huber, B.; Schroeder, P.; Stahl, K.; Haunold, W.; Georgil, H.W.; Slovik, S.; Pfanz, H. )

    1990-03-01

    Spruce (Picea abies L.) trees from the same clone were supplied with different, but low, amounts of plant available sulfate in the soil (9.7-18.1 milligrams per 100 grams of soil). Branches attached to the trees were enclosed in a dynamic gas exchange cuvette and analyzed for the emission of volatile sulfur compounds. Independent of the sulfate supply in the soil, H{sub 2}S was the predominant reduced sulfur compound continuously emitted from the branches with high rates during the day and low rates in the night. In the light, as well as in the dark, the rates of H{sub 2}S emission increased exponentially with increasing water vapor flux from the needles. Approximately 1 nanomole of H{sub 2}S was found to be emitted per mole of water. When stomata were closed completely, only minute emission of H{sub 2}S was observed. Apparently, H{sub 2}S emission from the needles is highly dependent on stromatal aperture, and permeation through the cuticle is negligible. In several experiments, small amounts of dimethylsulfide and carbonylsulfide were also detected in a portion of the samples. However, SO{sub 2} was the only sulfur compound consistently emitted from branches of spruce trees in addition to H{sub 2}S. Emission of SO{sub 2} mainly proceeded via an outburst starting before the beginning of the light period. The total amount of SO{sub 2} emitted from the needles during this outburst was correlated with the plant available sulfate in the soil. The diurnal changes in sulfur metabolism that may result in an outburst of SO{sub 2} are discussed.

  7. Responses of DMS in the seawater and atmosphere to iron enrichment in the subarctic western North Pacific (SEEDS-II)

    NASA Astrophysics Data System (ADS)

    Nagao, Ippei; Hashimoto, Shinya; Suzuki, Koji; Toda, Shuji; Narita, Yasushi; Tsuda, Atsushi; Saito, Hiroaki; Kudo, Isao; Kato, Shungo; Kajii, Yoshizumi; Uematsu, Mitsuo

    2009-12-01

    Simultaneous measurements of dimethylsulfide (DMS) in the seawater and atmosphere were conducted during SEEDS-II to investigate the responses of DMS to iron (Fe) fertilization in the subarctic North Pacific. No significant increases in the seawater DMS (DMSw) concentration were observed inside the fertilized patch compared to those outside the patch, while particulate dimethylsulfoniopropionate (DMSPp) concentration inside the patch increased 2-fold compared to those outside the patch in the phytoplankton bloom of major DMSP producers such as prasinophytes, cryptophytes, diatoms and prymnesiophytes. In the decline phase of the bloom, maximum DMSw was observed both inside the patch (ca. 6.2 nM) and outside the patch (ca. 9.3 nM). In this period, increases in mesozooplankton and decreases in the DMSP producers (prymnesiophytes and diatoms) were observed both sides of the patch, but larger inside the patch than outside the patch. Large decreases in the DMSPp inside the patch, which was probably related to the large increases in mesozooplankton inside the patch, did not result in increases in the DMSw concentration. Considering biological and nonbiological parameters, we discussed these results, although they could not be completely explained. Unfortunately, the impact of Fe fertilization on the atmospheric DMS (DMSa) concentration was not detected due to no significant changes in DMSw. However, it is noted that DMSa concentrations were dependent on the sea-air DMS flux in the air from higher latitudes and/or the Eurasian continent, though the DMS flux was a minor role to the budget of DMSw. Therefore if DMSw were significantly changed by Fe fertilization, DMSa might be affected through changes in the sea-air flux in this condition.

  8. DMSP: tetrahydrofolate methyltransferase from the marine sulfate-reducing bacterium strain WN

    NASA Astrophysics Data System (ADS)

    Jansen, M.; Hansen, T. A.

    2000-08-01

    Dimethylsulfoniopropionate (DMSP), an important compatible solute of many marine algae, can be metabolised by bacteria via cleavage to dimethylsulfide and acrylate or via an initial demethylation. This is the first report on the purification of an enzyme that specifically catalyses the demethylation of DMSP. The enzyme was isolated from the sulfate-reducing bacterium strain WN, which grows on DMSP and demethylates it to methylthiopropionate. DMSP:tetrahydrofolate (THF) methyltransferase from strain WN was purified 76-fold [to a specific activity of 40.5 μmol min -1 (mg protein) -1]. SDS polyacrylamide gel electrophoresis showed two bands of approximately 10 and 35 kDa; in particular the 35 kDa polypeptide became significantly enriched during the purification. Storage of the purified fraction at -20°C under nitrogen resulted in a 99% loss of activity in two days. The activity could be partially restored by addition of 200 μM cyanocobalamin, hydroxocobalamin or coenzyme B 12. ATP did not have any positive effect on activity. Reduction of the assay mixture by titanium(III)nitrilotriacetic acid slightly stimulated the activity. Gel filtration chromatography revealed a native molecular mass between 45 and 60 kDa for the DMSP:THF methyltransferase. The enzyme was most active at 35°C and pH 7.8. Glycine betaine, which can be considered an N-containing structural analogue of DMSP, did not serve as a methyl donor for DMSP:THF methyltransferase. Various sulfur-containing DMSP-analogues were tested but only methylethylsulfoniopropionate served as methyl donor. None of these compounds inhibited methyl transfer from DMSP to THF. Strain WN did not grow on any of the sulfur-containing DMSP-analogues.

  9. Annual contribution of different plankton size classes to particulate dimethylsulfoniopropionate in a marine perturbed ecosystem

    NASA Astrophysics Data System (ADS)

    Jean, Natacha; Bogé, Gérard; Jamet, Jean-Louis; Richard, Simone; Jamet, Dominique

    2005-01-01

    Dimethylsulfoniopropionate (DMSP) concentrations were observed from October 1999 to September 2000 in a Mediterranean ecosystem (Little Bay of Toulon) submitted to eutrophication. DMSP was measured in the particulate material (DMSP p), and more specifically in the >90, 5-90 and 0.2-5 μm fractions. DMSP was first converted into dimethylsulfide (DMS) by a cold alkali treatment. DMS was then analysed by gas chromatography equipped with a flame photometric detector (FPD). DMSP p concentrations were relatively high, showing a strong temporal variability with maxima in February-March (58.8 nM). The most elevated values were recorded in the 5-90 μm size class, and represented between 60% and 100% of the total DMSP p. This fraction was mostly composed of Dinoflagellates whose biomass was significantly correlated with DMSP p concentrations. These concentrations showed better correlations with Ceratium furca, Dinophysis acuminata, Prorocentrum arcuatum and also Alexandrium minutum. The intracellular contents of DMSP were much higher in Dinoflagellates (124.9±5.7 mM) than in Diatoms (25.1±1.1 mM). A. minutum produced the strongest intracellular concentrations (3387.6±121.9 mM). High DMSP contents were also found in D. acuminata (477.4±64.3 mM) and P. arcuatum (442.2±22.9 mM). The >90 μm size class had a minor importance in DMSP production, generally below 20% of the total DMSP p. However, DMSP in the >90 μm fraction was well correlated with cladoceran abundance. Plankton cells between 0.2 and 5 μm contained a low part of the DMSP p pool, lower than 20%. Besides, no correlation was found between their algal abundances and DMSP in the 0.2-5 μm size class. Temperature and photoperiod could have influenced the Dinoflagellate development, and consequently, the DMSP p concentrations. The strong autumnal rains affected the composition of the phytoplankton community and the production of sulfur compounds. These particular climatic conditions have induced an increase in

  10. Modal structure of chemical mass size distribution in the high Arctic aerosol

    NASA Astrophysics Data System (ADS)

    Hillamo, Risto; Kerminen, Veli-Matti; Aurela, Minna; MäKelä, Timo; Maenhaut, Willy; Leek, Caroline

    2001-11-01

    dimethylsulfide (DMS) emissions from biogenic processes in seawater, followed by gas-to-particle conversion, formation of particulate sulfate and methane sulfonate (MSA) and neutralization by ammonia.

  11. Relationship between methanesulfonate (MS-) in atmospheric particulate and remotely sensed phytoplankton activity in oligo-mesotrophic central Mediterranean Sea

    NASA Astrophysics Data System (ADS)

    Becagli, S.; Lazzara, L.; Fani, F.; Marchese, C.; Traversi, R.; Severi, M.; di Sarra, A.; Sferlazzo, D.; Piacentino, S.; Bommarito, C.; Dayan, U.; Udisti, R.

    2013-11-01

    The coupling between oceanic and atmospheric sulfur cycles is fundamental for the understanding of the role of sulfate particles as potential climate regulators. We discuss existing relationships among methanesulfonate (MS- - one of the end products of oxidation of biogenic dimethylsulfide - DMS) in the atmospheric particulate, phytoplankton biomass, and remotely-sensed activity in the central Mediterranean. The MS- concentration in the aerosol particles is based on PM10 sampling (from 2005 to 2008) of atmospheric aerosols at the island of Lampedusa (35.5°N, 12.6°E) in the central Mediterranean Sea. The marine primary production in the sea sector surrounding the sampling site is obtained by using Ocean Color remote sensed data (SeaWiFS, MODIS-Aqua). In particular, primary production is calculated using a bio-optical model of sea reflectance and a Wavelength-Depth-Resolved Model (WDRM), fed by elaborated satellite data (chlorophyll concentration in the euphotic layer - Chl, sea surface temperature) and daily solar surface irradiance measurements. The multi-year evolution of MS- atmospheric concentration shows a well-defined seasonal cycle with a summer maximum, corresponding to the annual peak of solar radiation and a minimum of phytoplankton biomass (expressed as Chl). Statistically significant linear relationships between monthly means of atmospheric MS- and both the phytoplankton productivity index PB (r2 = 0.84, p < 0.001) and the solar radiation dose (SRD; r2 = 0.87, p < 0.001) in the upper mixed layer of the sea around Lampedusa are found. These correlations are mainly driven by the common seasonal pattern and suggest that DMS production in the marine surface layer is mainly related to the phytoplankton physiology. High values of PB are also the expression of stressed cells. The main stress factors in Mediterranean Sea during summer are high irradiance and shallow depth of the upper mixed layer, which lead to enhanced DMS emissions and higher MS- amounts in

  12. Pollution Levels in Fog at the Chilean Coast

    NASA Astrophysics Data System (ADS)

    Sträter, E.; Klemm, O.; Westbeld, A.

