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

Science.gov (United States)

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.

Use of infochemicals to attract carrion beetles into pitfall traps

Czech Academy of Sciences Publication Activity Database

Podskalská, H.; Růžička, J.; Hoskovec, Michal; Šálek, M.

2009-01-01

Roč. 132, č. 1 (2009), s. 59-64 ISSN 0013-8703 Institutional research plan: CEZ:AV0Z40550506 Keywords : burying beetles * dimethylsulfide * dimethyldisulfide * dimethyltrisulfide Subject RIV: CC - Organic Chemistry Impact factor: 1.568, year: 2009

DMSP synthesis and exudation in phytoplankton : a modeling approach

NARCIS (Netherlands)

Laroche, D; Vézina, A.F; Levasseur, M; Gosselin, M; Stefels, J.; Keller, M.D; Matrai, P.A; Kwint, R.L J

1999-01-01

In the marine environment, phytoplankton are the fundamental producers of dimethylsulfoniopropionate (DMSP), the precursor of the climatically active gas dimethylsulfide (DMS). DMSP is released by exudation, cell autolysis, and zooplankton grazing during phytoplankton blooms. In this study, we

PRODUCTION OF DMS FROM DISSOLVED DMSP IN AXENIC CULTURES OF THE MARINE-PHYTOPLANKTON SPECIES PHAEOCYSTIS SP

NARCIS (Netherlands)

STEFELS, J; VANBOEKEL, WHM

In the marine environment, production of dimethylsulfide (DMS) from dissolved dimethylsulfoniopropionate (DMSP(d)) - an algal osmolyte - is thought to occur mainly through bacterial activity. We have investigated the possibility that phytoplankton cells convert DMSP(d) into DMS, using axenic batch

Temperature, light, and the dimethylsulfoniopropionate (DMSP) content of Emiliania huxleyi (Prymnesiophyceae)

NARCIS (Netherlands)

van Rijssel, M; Gieskes, W.W C

The precursor of the volatile S-compound dimethylsulfide (DMS), dimethylsulfoniopropionate (DMSP), is produced by marine microalgae, notably by Prymnesiophyceae. The production of DMSP by an axenic isolate of Emiliania huxleyi (Lohm.) Hay et Mohler under different temperature and light conditions

Technical note: Examining ozone deposition over seawater

Science.gov (United States)

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...

An updated climatology of surface dimethlysulfide concentrations and emission fluxes in the global ocean

NARCIS (Netherlands)

Lana, A.; Bell, T. G.; Simo, R.; Vallina, S. M.; Ballabrera-Poy, J.; Kettle, A. J.; Dachs, J.; Bopp, L.; Saltzman, E. S.; Stefels, J.; Johnson, J. E.; Liss, P. S.

2011-01-01

The potentially significant role of the biogenic trace gas dimethylsulfide (DMS) in determining the Earth's radiation budget makes it necessary to accurately reproduce seawater DMS distribution and quantify its global flux across the sea/air interface. Following a threefold increase of data (from

Biological control of short-term variations in the concentration of DMSP and DMS during a Phaeocystis spring bloom

NARCIS (Netherlands)

van Duyl, FC; Gieskes, WWC; Kop, AJ; Lewis, WE

1998-01-01

In the spring of 1995. short-term variations in the concentration of particulate and dissolved dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) were monitored in the western Wadden Sea, a shallow coastal region in open connection with the North Sea. Significant correlations were found

UV radiation induced stress does not affect DMSP synthesis in the marine prymnesiophyte Emiliania huxleyi

NARCIS (Netherlands)

van Rijssel, M; Buma, A.G.J.

2002-01-01

A possible coupling between UV radiation (UVR; 280 to 400 nm) induced stress and the production of dimethylsulfoniopropionate (DMSP), the precursor of the climate-regulating gas dimethylsulfide (DMS), was investigated in the marine prymnesiophyte Emiliania huxleyi. To this end, axenic cultures of E.

Involvement of methyltransferases enzymes during the energy ...

African Journals Online (AJOL)

The methyl group transfer from dimethylsulfide (DMS), trimethylamine and methanol to 2-mercaptoethanesulfonic acid (coenzyme M) were investigated from cell extracts of Methanosarcina semesiae sp. nov. to evaluate whether the enzyme systems involved were constitutive or inductive. The extracts from cells grown on ...