    2010-07-01

    oceanic dimethylsulfide (DMS). With regard to the back trajectories, the air masses generally reach the study site from southerly directions after travelling along the Chilean coast. Presumably the air masses pick up pollutants in the densely populated cities, industrial plants and power plants along the Chilean coast and transport them over hundreds of kilometers to Patache. Here, they were detected as ingredients in fog water and lead to high pollution levels therein.

  13. Latitudinal distributions of atmospheric MSA and MSA/nss-SO42- ratios in summer over the high latitude regions of the Southern and Northern Hemispheres

    NASA Astrophysics Data System (ADS)

    Chen, Liqi; Wang, Jianjun; Gao, Yuan; Xu, Guojie; Yang, Xulin; Lin, Qi; Zhang, Yuanhui

    2012-05-01

    To characterize the spatial distributions of methane-sulfonic acid (MSA) as represented by measured aerosol methane sulfonate (MS) and its relationships with non-sea-salt (nss) sulfate (SO42-) in the marine atmospheric boundary layer over high-latitude regions, bulk aerosol samples were collected during eight cruises during the Chinese National Antarctic and Arctic Research Expeditions from 1998 to 2008. The concentrations of MSA (an indicator of marine biogenic sulfur production), sulfate, sodium and chloride in samples were analyzed using ion chromatography. Increases in the aerosol MSA concentrations and MSA/nss-SO42- ratios were observed as functions of latitudes in the Pacific Ocean, more abruptly near high southern latitudes as compared to those in high northern latitudes. The MSA concentrations increased from 0.011 μg m-3 near the equator to 0.26 μg m-3 at 63°S, 23°W and from 0.0013 μg m-3 at northern midlatitudes to 0.19 μg m-3 at 58°N, 175°E. However, MSA decreased in the latitudes north of 58°N in the Pacific, where air temperature was lower. MSA/nss-SO42- ratios increased from 0.024 near the equator to 0.93 at 62°S, 4°E and from 0.0031 around northern midlatitudes to 0.39 at 68°N, 169°W. The MSA concentrations were more correlated with MSA/nss-SO42- (R2 = 0.43, n = 60) in Southern Hemisphere than Northern Hemisphere (R2 = 0.091, n = 40). No significant correlation was found between MSA/nss-SO42- and air temperature at high latitudes, indicating latitudinal temperature variations were not a main factor responsible for the MSA/nss-SO42- variation in those regions. Substantial increases in the concentrations of MSA in coastal Antarctica may indicate additional sources of biogenic S besides the emissions of dimethylsulfide from the sea.

  14. Gas-aerosol relationships of H2SO4, MSA, and OH: Observations in the coastal marine boundary layer at Mace Head, Ireland

    NASA Astrophysics Data System (ADS)

    Berresheim, H.; Elste, T.; Tremmel, H. G.; Allen, A. G.; Hansson, H.-C.; Rosman, K.; Dal Maso, M.; MäKelä, J. M.; Kulmala, M.; O'Dowd, C. D.

    2002-10-01

    Atmospheric concentrations of gaseous sulfuric acid (H2SO4), methane sulfonic acid (MSA), and hydroxyl radicals (OH) were measured by chemical ionization mass spectrometry (CIMS) during the second New Particle Formation and Fate in the Coastal Environment (PARFORCE) campaign in June 1999 at Mace Head, Ireland. Overall median concentrations in marine background air were 1.5, 1.2, and 0.12 × 106 cm-3, respectively. H2SO4 was also present at night indicating significant contributions from nonphotochemical sources. A strong correlation was found between daytime OH and H2SO4 levels in clean marine air suggesting a fast local production of H2SO4 from sulfur precursor gases. Steady state balance calculations of ambient H2SO4 levels agreed with measured concentrations if either very low H2SO4 sticking coefficients (0.02-0.03) or sources in addition to the SO2 + OH reaction were assumed. Overall, variations in ambient H2SO4 levels showed no correlation with either the tidal cycle or ultrafine particle (UFP) concentrations. However, on particular days an anticorrelation between H2SO4 and UFP levels was occasionally observed providing evidence for the contribution of H2SO4 to new particle formation and/or particle growth. Gaseous MSA concentrations were inversely correlated with dew point temperature reflecting a highly sensitive gas-particle partitioning equilibrium of this compound. The present observations seriously question the general use of MSA as a conservative tracer to infer the relative production yield of H2SO4 from dimethylsulfide (DMS) oxidation. MSA/H2SO4 concentration ratios typically ranged between 0.06 and 1.0 in marine air at ground level. Measured diel OH profiles showed a significant deviation from concurrent variations of the ozone photolysis frequency. They also showed up to 1 order of magnitude lower values compared to OH concentrations calculated with a simple photochemical box model. These differences were most pronounced during particle nucleation

  15. Volatile Organic Compound (VOC) Emissions from Dairy Cows and Their Waste

    NASA Astrophysics Data System (ADS)

    Shaw, S.; Holzinger, R.; Mitloehner, F.; Goldstein, A.

    2005-12-01

    Biogenic VOCs are typically defined as those directly emitted from plants, but approximately 6% of global net primary production is consumed by cattle that carry out enteric fermentation and then emit VOCs that could also be considered biogenic. Current regulatory estimates suggest that dairy cattle in central California emit VOCs at rates comparable to those from passenger vehicles in the region, and thus contribute significantly to the extreme non-attainment of ozone standards there. We report PTR-MS measurements of ammonia and VOCs, and cavity-enhanced-absorption gas analyzer (Los Gatos Research, Inc.) measurements of CH4, emitted from dairy cattle in various stages of pregnancy/lactation and their waste. Experiments were conducted in chambers at UC Davis that simulate freestall cow housing conditions. CH4 fluxes ranged from 125-374 lb/cow/year. The compounds with the highest fluxes from '3 cows+waste' treatments were: ammonia (1-18), methanol (0-2.3), acetone+propanal (0.2-0.7), dimethylsulfide (0-0.4), and mass 109 (likely ID = p-cresol; 0-0.3) in lb/cow/year. Mass 60 (likely ID = trimethylamine) and acetic acid were also abundant. There were 10s of additional compounds with detectable, but small, emissions. A few compounds that were likely emitted (i.e. ethanol, formaldehyde, and dimethylamine) were not quantified by the PTR-MS. The total flux for all measured organic gases (TOG = CH4 + PTR-MS VOCs(including acetone+propanal)) averaged 246±45 lb/cow/year for '3 cows+waste' treatments, and was dominated by methane (>98%). TOG flux for 'waste only' treatments averaged 1.1±0.1 lb/cow/year, and was instead dominated by VOC (>84%). The PTR-MS VOCs as a percent of TOG (0.6±0.2%) emitted from '3 cows+waste' treatments in chamber conditions was a factor of 10 smaller than that currently estimated by the California Air Resources Board. In addition, the ozone forming potentials of the most abundant VOCs are only about 10% those of typical combustion or plant

  16. Molecular analysis of volatile metabolites released specifically by staphylococcus aureus and pseudomonas aeruginosa

    PubMed Central

    2012-01-01

    Background The routinely used microbiological diagnosis of ventilator associated pneumonia (VAP) is time consuming and often requires invasive methods for collection of human specimens (e.g. bronchoscopy). Therefore, it is of utmost interest to develop a non-invasive method for the early detection of bacterial infection in ventilated patients, preferably allowing the identification of the specific pathogens. The present work is an attempt to identify pathogen-derived volatile biomarkers in breath that can be used for early and non- invasive diagnosis of ventilator associated pneumonia (VAP). For this purpose, in vitro experiments with bacteria most frequently found in VAP patients, i.e. Staphylococcus aureus and Pseudomonas aeruginosa, were performed to investigate the release or consumption of volatile organic compounds (VOCs). Results Headspace samples were collected and preconcentrated on multibed sorption tubes at different time points and subsequently analyzed with gas chromatography mass spectrometry (GC-MS). As many as 32 and 37 volatile metabolites were released by S. aureus and P. aeruginosa, respectively. Distinct differences in the bacteria-specific VOC profiles were found, especially with regard to aldehydes (e.g. acetaldehyde, 3-methylbutanal), which were taken up only by P. aeruginosa but released by S. aureus. Differences in concentration profiles were also found for acids (e.g. isovaleric acid), ketones (e.g. acetoin, 2-nonanone), hydrocarbons (e.g. 2-butene, 1,10-undecadiene), alcohols (e.g. 2-methyl-1-propanol, 2-butanol), esters (e.g. ethyl formate, methyl 2-methylbutyrate), volatile sulfur compounds (VSCs, e.g. dimethylsulfide) and volatile nitrogen compounds (VNCs, e.g. 3-methylpyrrole). Importantly, a significant VOC release was found already 1.5 hours after culture start, corresponding to cell numbers of ~8*106 [CFUs/ml]. Conclusions The results obtained provide strong evidence that the detection and perhaps even identification of bacteria

  17. Phytoplankton bloom dynamics in coastal ecosystems: A review with some general lessons from sustained investigation of San Francisco Bay, California

    USGS Publications Warehouse

    Cloern, James E.

    1996-01-01

    Phytoplankton blooms are prominent features of biological variability in shallow coastal ecosystems such as estuaries, lagoons, bays, and tidal rivers. Long-term observation and research in San Francisco Bay illustrates some patterns of phytoplankton spatial and temporal variability and the underlying mechanisms of this variability. Blooms are events of rapid production and accumulation of phytoplankton biomass that are usually responses to changing physical forcings originating in the coastal ocean (e.g., tides), the atmosphere (wind), or on the land surface (precipitation and river runoff). These physical forcings have different timescales of variability, so algal blooms can be short-term episodic events, recurrent seasonal phenomena, or rare events associated with exceptional climatic or hydrologic conditions. The biogeochemical role of phytoplankton primary production is to transform and incorporate reactive inorganic elements into organic forms, and these transformations are rapid and lead to measurable geochemical change during blooms. Examples include the depletion of inorganic nutrients (N, P, Si), supersaturation of oxygen and removal of carbon dioxide, shifts in the isotopic composition of reactive elements (C, N), production of climatically active trace gases (methyl bromide, dimethylsulfide), changes in the chemical form and toxicity of trace metals (As, Cd, Ni, Zn), changes in the biochemical composition and reactivity of the suspended particulate matter, and synthesis of organic matter required for the reproduction and growth of heterotrophs, including bacteria, zooplankton, and benthic consumer animals. Some classes of phytoplankton play special roles in the cycling of elements or synthesis of specific organic molecules, but we have only rudimentary understanding of the forces that select for and promote blooms of these species. Mounting evidence suggests that the natural cycles of bloom variability are being altered on a global scale by human

  18. Physico-chemical characterization of total suspended particulate matter over two coastal stations of Antarctica and adjoining ocean

    NASA Astrophysics Data System (ADS)

    Ali, Kaushar; Trivedi, D. K.; Sahu, Saroj

    2015-12-01

    Physical and chemical characteristics of the total suspended particulate matter (TSPM) measured during 11 January-21 March, 2009 and 09 December 2009-09 January, 2010 over two stations of Antarctica (Larsemann Hills and Maitri) and adjoining ocean are investigated. It is found that the concentration of TSPM is low over all the observational locations. Day-to-day variation in the concentration of TSPM is mainly controlled by variation in the weather systems and associated meteorological parameters. Average concentration of TSPM over Larsemann Hills is 7.6 μg/m3 during Jan-Mar 2009 and 2.4 μg/m3 during Dec. 2009-Jan 2010. It is 9.0 μg/m3 over Maitri during Jan-Mar 2009. On excluding the TSPM data of the disturbed weather days during Jan-Mar 2009, the concentration of TSPM is found to be 4.2 μg/m3 over Larsemann Hills and 4.3 μg/m3 over Maitri. The TSPM at all the observational locations is acidic in nature with a maximum pH value of 5.56 at Larsemann Hills. The pH value of TSPM over Maitri is found to be 5.28. The acidic nature of TSPM indicates the absence of sufficient neutralizing alkaline minerals. Among the measured chemical anions Cl- dominates at all the locations except at Maitri where SO42- ion shows maximum concentration. The dominant cation is Na+ at all the observational stations. Sizeable fraction of SO42- is found at all the observational locations. Abundance of SO42- in the atmosphere of Antarctica and its surrounding region is mainly due to emission of dimethylsulfide (DMS) phytoplankton and its oxidation finally to SO42- particles by gas-to-particle conversion. The highest concentration of SO42- over Maitri is attributed to the contribution from anthropogenic activity at Maitri, in addition to the biogenic SO42- . NH4+ plays dominant role in neutralizing the acidic components of the aerosols.

  19. Methyl-methionine as a precursor for methyl chloride and dimethyl sulphide produced in terrestrial salt lakes

    NASA Astrophysics Data System (ADS)

    Mulder, I.; Krause, T.; Studenroth, S.; Tubbesing, C.; Kotte, K.; Schöler, H. F.

    2012-04-01

    Volatile organic halocarbons (VOX) play an important role in the photochemical processes of the lower atmosphere and information on the geogenic origin of these compounds will help to understand global VOX budgets and fluxes. However, investigations concerned with occurrence of VOX in fluid inclusions of rocks and minerals are scarce (Harnisch and Eisenhauer, 1998; Svensen et al., 2009). The composition of volatile organic carbons (VOC) trapped in fluid inclusions of halite crystals deposited in recent salt pans was analysed using a purge and trap GC-MS technique. Besides an array of identified volatile compounds we noticed the occurrence of chloromethane (MeCl), dimethylsulfide (DMS) or both in most of a divers set of samples. Methyl chloride with an atmospheric burden of 4 to 5 Tg, is the most abundant halocarbon in the atmosphere. It plays a significant role in chlorine-catalyzed ozone destruction in the stratosphere (Keppler et al., 2005; Montzka and Frazer, 2003). DMS is the major natural, mainly marine, source of sulphur in the atmosphere and contributes to both the tropospheric burden of sulphur as well as cloud properties via oxidation to acidic aerosols (Kloster et al., 2006; Sievert et al., 2007). It is also known that a conversion of methionine (MET) to dimethylsulfonium-propionate by phytoplankton takes place, which in turn serves as the main precursor for DMS emission from the surface ocean to the atmosphere (Sievert et al., 2007). In search of a possible precursor for the above mentioned two compounds we hypothesize that the compounds trapped in the fluid inclusions represent compounds originally formed in the immediately subjacent sediment. MET, as one of three sulfur containing amino acids, could potentially serve as a precursor for MeCl and DMS formed in salt lake environments. To test these hypotheses, we measured selected sediment samples that correspond to the previously measured salt samples. Separately, we studied the temperature dependence of

  20. DMSP and DMS dynamics during a mesoscale iron fertilization experiment in the Northeast Pacific Part II: Biological cycling

    NASA Astrophysics Data System (ADS)

    Merzouk, Anissa; Levasseur, Maurice; Scarratt, Michael G.; Michaud, Sonia; Rivkin, Richard B.; Hale, Michelle S.; Kiene, Ronald P.; Price, Neil M.; Li, William K. W.

    2006-10-01

    Dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) biological cycling rates were determined during SERIES, a mesoscale iron-fertilization experiment conducted in the high-nutrient low-chlorophyll (HNLC) waters of the northeast subarctic Pacific. The iron fertilization resulted in the rapid development of a nanoplankton assemblage that persisted for 11 days before abruptly crashing. The nanoplankton bloom was followed by a diatom bloom, accompanied by an important increase in bacterial abundance and production. These iron-induced alterations of the plankton assemblage coincided with changes in the size and biological cycling of the DMSP and DMS pools. The initial nanoplankton bloom resulted in increases in particulate DMSP (DMSPp; 77-180 nmol L -1), dissolved DMSP (DMSPd; 1-24 nmol L -1), and biological gross (0.11-0.78 nmol L -1 h -1) and net (0.04-0.74 nmol L -1 h -1) DMS production rates. During the nanoplankton bloom, DMSPd consumption by bacteria exceeded their sulfur demand and the excess sulfur was probably released as DMS, consistent with the high gross DMS production rates observed during that period. The crash of the nanoplankton bloom was marked by the rapid decline of DMSPp, DMSPd, and gross DMS production to their initial values. Following the crash of the nanoplankton bloom, bacterial production and estimated sulfur demand reached transient maxima of 9.3 μg C L -1 d -1 and 14.2 nmol S L -1 d -1, respectively. During this period of high bacterial production, bacterial DMSPd consumption was also very high (6 nmol L -1 h -1), but none of the consumed DMSPd was converted into DMS and a net biological DMS consumption was measured. This transient period initiated a rapid decrease in DMS concentrations inside the iron-enriched patch, which persisted during the following diatom bloom due to low biological gross and net DMS production that prevented the replenishment of DMS. Our results show that the impact of Fe fertilization on DMS production in

  1. BIOSIGNATURE GASES IN H{sub 2}-DOMINATED ATMOSPHERES ON ROCKY EXOPLANETS

    SciTech Connect

    Seager, S.; Bains, W.; Hu, R.

    2013-11-10

    Super-Earth exoplanets are being discovered with increasing frequency and some will be able to retain stable H{sub 2}-dominated atmospheres. We study biosignature gases on exoplanets with thin H{sub 2} atmospheres and habitable surface temperatures, using a model atmosphere with photochemistry and a biomass estimate framework for evaluating the plausibility of a range of biosignature gas candidates. We find that photochemically produced H atoms are the most abundant reactive species in H{sub 2} atmospheres. In atmospheres with high CO{sub 2} levels, atomic O is the major destructive species for some molecules. In Sun-Earth-like UV radiation environments, H (and in some cases O) will rapidly destroy nearly all biosignature gases of interest. The lower UV fluxes from UV-quiet M stars would produce a lower concentration of H (or O) for the same scenario, enabling some biosignature gases to accumulate. The favorability of low-UV radiation environments to accumulate detectable biosignature gases in an H{sub 2} atmosphere is closely analogous to the case of oxidized atmospheres, where photochemically produced OH is the major destructive species. Most potential biosignature gases, such as dimethylsulfide and CH{sub 3}Cl, are therefore more favorable in low-UV, as compared with solar-like UV, environments. A few promising biosignature gas candidates, including NH{sub 3} and N{sub 2}O, are favorable even in solar-like UV environments, as these gases are destroyed directly by photolysis and not by H (or O). A more subtle finding is that most gases produced by life that are fully hydrogenated forms of an element, such as CH{sub 4} and H{sub 2}S, are not effective signs of life in an H{sub 2}-rich atmosphere because the dominant atmospheric chemistry will generate such gases abiologically, through photochemistry or geochemistry. Suitable biosignature gases in H{sub 2}-rich atmospheres for super-Earth exoplanets transiting M stars could potentially be detected in transmission

  2. Parameter sensitivities in a 1-D model for DMS and sulphur cycling in the upper ocean

    NASA Astrophysics Data System (ADS)

    Steiner, N.; Denman, K.