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

NARCIS (Netherlands)

Le Clainche, Yvonnick; Vezina, 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, Veronique; Simo, Rafel; Six, Katharina D.; Stefels, Jacqueline

2010-01-01

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

Marine Microbial Production of Dimethylsulfide From Dissolved Dimethylsulfoniopropionate

Science.gov (United States)

1993-02-01

Kirst. 1990. The P3-dimethylsulphonio- propionate (DMSP) content of macroalgae from Antarctica and Southern Chile. Botanica Mar. 33:143-146. 85. Karsten...Oceanography Teaching Bldg. Gifts & Exchanges University of Washington Library Seattle, WA 98195 Bedford Institute of Oceanography Library P.O. Box 1006

A measurement system for vertical seawater profiles close to the air-sea interface

Science.gov (United States)

Sims, Richard P.; Schuster, Ute; Watson, Andrew J.; Yang, Ming Xi; Hopkins, Frances E.; Stephens, John; Bell, Thomas G.

2017-09-01

This paper describes a near-surface ocean profiler, which has been designed to precisely measure vertical gradients in the top 10 m of the ocean. Variations in the depth of seawater collection are minimized when using the profiler compared to conventional CTD/rosette deployments. The profiler consists of a remotely operated winch mounted on a tethered yet free-floating buoy, which is used to raise and lower a small frame housing sensors and inlet tubing. Seawater at the inlet depth is pumped back to the ship for analysis. The profiler can be used to make continuous vertical profiles or to target a series of discrete depths. The profiler has been successfully deployed during wind speeds up to 10 m s-1 and significant wave heights up to 2 m. We demonstrate the potential of the profiler by presenting measured vertical profiles of the trace gases carbon dioxide and dimethylsulfide. Trace gas measurements use an efficient microporous membrane equilibrator to minimize the system response time. The example profiles show vertical gradients in the upper 5 m for temperature, carbon dioxide and dimethylsulfide of 0.15 °C, 4 µatm and 0.4 nM respectively.

A measurement system for vertical seawater profiles close to the air–sea interface

Directory of Open Access Journals (Sweden)

R. P. Sims

2017-09-01

Full Text Available This paper describes a near-surface ocean profiler, which has been designed to precisely measure vertical gradients in the top 10 m of the ocean. Variations in the depth of seawater collection are minimized when using the profiler compared to conventional CTD/rosette deployments. The profiler consists of a remotely operated winch mounted on a tethered yet free-floating buoy, which is used to raise and lower a small frame housing sensors and inlet tubing. Seawater at the inlet depth is pumped back to the ship for analysis. The profiler can be used to make continuous vertical profiles or to target a series of discrete depths. The profiler has been successfully deployed during wind speeds up to 10 m s−1 and significant wave heights up to 2 m. We demonstrate the potential of the profiler by presenting measured vertical profiles of the trace gases carbon dioxide and dimethylsulfide. Trace gas measurements use an efficient microporous membrane equilibrator to minimize the system response time. The example profiles show vertical gradients in the upper 5 m for temperature, carbon dioxide and dimethylsulfide of 0.15 °C, 4 µatm and 0.4 nM respectively.

Interactive effects of vertical mixing, solar radiation and microbial activity on oceanic dimethylated sulfur cycling

OpenAIRE

Galí Tàpias, Martí

2012-01-01

The production and subsequent emission of volatile compounds is one of the numerous ways by which microbial plankton participate in the cycling of elements and influence the Earth's climate. Dimethylsulfide (DMS), produced by enzymatic decomposition of the algal intracellular compound dimethylsulfoniopropionate (DMSP), is the more abundant organic volatile in the upper ocean. Its global emission amounts ca. 28 Tg S per year, and represents the main biogenic source of sulfur to the troposphere...

Correlation between Satellite-Derived Aerosol Characteristics and Oceanic Dimethylsulfide (DMS)

Science.gov (United States)

1988-12-01

intensity gained by multiple scattering into the beam from all directions and the beam addition term accounting for single scattering events. The physical...the extinction and scattering coefficients are the integracion over radius of the product of the cross sectional area of aerosol particles, the...the same photon more than once is small. Therefore, the multiple interaction term can be neglected and a single scattering approximation is made. The

Study of the role of microbes as source and sink of Dimethyl Sulphide in Dona Paula bay

Digital Repository Service at National Institute of Oceanography (India)

Kumar, S.S.