    2008-07-01

    We have developed a marine DMS (dimethylsulfide) module and implemented it in a 1-D coupled atmosphere-ocean-biogeochemical model. In developing the marine sulphur model we have found that several parameters used in the model are not known to even an order of magnitude. Our approach is used to test the model's sensitivity to these parameters. A parameter change of ±25% is applied to test the respective range of changes in the DMS fluxes. The model is run for a 3-year time period as well as for the time period of the Subarctic Ecosystem Response to Iron Enrichment Study (SERIES) in July 2002. The simulated seasonal cycle is in agreement with available observations: Near surface DMS concentrations vary from 1.5nmolL-1 in winter to 13.5nmolL-1 in summer. Simulated DMS production is found to be most sensitive to variations of the S:N ratio and the bacterial consumption rate of DMS. Implementing light or UV limited bacterial activity shows a negligible effect in winter and increases DMS concentrations by 0.2- 0.6nmolL-1 in summer. Similarly a yield increase under UV stress increases summer values by 1- 2nmolL-1. The simulated diel cycle in surface DMS concentration is no more than 2.5nmolL-1, even when light-dependent changes in bacterial activity are considered. Simulating the DMS response to iron fertilization with the standard run leads to overestimation during an initial bloom of small phytoplankton. While implementing light-dependent bacterial activity has a minor effect, the implementation of yields that depend on nutrient availability significantly improves the results. The model confirms earlier results showing the importance of including atmospheric DMS concentrations in gas flux calculations when there are high surface concentrations and small atmospheric boundary layer heights. Simulated summer concentrations in the upper layer can be underestimated by 2nmolL-1 or more if the atmospheric concentration is set to zero. Our study shows that inclusion of

  3. Aerosol Composition, Chemistry, and Source Characterization during the 2008 VOCALS Experiment

    NASA Astrophysics Data System (ADS)

    Lee, Y.; Springston, S.; Jayne, J. T.; Wang, J.; Senum, G.; Hubbe, J.; Alexander, L.; Brioude, J.; Spak, S.; Mena-Carrasco, M.; Kleinman, L. I.; Daum, P. H.

    2009-12-01

    Chemical composition of fine aerosol particles over the northern Chilean coastal waters was determined on board the US DOE G-1 aircraft during the VOCALS (VAMOS Ocean-Cloud-Atmosphere-Land Study) field experiment between October 16 and November 15, 2008. Chemical species determined included SO42-, NO3-, NH4+, and total organics (Org) using an Aerodyne Aerosol Mass Spectrometer, and SO42-, NO3-, NH4+, Na+, Cl-, CH3SO3-, Mg2+, Ca2+, and K+ using a particle-into-liquid sampler-ion chromatography technique. The results show the marine boundary layer (MBL) aerosol mass was dominated by non-sea-salt SO42- followed by Na+, Cl-, Org, NO3-, and NH4+, in decreasing importance; CH3SO3-, Ca2+, and K+ rarely exceeded their respective limits of detection. The SO42- aerosols were strongly acidic as the equivalent NH4+ to SO42- ratio was only ~0.25 on average. NaCl particles, presumably of sea-salt origin, showed chloride deficits but retained Cl- typically more than half the equivalency of Na+, and are believed to be externally mixed with the acidic sulfate aerosols. Nitrate was observed only on sea-salt particles, consistent with adsorption of HNO3 on non-acidic sea-salt aerosols, responsible partly for the Cl- deficit. Dust particles appeared to play a minor role judging from the small volume differences between that derived from the observed mass concentrations and that calculated based on particle size distributions. Because SO42- concentrations in the study domain were substantial (~0.5 - ~3 μg/m3) with a strong gradient (highest near the shore decreasing with distance from land), and the ocean-emitted dimethylsulfide and its unique oxidation product, CH3SO3-, were very low (i.e., ≤ 40 parts per trillion and <0.05 μg/m3, respectively), the observed SO42- aerosols are believed to be primarily of terrestrial origin. Back trajectory calculations indicate sulfur emissions from smelters and power plants along coastal regions of Peru and Chile are the main sources of these SO4

  4. Aerosol composition, chemistry, and source characterization during the 2008 VOCALS Experiment

    SciTech Connect

    Lee, Y.; Springston, S.; Jayne, J.; Wang, J.; Senum, G.; Hubbe, J.; Alexander, L.; Brioude, J.; Spak, S.; Mena-Carrasco, M.; Kleinman, L.; Daum, P.

    2010-03-15

    Chemical composition of fine aerosol particles over the northern Chilean coastal waters was determined onboard the U.S. DOE G-1 aircraft during the VOCALS (VAMOS Ocean-Cloud-Atmosphere-Land Study) field campaign between October 16 and November 15, 2008. SO42-, NO3-, NH4+, and total organics (Org) were determined using an Aerodyne Aerosol Mass Spectrometer, and SO42-, NO3-, NH4+, Na+, Cl-, CH3SO3-, Mg2+, Ca2+, and K+ were determined using a particle-into-liquid sampler-ion chromatography technique. The results show the marine boundary layer (MBL) aerosol mass was dominated by non- sea-salt SO42- followed by Na+, Cl-, Org, NO3-, and NH4+, in decreasing importance; CH3SO3-, Ca2+, and K+ rarely exceeded their respective limits of detection. The SO42- aerosols were strongly acidic as the equivalent NH4+ to SO42- ratio was only {approx}0.25 on average. NaCl particles, presumably of sea-salt origin, showed chloride deficits but retained Cl- typically more than half the equivalency of Na+, and are externally mixed with the acidic sulfate aerosols. Nitrate was observed only on sea-salt particles, consistent with adsorption of HNO3 on sea-salt aerosols, responsible for the Cl- deficit. Dust particles appeared to play a minor role, judging from the small volume differences between that derived from the observed mass concentrations and that calculated based on particle size distributions. Because SO42- concentrations were substantial ({approx}0.5 - {approx}3 {micro}g/m3) with a strong gradient (highest near the shore), and the ocean-emitted dimethylsulfide and its unique oxidation product, CH3SO3-, were very low (i.e., {le} 40 parts per trillion and <0.05 {micro}g/m3, respectively), the observed SO42- aerosols are believed to be primarily of terrestrial origin. Back trajectory calculations indicate sulfur emissions from smelters and power plants along coastal regions of Peru and Chile are the main sources of these SO4- aerosols. However, compared to observations, model

  5. Analysis of small scale turbulent structures and the effect of spatial scales on gas transfer

    NASA Astrophysics Data System (ADS)

    Schnieders, Jana; Garbe, Christoph

    2014-05-01

    processes on interfacial transport and relate it to gas transfer. References [1] T. G. Bell, W. De Bruyn, S. D. Miller, B. Ward, K. Christensen, and E. S. Saltzman. Air-sea dimethylsulfide (DMS) gas transfer in the North Atlantic: evidence for limited interfacial gas exchange at high wind speed. Atmos. Chem. Phys. , 13:11073-11087, 2013. [2] J Schnieders, C. S. Garbe, W.L. Peirson, and C. J. Zappa. Analyzing the footprints of near surface aqueous turbulence - an image processing based approach. Journal of Geophysical Research-Oceans, 2013.

  6. Modelling marine emissions and atmospheric distributions of halocarbons and DMS: the influence of prescribed water concentration vs. prescribed emissions

    NASA Astrophysics Data System (ADS)

    Lennartz, S. T.; Krysztofiak-Tong, G.; Marandino, C. A.; Sinnhuber, B.-M.; Tegtmeier, S.; Ziska, F.; Hossaini, R.; Krüger, K.; Montzka, S. A.; Atlas, E.; Oram, D.; Keber, T.; Bönisch, H.; Quack, B.

    2015-06-01

    Marine produced short-lived trace gases such as dibromomethane (CH2Br2), bromoform (CHBr3), methyliodide (CH3I) and dimethylsulfide (DMS) significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and the Earth's radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model real-time conditions at ocean surface and atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions) of VSLS. We show that differences between prescribing emissions and prescribing concentrations (-28 % for CH2Br2 to +11 % for CHBr3) result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air-sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of different air

  7. Inorganic bromine in the marine boundary layer: a critical review

    NASA Astrophysics Data System (ADS)

    Sander, R.; Keene, W. C.; Pszenny, A. A. P.; Arimoto, R.; Ayers, G. P.; Baboukas, E.; Cainey, J. M.; Crutzen, P. J.; Duce, R. A.; Hönninger, G.; Huebert, B. J.; Maenhaut, W.; Mihalopoulos, N.; Turekian, V. C.; van Dingenen, R.

    2003-06-01

    dimethylsulfide (DMS) and hydrocarbons in the gas phase and S(IV) in aerosol solutions, and thereby potentially influence climate. The diurnal cycle of gas-phase Br and the corresponding particulate Br deficits are correlated. Higher values of Br in the gas phase during daytime are consistent with expectations based on photochemistry. Mechanisms that explain the widely reported accumulation of particulate Br in submicrometer aerosols are not yet understood. We expect that the importance of inorganic Br cycling will vary in the future as a function of both increasing acidification of the atmosphere (through anthropogenic emissions) and climate changes. The latter affects bromine cycling via meteorological factors including global wind fields (and the associated production of sea-salt aerosol), temperature, and relative humidity.