, Rassoulzadegan F, Krajka B, Nguyen BC, Mihalopoulos N, Buat- Menard P (1990) Production of dimethylsulfonium propionate (DMSP) and Dimethylsulfide (DMS) by a microbial food web. Limnology and Oceanography 35:1810 - 1821 Belviso S, Moulin C. Bopp L, Stefels J...-like dimethyl sulfide- producing marine isolate. Applied and Environmental Microbiology 61: 21 - 26 de Souza M P &Yoch D C (1996) N-terminal amino acid sequences and comparison of DMSP lyases from Pseudomonas doudoroffii and Alcaligenes strain M3A,. In R P...

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

DEFF Research Database (Denmark)

Du, Lin; Tang, Shanshan; Hansen, Anne Schou

2017-01-01

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 Osingle bondH⋯O and Osingle bondH⋯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...

Strong relationship between DMS and the solar radiation dose over the global surface ocean.

Science.gov (United States)

Vallina, Sergio M; Simó, Rafel

2007-01-26

Marine biogenic dimethylsulfide (DMS) is the main natural source of tropospheric sulfur, which may play a key role in cloud formation and albedo over the remote ocean. Through a global data analysis, we found that DMS concentrations are highly positively correlated with the solar radiation dose in the upper mixed layer of the open ocean, irrespective of latitude, plankton biomass, or temperature. This is a necessary condition for the feasibility of a negative feedback in which light-attenuating DMS emissions are in turn driven by the light dose received by the pelagic ecosystem.

Organic sulfur metabolisms in hydrothermal environments.

Science.gov (United States)

Rogers, Karyn L; Schulte, Mitchell D

2012-07-01

Sulfur is central to the metabolisms of many organisms that inhabit extreme environments. While biotic and abiotic cycling of organic sulfur compounds has been well documented in low-temperature anaerobic environments, cycling of organic sulfur in hydrothermal environments has received less attention. Recently published thermodynamic data have been used to estimate aqueous alkyl thiol and sulfide activities in deep-sea hydrothermal systems. Here we use geochemical mixing models to predict fluid compositions that result from mixing end-member hydrothermal fluid from the East Pacific Rise with bottom seawater. These fluid compositions are combined with estimates of methanethiol and dimethylsulfide activities to evaluate energy yields for potential organic sulfur-based metabolisms under hydrothermal conditions. Aerobic respiration has the highest energy yields (over -240 kJ/mol e⁻) at lower temperature; however, oxygen is unlikely to persist at high temperatures, restricting aerobic respiration to mesophilic communities. Nitrite reduction to N₂ has the highest energy yields at higher temperatures (greater than ∼40 °C). Nitrate and nitrite reduction to ammonium also yield significant energy (up to -70 kJ/mol e⁻). Much lower, but still feasible energy yields are calculated for sulfate reduction, disproportionation, and reduction with H₂. Organic compound family and the activity of methanethiol and dimethylsulfide were less important than metabolic strategy in determining overall energy yields. All metabolic strategies considered were exergonic within some portion of the mixing regime suggesting that organic sulfur-based metabolisms may be prevalent within deep-sea hydrothermal vent microbial communities. © 2012 Blackwell Publishing Ltd.

Baseline atmospheric program Australia 1993

International Nuclear Information System (INIS)

Francey, R.J.; Dick, A.L.; Derek, N.

1996-01-01

This publication reports activities, program summaries and data from the Cape Grim Baseline Air Pollution Station in Tasmania, during the calendar year 1993. These activities represent Australia's main contribution to the Background Air Pollution Monitoring Network (BAPMoN), part of the World Meteorological Organization's Global Atmosphere Watch (GAW). The report includes 5 research reports covering trace gas sampling, ozone and radon interdependence, analysis of atmospheric dimethylsulfide and carbon-disulfide, sampling of trace gas composition of the troposphere, and sulfur aerosol/CCN relationship in marine air. Summaries of program reports for the calendar year 1993 are also included. Tabs., figs., refs

Variations in concentrations and fluxes of dimethylsulfide (DMS) from the Indian estuaries

Digital Repository Service at National Institute of Oceanography (India)

Viswanadham, R.; Bharathi, M.D.; Sarma, V.V.S.S.

to inhibition of phytoplankton growth by suspended load and low flushing rates. Key words: DMS; Fluxes; River discharge; Nutrients inputs; Indian Monsoonal estuaries 2    1. Introduction Dimethyl sulfide (DMS) is an important biogenic sulfur gas, produced....R. Dolan, and M. Corn. 1996. Assessment of the role of copepods and ciliates in the release to solution of particulate DMSP. Marine Ecology Progress Series 141: 119- 127. Dacey, J.W.H., and S.G. Wakeham. 1986. Oceanic dimethyl sulfide: production during...