  8. Inorganic bromine in the marine boundary layer: a critical review

    NASA Astrophysics Data System (ADS)

    Sander, R.; Keene, W. C.; Pszenny, A. A. P.; Arimoto, R.; Ayers, G. P.; Baboukas, E.; Cainey, J. M.; Crutzen, P. J.; Duce, R. A.; Hönninger, G.; Huebert, B. J.; Maenhaut, W.; Mihalopoulos, N.; Turekian, V. C.; van Dingenen, R.

    2003-09-01

    Br and Cl. Subsequent transformations can destroy tropospheric ozone, oxidize dimethylsulfide (DMS) and hydrocarbons in the gas phase and S(IV) in aerosol solutions, and thereby potentially influence climate. The diurnal cycle of gas-phase Br and the corresponding particulate Br deficits are correlated. Higher values of Br in the gas phase during daytime are consistent with expectations based on photochemistry. We expect that the importance of inorganic Br cycling will vary in the future as a function of both increasing acidification of the atmosphere (through anthropogenic emissions) and climate changes. The latter affects bromine cycling via meteorological factors including global wind fields (and the associated production of sea-salt aerosol), temperature, and relative humidity.

  9. Transparent organosilica photocatalysts activated by visible light: photophysical and oxidative properties at the gas-solid interface.

    PubMed

    Arzoumanian, Emmanuel; Ronzani, Filippo; Trivella, Aurélien; Oliveros, Esther; Sarakha, Mohamed; Richard, Claire; Blanc, Sylvie; Pigot, Thierry; Lacombe, Sylvie

    2014-01-08

    The photophysical properties of several photosensitizers (PSs) included or grafted in silica monoliths were compared to their properties in solution. The effects of the solid support on their steady-state and transient absorption spectra, on their quantum yields of singlet oxygen ((1)O2) production, and on their ability to photoinduce the oxidation of dimethylsulfide (DMS) were investigated. Two cyanoanthracene derivatives (9,14-dicyanobenzo[b]triphenylene, DBTP, and 9,10-dicyanoanthracene, DCA), as well as three phenothiazine dyes (methylene blue, MB(+), new methylene blue, NMB(+), methylene violet, MV), were encapsulated in silica, analyzed and compared to two reference PSs (perinaphthenone, PN and rose bengal, RB). A DBTP derivative (3-[N-(N″-triethoxysilylpropyl-N'-hexylurea)]carboxamido-9,14-dicyanobenzo[b]triphenylene, 3) was also prepared and grafted onto silica. Thanks to the transparency and the free-standing shape of the monoliths, the complete spectroscopic characterization of the supported PSs was carried out directly at the gas-solid interface. The influence of the silica network, the PS, and the adsorption/grafting link between the PS and silica was investigated. The effects of PS concentration, gaseous atmosphere, humidity, and hydrophobicity on the production of (1)O2 were analyzed. With all PSs, (1)O2 production was very efficient (quantum yields of (1)O2 production, relative to PN, between 0.6 and 1), and this species was the only one involved in the pollutant photooxidation. The influence of the matrix on the PSs' photophysics could be considered as negligible. In contrast, the matrix effect on DMS photooxidation was extremely important: the gas diffusion inside the porous structure, and thus, the photoactivity of the materials, strictly depended on silica's surface area and porosity. Our results highlight the suitability of these silica structures as inert supports for the study of the photosensitizing properties at the gas-solid interface

  10. Synthesis, structural characterization, and reactivity studies of 5-CF3SO3-B10H13.

    PubMed

    Berkeley, Emily R; Ewing, William C; Carroll, Patrick J; Sneddon, Larry G

    2014-05-19

    In contrast to previous reactions carried out in cyclopentane solvent at room temperature that produced 6-TfO-B10H13 (TfO = CF3SO3), the reaction of closo-B10H10(2-) with a large excess of trifluoromethanesulfonic acid in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (bmimOTf) gave exclusively the previously unknown 5-TfO-B10H13 isomer. Experimental and computational studies demonstrated that the difference in the products of the two reactions is a result of 6-TfO-B10H13 isomerizing to 5-TfO-B10H13 above room temperature in bmimOTf solutions. Reactivity studies showed that 5-TfO-B10H13: (1) is deprotonated by reaction with 1,8-bis(dimethylamino)naphthalene to form the 5-TfO-B10H12(1-) anion; (2) reacts with alcohols to produce 6-RO-B10H13 boryl ethers (R = Me and 4-CH3O-C6H4); (3) undergoes olefin-hydroboration reactions to form 5-TfO-6,9-R2-B10H11 derivatives; and (4) forms a 5-TfO-6,9-(Me2S)2-B10H11 adduct at its Lewis acidic 6,9-borons upon reaction with dimethylsulfide. The 5-TfO-6,9-(Me2S)2-B10H11 adduct was also found to undergo alkyne-insertion reactions to form a range of previously unreported triflate-substituted 4-TfO-ortho-carboranes (1-R-4-TfO-1,2-C2B10H10) and reactions with triethylamine or ammonia to form the first TfO-substituted decaborate [R3NH(+)]2[2-TfO-B10H9(2-)], and [R3NH(+)]2[1-TfO-B10H9(2-)] (R = H, Et) salts.

  11. Theoretical spectroscopic characterization at low temperatures of detectable sulfur-organic compounds: ethyl mercaptan and dimethyl sulfide.

    PubMed

    Senent, M L; Puzzarini, C; Domínguez-Gómez, R; Carvajal, M; Hochlaf, M

    2014-03-28

    Highly correlated ab initio methods are used for the spectroscopic characterization of ethyl mercaptan (CH3CH2 (32)SH, ETSH) and dimethyl sulfide (CH3 (32)SCH3, DMS), considering them on the vibrational ground and excited torsional states. Since both molecules show non-rigid properties, torsional energy barriers and splittings are provided. Equilibrium geometries and the corresponding rotational constants are calculated by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The ground and excited states rotational constants are then determined using vibrational corrections obtained from CCSD/cc-pVTZ force-field calculations, which are also employed to determine anharmonic frequencies for all vibrational modes. CCSD(T) and CCSD force fields are employed to predict quartic and sextic centrifugal-distortion constants, respectively. Equilibrium rotational constants are also calculated using CCSD(T)-F12. The full-dimensional anharmonic analysis does not predict displacements of the lowest torsional excited states due to Fermi resonances with the remaining vibrational modes. Thus, very accurate torsional transitions are calculated by solving variationally two-dimensional Hamiltonians depending on the CH3 and SH torsional coordinates of ethyl mercaptan or on the two methyl groups torsions of dimethyl-sulfide. For this purpose, vibrationally corrected potential energy surfaces are computed at the CCSD(T)/aug-cc-pVTZ level of theory. For ethyl mercaptan, calculations show large differences between the gauche (g) and trans (t) conformer spectral features. Interactions between rotating groups are responsible for the displacements of the g-bands with respect to the t-bands that cannot therefore be described with one-dimensional models. For DMS, the CCSD(T) potential energy surface has been semi-empirically adjusted to reproduce experimental data. New assignments are

  12. Nonlinear Source -" Receptor Relationship due to Interactions between Atmospheric Constituents, Water Cycle and Biogenic Emissions

    NASA Astrophysics Data System (ADS)

    Kinne, S.; Feichter, J.; Rast, S.; Bey, I.; Folberth, G.; Pozzoli, L.; Kloster, S.; Stier, P.

    2007-05-01

    result in different climate sensitivity will be raised. Feichter J, Roeckner E, Lohmann U., Liepert B (2004): Nonlinear aspects of the climate response to greenhouse gas and aerosol forcing, Journal of Climate; 17, No 12, 2384-2398. Kloster, S. , Feichter, J., Maier-Reimer, E., Roeckner, Wetzel, P., Six, K.D., Stier, P. and Esch, M., (2007): Response of dimethylsulfide (DMS) in the ocean and atmosphere to global warming, J. Geophys. Res. (subm). Stier, P., J. Feichter, S. Kloster, E. Vignati, and J. Wilson (2006): Emission-Induced Nonlinearities in the Global Aerosol System - Results from the ECHAM5-HAM Aerosol-Climate Model, J. Clim Pozzoli L, I Bey, S Rast, M Schultz, P Stier and Feichter, (2007): Trace gas and aerosol interactions in a global coupled model of chemistry-aerosol-climate (to be subm.).

  13. Air Pollution Source/receptor Relationships in South Coast Air Basin, CA

    NASA Astrophysics Data System (ADS)

    Gao, Ning

    This research project includes the application of some existing receptor models to study the air pollution source/receptor relationships in the South Coast Air Basin (SoCAB) of southern California, the development of a new receptor model and the testing and the modifications of some existing models. These existing receptor models used include principal component factor analysis (PCA), potential source contribution function (PSCF) analysis, Kohonen's neural network combined with Prim's minimal spanning tree (TREE-MAP), and direct trilinear decomposition followed by a matrix reconstruction. The ambient concentration measurements used in this study are a subset of the data collected during the 1987 field exercise of Southern California Air Quality Study (SCAQS). It consists of a number of gaseous and particulate pollutants analyzed from samples collected by SCAQS samplers at eight sampling sites, Anaheim, Azusa, Burbank, Claremont, Downtown Los Angeles, Hawthorne, Long Beach, and Rubidoux. Based on the information of emission inventories, meteorology and ambient concentrations, this receptor modeling study has revealed mechanisms that influence the air quality in SoCAB. Some of the mechanisms affecting the air quality in SoCAB that were revealed during this study include the following aspects. The SO_2 collected at sampling sites is mainly contributed by refineries in the coastal area and the ships equipped with oil-fired boilers off shore. Combustion of fossil fuel by automobiles dominates the emission of NO_{rm x} that is subsequently transformed and collected at sampling sites. Electric power plants also contribute HNO_3 to the sampling sites. A large feedlot in the eastern region of SoCAB has been identified as the major source of NH_3. Possible contributions from other industrial sources such as smelters and incinerators were also revealed. The results of this study also suggest the possibility of DMS (dimethylsulfide) and NH_3 emissions from off-shore sediments

  14. Seasonal and interannual variabilities of coccolithophore blooms in the Bay of Biscay and the Celtic Sea observed from a 18-year time-series of non-algal Suspended Particulate Matter images

    NASA Astrophysics Data System (ADS)

    Perrot, Laurie; Gohin, Francis; Ruiz-Pino, Diana; Lampert, Luis

    2016-04-01

    Coccolithophores belong to the nano-phytoplankton size-class and produce CaCO3 scales called coccoliths which form the «shell» of the algae cell. Coccoliths are in the size range of a few μm and can also be detached from the cell in the water. This phytoplankton group has an ubiquitous distribution in all oceans but blooms only in some oceanic regions, like the North East Atlantic ocean and the South Western Atlantic (Patagonian Sea). At a global scale coccolithopore blooms are studied in regard of CaCO3 production and three potential feedback on climate change: albedo modification by the way of dimethylsulfide (DMS) production and atmospheric CO2 source by calcification and a CO2 pump by photosynthesis. As the oceans are more and more acidified by anthropogenic CO2 emissions, coccolithophores generally are expected to be negatively affected. However, recent studies have shown an increase in coccolithophore occurrence in the North Atlantic. A poleward expansion of the coccolithophore Emiliana Huxleyi has also been pointed out. By using a simplified fuzzy method applied to a 18-year time series of SeaWiFS (1998-2002) and MODIS (2003-2015) spectral reflectance, we assessed the seasonal and inter-annual variability of coccolithophore blooms in the vicinity of the shelf break in the Bay of Biscay and the Celtic Sea After identification of the coccolith pixels by applying the fuzzy method, the abundance of coccoliths is assessed from a database of non-algal Suspended Particulate Matter (SPM). Although a regular pattern in the phenology of the blooms is observed, starting south in April in Biscay and moving northwards until July in Ireland, there is a high seasonal and interannual variability in the extent of the blooms. Year 2014 shows very low concentrations of detached coccoliths (twice less than average) from space and anomalies point out the maximum level in 2001. Non-algal SPM, derived from a procedure defined for the continental shelf, appears to be well

  15. WRF-Chem model predictions of the regional impacts of N2O5 heterogeneous processes on night-time chemistry over north-western Europe

    SciTech Connect

    Lowe, Douglas; Archer-Nicholls, Scott; Morgan, Will; Allan, James D.; Utembe, Steve; Ouyang, Bin; Aruffo, Eleonora; Le Breton, Michael; Zaveri, Rahul A.; di Carlo, Piero; Percival, Carl; Coe, H.; Jones, Roderic L.; McFiggans, Gordon

    2015-02-09

    3 oxidation of VOCs across the whole region was found to be 100–300 times slower than the daytime OH oxidation of these compounds. The difference in contribution was less for alkenes (× 80) and comparable for dimethylsulfide (DMS). However the suppression of NO3 mixing ratios across the domain by N2O5 heterogeneous chemistry has only a very slight, negative, influence on this oxidative capacity. The influence on regional particulate nitrate mass loadings is stronger. Night-time N2O5 heterogeneous chemistry maintains the production of particulate nitrate within polluted regions: when this process is taken into consideration, the daytime peak (for the 95th percentile) of PM10 nitrate mass loadings remains around 5.6 μg kg−1air, but the night-time minimum increases from 3.5 to 4.6 μg kg−1air. The sustaining of higher particulate mass loadings through the night by this process improves model skill at matching measured aerosol nitrate diurnal cycles and will negatively impact on regional air quality, requiring this process to be included in regional models.

  16. Oceanic isoprene and DMS distributions during low-productive conditions in the Indian Ocean

    NASA Astrophysics Data System (ADS)

    Booge, Dennis; Zavarsky, Alexander; Bell, Thomas; Marandino, Christa

    2015-04-01

    Despite their low abundances compared to the long lived greenhouse gases such as carbon dioxide and methane, short-lived trace gases produced in the oceans have been recognized as playing an important role in atmospheric chemistry and climate. Both isoprene and dimethylsulfide (DMS) are biogenic trace gases produced in the ocean and due to their supersaturation in the surface ocean are emitted to the atmosphere. Once emitted, they produce secondary organic aerosols via fast oxidation processes in the atmosphere (isoprene has a lifetime on approximately 1 hour and DMS 1 day). Consequently, both are hypothesized to significantly impact the radiative balance of the marine atmosphere. However, the strength of this impact is controversial. It is known that the emissions of these compounds to the atmosphere are critically controlled by surface ocean biogeochemical and physical factors which are, especially for isoprene, poorly quantified and unpredictable. Therefore, in order to more fully understand the role of isoprene and DMS on the marine atmosphere, more studies of their distributions, controlling factors, and air-sea exchange are urgently needed. Here we present preliminary measurements of isoprene and DMS concentrations from the SPACES and OASIS campaigns onboard the R/V Sonne that took place from July 8th to August 7th starting in Durban, South Africa and ending in Malé, Maledives. An improved purge and trap technique coupled with a gas chromatograph-mass spectrometer (GC-MS) was used to measure isoprene and DMS in one run for both surface and depth profile samples. In addition, an atmospheric pressure chemical ionization mass spectrometer (AP-CIMS) was used to perform continuous surface measurements of these compounds. The discrete surface measurements were made every three hours using a submersible pump located in the ship's moonpool at 6 m depth. For depth profile measurements samples were taken from 5 m to about 100 m depth. There have been no reported

  17. Investigations of Methane Production in Hypersaline Environments

    NASA Technical Reports Server (NTRS)

    Bebout, Brad M.

    2015-01-01

    produced by these sediments. Substrate limitation of methanogenesis in these environments, and not methane oxidation, would explain the isotopic values of the methane in these environments. Incubations with both isotopically labeled and unlabeled putative substrates for methanogenesis have shown that the substrates most important for methanogenesis in these environments are the so-called non-competitive substrates, e.g., methylamines, dimethylsulfide, and methanol. Acetate and bicarbonate appear not to be important substrates for methanogens in these environments. Extraction of DNA and analysis of a gene used for methane production (mcrA) has revealed that the community composition of methanogens is consistent with organisms known to use non-competitive substrates. Our work has shown that hypersaline environments have the potential to both produce and preserve methane for analysis, e.g., by capable rovers. Our work expends the range of methane isotopic values now known to be produced by active methanogenesis

  18. WRF-Chem model predictions of the regional impacts of N2O5 heterogeneous processes on night-time chemistry over north-western Europe

    DOE PAGES

    Lowe, Douglas; Archer-Nicholls, Scott; Morgan, Will; ...

    2015-02-09

    alkenes (× 80) and comparable for dimethylsulfide (DMS). However the suppression of NO3 mixing ratios across the domain by N2O5 heterogeneous chemistry has only a very slight, negative, influence on this oxidative capacity. The influence on regional particulate nitrate mass loadings is stronger. Night-time N2O5 heterogeneous chemistry maintains the production of particulate nitrate within polluted regions: when this process is taken into consideration, the daytime peak (for the 95th percentile) of PM10 nitrate mass loadings remains around 5.6 μg kg−1air, but the night-time minimum increases from 3.5 to 4.6 μg kg−1air. The sustaining of higher particulate mass loadings through the night by this process improves model skill at matching measured aerosol nitrate diurnal cycles and will negatively impact on regional air quality, requiring this process to be included in regional models.« less

  19. Effect of ocean acidification and elevated fCO2 on trace gas production by a Baltic Sea summer phytoplankton community

    NASA Astrophysics Data System (ADS)

    Webb, Alison L.; Leedham-Elvidge, Emma; Hughes, Claire; Hopkins, Frances E.; Malin, Gill; Bach, Lennart T.; Schulz, Kai; Crawfurd, Kate; Brussaard, Corina P. D.; Stuhr, Annegret; Riebesell, Ulf; Liss, Peter S.

    2016-08-01

    The Baltic Sea is a unique environment as the largest body of brackish water in the world. Acidification of the surface oceans due to absorption of anthropogenic CO2 emissions is an additional stressor facing the pelagic community of the already challenging Baltic Sea. To investigate its impact on trace gas biogeochemistry, a large-scale mesocosm experiment was performed off Tvärminne Research Station, Finland, in summer 2012. During the second half of the experiment, dimethylsulfide (DMS) concentrations in the highest-fCO2 mesocosms (1075-1333 µatm) were 34 % lower than at ambient CO2 (350 µatm). However, the net production (as measured by concentration change) of seven halocarbons analysed was not significantly affected by even the highest CO2 levels after 5 weeks' exposure. Methyl iodide (CH3I) and diiodomethane (CH2I2) showed 15 and 57 % increases in mean mesocosm concentration (3.8 ± 0.6 increasing to 4.3 ± 0.4 pmol L-1 and 87.4 ± 14.9 increasing to 134.4 ± 24.1 pmol L-1 respectively) during Phase II of the experiment, which were unrelated to CO2 and corresponded to 30 % lower Chl a concentrations compared to Phase I. No other iodocarbons increased or showed a peak, with mean chloroiodomethane (CH2ClI) concentrations measured at 5.3 (±0.9) pmol L-1 and iodoethane (C2H5I) at 0.5 (±0.1) pmol L-1. Of the concentrations of bromoform (CHBr3; mean 88.1 ± 13.2 pmol L-1), dibromomethane (CH2Br2; mean 5.3 ± 0.8 pmol L-1), and dibromochloromethane (CHBr2Cl, mean 3.0 ± 0.5 pmol L-1), only CH2Br2 showed a decrease of 17 % between Phases I and II, with CHBr3 and CHBr2Cl showing similar mean concentrations in both phases. Outside the mesocosms, an upwelling event was responsible for bringing colder, high-CO2, low-pH water to the surface starting on day t16 of the experiment; this variable CO2 system with frequent upwelling events implies that the community of the Baltic Sea is acclimated to regular significant declines in pH caused by up to 800 µatm fCO2. After

  20. The SOLAS air-sea gas exchange experiment (SAGE) 2004

    NASA Astrophysics Data System (ADS)

    Harvey, Mike J.; Law, Cliff S.; Smith, Murray J.; Hall, Julie A.; Abraham, Edward R.; Stevens, Craig L.; Hadfield, Mark G.; Ho, David T.; Ward, Brian; Archer, Stephen D.; Cainey, Jill M.; Currie, Kim I.; Devries, Dawn; Ellwood, Michael J.; Hill, Peter; Jones, Graham B.; Katz, Dave; Kuparinen, Jorma; Macaskill, Burns; Main, William; Marriner, Andrew; McGregor, John; McNeil, Craig; Minnett, Peter J.; Nodder, Scott D.; Peloquin, Jill; Pickmere, Stuart; Pinkerton, Matthew H.; Safi, Karl A.; Thompson, Rona; Walkington, Matthew; Wright, Simon W.; Ziolkowski, Lori A.

    2011-03-01

    only doubled relative to the unfertilised surrounding waters by the end of the experiment. After 15 days and four iron additions totalling 1.1 ton Fe 2+, this was a very modest response compared to other mesoscale iron enrichment experiments. An investigation of the factors limiting bloom development considered co-limitation by light and other nutrients, the phytoplankton seed-stock and grazing regulation. Whilst incident light levels and the initial Si:N ratio were the lowest recorded in all FeAXs to date, there was only a small seed-stock of diatoms (less than 1% of biomass) and the main response to iron addition was by the picophytoplankton. A high rate of dilution of the fertilised patch relative to phytoplankton growth rate, the greater than expected depth of the surface mixed layer and microzooplankton grazing were all considered as factors that prevented significant biomass accumulation. In line with the limited response, the enhanced biological draw-down of pCO 2 was small and masked by a general increase in pCO 2 due to mixing with higher pCO 2 waters. The DMS precursor DMSP was kept in check through grazing activity and in contrast to most FeAX's dissolved dimethylsulfide (DMS) concentration declined through the experiment. SAGE is an important low-end member in the range of responses to iron addition in FeAX's. In the context of iron fertilisation as a geoengineering tool for atmospheric CO 2 removal, SAGE has clearly demonstrated that a significant proportion of the low iron ocean may not produce a phytoplankton bloom in response to iron addition.

  1. Relationships linking primary production, sea ice melting, and biogenic aerosol in the Arctic

    NASA Astrophysics Data System (ADS)

    Becagli, S.; Lazzara, L.; Marchese, C.; Dayan, U.; Ascanius, S. E.; Cacciani, M.; Caiazzo, L.; Di Biagio, C.; Di Iorio, T.; di Sarra, A.; Eriksen, P.; Fani, F.; Giardi, F.; Meloni, D.; Muscari, G.; Pace, G.; Severi, M.; Traversi, R.; Udisti, R.

    2016-07-01

    This study examines the relationships linking methanesulfonic acid (MSA, arising from the atmospheric oxidation of the biogenic dimethylsulfide, DMS) in atmospheric aerosol, satellite-derived chlorophyll a (Chl-a), and oceanic primary production (PP), also as a function of sea ice melting (SIM) and extension of the ice free area in the marginal ice zone (IF-MIZ) in the Arctic. MSA was determined in PM10 samples collected over the period 2010-2012 at two Arctic sites, Ny Ålesund (78.9°N, 11.9°E), Svalbard islands, and Thule Air Base (76.5°N, 68.8°W), Greenland. PP is calculated by means of a bio-optical, physiologically based, semi-analytical model in the potential source areas located in the surrounding oceanic regions (Barents and Greenland Seas for Ny Ålesund, and Baffin Bay for Thule). Chl-a peaks in May in the Barents sea and in the Baffin Bay, and has maxima in June in the Greenland sea; PP follows the same seasonal pattern of Chl-a, although the differences in absolute values of PP in the three seas during the blooms are less marked than for Chl-a. MSA shows a better correlation with PP than with Chl-a, besides, the source intensity (expressed by PP) is able to explain more than 30% of the MSA variability at the two sites; the other factors explaining the MSA variability are taxonomic differences in the phytoplanktonic assemblages, and transport processes from the DMS source areas to the sampling sites. The taxonomic differences are also evident from the slopes of the correlation plots between MSA and PP: similar slopes (in the range 34.2-36.2 ng m-3of MSA/(gC m-2 d-1)) are found for the correlation between MSA at Ny Ålesund and PP in Barents Sea, and between MSA at Thule and PP in the Baffin Bay; conversely, the slope of the correlation between MSA at Ny Ålesund and PP in the Greenland Sea in summer is smaller (16.7 ng m-3of MSA/(gC m-2 d-1)). This is due to the fact that DMS emission from the Barents Sea and Baffin Bay is mainly related to the MIZ

  2. Assessing microbial responses to iron enrichment in the Subarctic Northeast Pacific: Do microcosms reproduce the in situ condition?

    NASA Astrophysics Data System (ADS)

    Scarratt, M. G.; Marchetti, A.; Hale, M. S.; Rivkin, R. B.; Michaud, S.; Matthews, P.; Levasseur, M.; Sherry, N.; Merzouk, A.; Li, W. K. W.; Kiyosawa, H.

    2006-10-01

    A microcosm experiment was conducted in the NE Pacific in July 2002 to compare the microbial response between microcosms and the Subarctic Ecosystem Response to Iron-Enrichment Study (SERIES) in situ iron-enrichment experiment. Seawater microcosms (20 L) were incubated aboard ship under natural light using three treatments: (1) low-iron seawater amended with 4 nmol l -1 FeSO 4 (+Fe); (2) low-iron seawater amended with 4 nmol l -1 FeSO 4 and 86 nmol l -1 GeO 2 (+Fe+Ge); (3) seawater collected from the in situ Fe-enriched patch (PW). The +Fe+Ge treatment used germanium to control diatom growth to assess the role of diatoms in dimethylsulfoniopropionate (DMSP) production. The following variables were measured in the microcosms and in situ: chlorophyll a (chl a), nitrate ( NO3-), silicic acid (Si(OH) 4), phytoplankton abundance and species identification, bacterial abundance (including estimates of low- and high-DNA bacteria), bacterial production, bacterial specific growth rate, particulate and dissolved DMSP and dimethylsulfide (DMS) concentrations. There was little or no significant difference (ANCOVA) in the response of most variables between the +Fe and PW microcosms, but large differences were observed between both these treatments and the in situ data from the enriched patch. Chl a in all microcosms increased from ambient levels (approx. 0.5-1 μg l -1) to approx. 4.5-6.2 μg l -1 after 11 d incubation, when NO3- was fully depleted from all microcosms. During this same period, in situ chl a increased more slowly to a maximum of 2.9 μg l -1 on day 11. Nanophytoplankton and picophytoplankton were more abundant in the microcosms relative to the in situ community, which became dominated by large diatoms. Bacterial abundance was similar in the microcosms and in situ, but bacterial production was significantly higher in the microcosms. While neither DMSP d nor DMS accumulation showed significant differences between the microcosms and in situ , particulate DMSP

  3. Interactive effects of solar UV radiation and climate change on biogeochemical cycling.

    PubMed

    Zepp, R G; Erickson, D J; Paul, N D; Sulzberger, B

    2007-03-01

    exposure to increased UV-B radiation, and have synergistic effects on the penetration of light into aquatic ecosystems. Future changes in climate will enhance stratification of lakes and the ocean, which will intensify photodegradation of CDOM by UV radiation. The resultant increase in the transparency of water bodies may increase UV-B effects on aquatic biogeochemistry in the surface layer. Changing solar UV radiation and climate also interact to influence exchanges of trace gases, such as halocarbons (e.g., methyl bromide) which influence ozone depletion, and sulfur gases (e.g., dimethylsulfide) that oxidize to produce sulfate aerosols that cool the marine atmosphere. UV radiation affects the biological availability of iron, copper and other trace metals in aquatic environments thus potentially affecting metal toxicity and the growth of phytoplankton and other microorganisms that are involved in carbon and nitrogen cycling. Future changes in ecosystem distribution due to alterations in the physical and chemical climate interact with ozone-modulated changes in UV-B radiation. These interactions between the effects of climate change and UV-B radiation on biogeochemical cycles in terrestrial and aquatic systems may partially offset the beneficial effects of an ozone recovery.

  4. Methanogenesis in hypersaline environments -Analogs for Ancient Mars?

    NASA Astrophysics Data System (ADS)

    Bebout, Brad; Chanton, Jeff; Kelley, Cheryl; Tazaz, Amanda; Poole, Jennifer; García Maldonado, José Q.; López Cortés, Alejandro

    values, (ca. -60 to -30 o/oo). The hydrogen isotopic (δ 2 H) composition of the methane ranged from -450 to -350 o/oo. These combinations of carbon and hydrogen isotopic values include many outside of the range of values normally considered to be biogenic. Incubations of evaporitic minerals and sediments confirm, however, that the methane is indeed being produced within these sediments. Substrate limitation of methanogenesis in these environments, and not methane oxidation, can explain the isotopic values of the methane in these environments. Incubations with both isotopically labeled and unlabeled putative substrates for methanogenesis have shown that the substrates most important for methanogenesis in these environments are the so-called non competitive substrates, e.g., methylamines, dimethylsulfide, and methanol. Acetate and bicarbonate appear not to be important substrates for methanogens in these environments. Analysis of partial sequences of the methyl-CoM-reductase A gene (mcrA), involved in methane production, has revealed that the community composition of methanogens is consistent with organisms known to use non-competitive substrates. Our work has shown that hypersaline environments have the potential to both produce and preserve methane for analysis on other planets, e.g., by capable rovers on Mars. These studies expand the range of isotopic values now known to be produced by active methanogenesis, and offer explanations as to how methane with these particular stable isotopic values is produced.

  5. Biogeochemistry of DMS in Surface Waters

    NASA Technical Reports Server (NTRS)

    Dacey, J. W. H.

    1997-01-01

    Dimethylsulfide (DMS) is important in influencing the formation of aerosols in the troposphere over large areas of the world's oceans. Understanding the dynamics of aerosols is important to understanding the earth's radiation balance. In evaluating the factors controlling DMS in the troposphere it is vital to understand the dynamics of DMS in the surface ocean. The biogeochemical processes controlling DMS concentration in seawater are myriad; modeling and theoretical estimation are problematic. At the beginning of this project we believed that we were on the verge of simplifying the ship-track measurement of DMS, and we proposed to deploy such a system to develop a database relating high frequency DMS measurements to biological and physicochemical and optical properties of surface water that can be quantified by remote sensing techniques. We designed a system to measure DMS concomitantly with other basic chemical and biological data in a flow-through system. The project was collaborative between Woods Hole Oceanographic Institution (WHOI) and Bermuda Biological Station for Research (BBSR). The project on which we are reporting was budgeted for only one year with a one year no-cost extension. At WHOI our effort was directed towards designing traps which would be used to concentrate DMS from seawater and allow storage for subsequent analysis. At that time, GC systems were too large for easy long-term deployment on a research vessel like R/V Weatherbird, so we focused on simplifying the shipboard sampling procedure. Initial studies of sample recovery with high levels of DMS suggested that Carboxen 1000, a relatively new carbon molecular sieve, could be used as a stable storage medium. The affinity of Carboxen for DMS is several orders of magnitude higher than gold wool (another adsorbent used for DMS collection) on a weight or volume basis. Furthermore, Carboxen's affinity for DMS is also far less susceptible to humidity than gold wool. Unfortunately, further

  6. AEROCE - 10 Years of Atmospheric Chemistry at Bermuda

    NASA Astrophysics Data System (ADS)

    Savoie, D. L.

    2001-12-01

    concentrations of mineral dust occur during the summer when advection of air from lower latitudes frequently carries Saharan dust to the site. Along with the dust, Bermuda receives pollution from Europe as well as Africa. However, the major source for pollutants at Bermuda is North America. The highest concentrations of the pollutant aerosol species are associated with rapid and direct boundary layer transport from the United States. Natural processes also play an important role. Dimethylsulfide (DMS), emitted from biological sources in the ocean, is converted to aerosol products, contributing about 30 per cent of the annual mean nonsea-salt sulfate at Bermuda. Chlorine derived from sea-salt may play a significant role in atmospheric oxidation reactions. Another major issue addressed in AEROCE was the rate of transfer of the atmospheric species into the ocean. Removal by precipitation is the major sink for many types of marine aerosols. Scavenging ratios (SRs) are often used to characterize and parameterize the removal flux. When calculated from data averaged over long time periods (e.g., a year or more), SRs are reasonably consistent (within a factor of two) over extensive marine regions. Scavenging processes are, however, complex and vary greatly over time and space. This is reflected in monthly SRs that vary over factors of 2 to 5 at Bermuda, and in daily SRs that vary over an order of magnitude. Consequently, removal fluxes parameterized over short periods of time are still highly uncertain.

  7. Water Soluble Organic Compounds over the Eastern Mediterranean: Study of their occurrence and sources

    NASA Astrophysics Data System (ADS)

    Tziaras, T.; Spyros, A.; Mandalakis, M.; Apostolaki, M.; Stephanou, E. G.

    2010-05-01

    Fine marine aerosols influence the climate system by acting as cloud condensation nuclei (CCN) in the atmosphere. The organic chemical composition and origin of the marine fine particulate matter are still largely unknown, because of the insufficient reports on in situ studies, the large variability in the emission from the sea, from the complex transfer of gases and particles at the air-sea interface, and the transport of aerosol particles from very distant sources. As important processes of formation of marine organic aerosol production we consider: transport of terrestrial particles, secondary organic aerosol (SOA) formation from the oxidation of biogenic dimethyl-sulfide (DMS), and biogenic particle emissions through sea spray. Specific compounds related to the above-mentioned processes have been proposed as molecular markers: e.g. n-alkanoic acids and n-alkanes (terrestrial particles), levoglucosan (biomass burning aerosol), aminoacids (biological terrestrial or marine particles), methanesulphonate (MSA) (DMS oxidation), C8 and C9 dicarboxylic acids and oxo-carboxylic acids (marine SOA) and other short-chain dicarboxylic acids (marine or terrestrial SOA), and humic-like compounds (emission of marine organic carbon). In our study, we made an effort to characterize the water-soluble organic fraction of marine aerosols collected at a background sampling site of Eastern Mediterranean (Finokalia, N35o20', E25o40', Island of Crete, Greece). The sampling period was 2007-2008. In order to identify and quantify the water-soluble organic compounds of marine aerosols determined in the present study we have used gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS) and nuclear magnetic resonance spectroscopy (NMR) and ion chromatography (IC). The origin of air masses arriving in the study area was studied by using backward trajectories calculation (NOAA HYSPLIT Model). In addition, we have used the "MODIS fire products" for fire

  8. Tropospheric Aerosols

    NASA Astrophysics Data System (ADS)

    Buseck, P. R.; Schwartz, S. E.

    2003-12-01

    It is widely believed that "On a clear day you can see forever," as proclaimed in the 1965 Broadway musical of the same name. While an admittedly beautiful thought, we all know that this concept is only figurative. Aside from Earth's curvature and Rayleigh scattering by air molecules, aerosols - colloidal suspensions of solid or liquid particles in a gas - limit our vision. Even on the clearest day, there are billions of aerosol particles per cubic meter of air.Atmospheric aerosols are commonly referred to as smoke, dust, haze, and smog, terms that are loosely reflective of their origin and composition. Aerosol particles have arisen naturally for eons from sea spray, volcanic emissions, wind entrainment of mineral dust, wildfires, and gas-to-particle conversion of hydrocarbons from plants and dimethylsulfide from the oceans. However, over the industrial period, the natural background aerosol has been greatly augmented by anthropogenic contributions, i.e., those produced by human activities. One manifestation of this impact is reduced visibility (Figure 1). Thus, perhaps more than in other realms of geochemistry, when considering the composition of the troposphere one must consider the effects of these activities. The atmosphere has become a reservoir for vast quantities of anthropogenic emissions that exert important perturbations on it and on the planetary ecosystem in general. Consequently, much recent research focuses on the effects of human activities on the atmosphere and, through them, on the environment and Earth's climate. For these reasons consideration of the geochemistry of the atmosphere, and of atmospheric aerosols in particular, must include the effects of human activities. (201K)Figure 1. Impairment of visibility by aerosols. Photographs at Yosemite National Park, California, USA. (a) Low aerosol concentration (particulate matter of aerodynamic diameter less than 2.5 μm, PM2.5=0.3 μg m-3; particulate matter of aerodynamic diameter less than 10

  9. PERSPECTIVE: Snow matters in the polar regions

    NASA Astrophysics Data System (ADS)

    Sodeau, John

    2010-03-01

    Antarctica is not quite as chemically pristine as might sometimes be thought (Jones et al 2008). For example, as elsewhere, reduced sulfur species such as dimethylsulfide (DMS) are emitted from biogenic marine sources at the poles (Read et al 2008). Somewhat less well known is that inland (as opposed to coastal) field campaigns have also detected, within the Antarctic boundary layer (ABL), emissions containing unexpectedly high levels of diverse, oxidizing chemicals such as NOx, nitrate ions, formaldehyde, ozone and hydrogen peroxide (Honrath et al 1999, Hutterli et al 2004, Sumner and Shepson 1999). And then there are the halogen-containing compounds (Simpson et al 2007). The transformation of DMS to sulfate aerosols capable of acting as cloud condensation nuclei often proceeds via one main oxidized product of DMS, namely methanesulfonic acid (MSA). Two specific reactions have been well studied to date in this regard, namely DMS plus either OH or NO3 radicals. Corresponding reactions with halogen radicals, which also contribute to the oxidizing capacity of our atmosphere, have generally been considered to be of less importance. The reason for this view is that even though the reactivity of bromine- and iodine-containing radicals is much greater than that of OH, the halogens were thought to be relatively scarce in the polar atmosphere. However both BrO (and IO) have been detected in the Antarctic CHABLIS campaign, as discussed in depth in the Atmospheric Chemistry and Physics special issue of 2008, see Jones et al (2008). It was subsequently shown that calculated MSA production from the DMS/BrO reaction may be about an order of magnitude greater than when the OH radical was the oxidizing reactant. The recent analytical measurements by Antony et al (2010) of MSA, Br and NO3 found in snow along the Ingrid Christensen Coast of East Antarctica are important in the above field context. Hence it would appear that the concentrations of these ions in ice-cap sites are up