Exploring the aqueous vertical ionization of organic molecules by molecular simulation and liquid microjet photoelectron spectroscopy.

Science.gov (United States)

Tentscher, Peter R; Seidel, Robert; Winter, Bernd; Guerard, Jennifer J; Arey, J Samuel

2015-01-08

To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIEaq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIEaq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIEaq, was found to range from ≈-0.5 to -0.91 eV. The ΔVIEaq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIEaq appeared largely controlled by differences in solute-solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV.

A method for removing sulfur bearing compounds from paraffinous hydrocarbons or a directly distilled benzine fraction

Energy Technology Data Exchange (ETDEWEB)

Konyukhova, T.P.; Bolotskaya, I.A.; Mikhaylova, L.A.; Sadykov, A.N.; Shitovkin, N.T.; Vlasov, V.V.

1983-01-01

In the known method for removing sulfurorganic compounds from paraffinous hydrocarbons or a directly distilled gasoline fraction through their adsorption using natural zeolite, in order to increase the degree of purification, clinoptilolite (Kp), which contains SiO2 and A12O3 in a molar ratio of 10.6 to 16.7 is used as the natural zeolite. The purification of the paraffinous hydrocarbons through clinoptilolite adsorption as compared with mordenite adsorption makes it possible to increase the degree of their purification of ethylmercaptane and dimethylsulfide. The effectiveness of clinoptilolite is also confirmed in removing mercaptanes and sulfides from directly distilled gasoline fractions.

Dimethylsulfoniopropionate in six species of giant clams and the evolution of dimethylsulfide after death

Energy Technology Data Exchange (ETDEWEB)

Hill, R.W.; Hill, S.D. [Michigan State Univ., East Lansing, MI (United States). Dept. of Zoology; Dacey, J.W.H. [Woods Hole Oceanographic Inst., Woods Hole, MA (United States). Dept. of Biology; Edward, A. [Micronesia College, Pohnpei (Micronesia, Federated States); Hicks, W.A. [Michigan State Univ., East Lansing, MI (United States). Dept. of Bioichemistry and Molecular Biology

2004-05-01

Dimethylsulfoniopropionate (DMSP) could accumulate in large concentrations in animals living symbiotically with algae. The giant clam family Tridacnidae accumulates DMSP because they have a symbiotic relationship with dinoflagellates (or zooxanthellae). In this study, well preserved clam tissues from the western Pacific Islands were analyzed to provide definitive evidence of DMSP in the tissues. Six of the common species in the Tridacnidae family were examined. The objective was to test the hypothesis that dimethyl sulfide (DMS) is released from clam tissues soon after death due to the breakdown of DMSP tissue. In particular, it determined if DMS is responsible for the problem of potent odours and off-taste that have hindered the commercial success of giant clams mariculture. Gas chromatography and mass spectrometry was used in this study to measure DMSP concentrations in siphonal mantle, byssal mantle, adductor muscle and gill tissues. The formation of DMS by tissues after death was documented. It was suggested that since giant clams associate with dinoflagellates, they could accumulate DMSP to high concentrations which could affect multiple properties and functions. It was concluded that the perishability of giant clam tissues is most likely due to the high concentrations of DMS produced one day post mortem. 15 refs., 2 tabs., 4 figs.

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

Science.gov (United States)

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.

Determination of aromatic fragment content in phenol-containing fractions of solid fuel conversion products using nuclear magnetic resonance spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Kanitskaya, L.V.; Kushnarev, D.F.; Polonov, V.M.; Kalabin, G.A.

1986-03-01

Optimum conditions are determined for obtaining quantitative nuclear magnetic resonance /sup 13/C spectra of fragments in phenol-containing fraction of coal products. Causes are analyzed of residual signals in spectra of un-protonized carbon atoms. The tests were carried out on: low-temperature carbonization tar and phenol fraction obtained during medium-temperature coking of Cherenkhovskii coal (which contains 84.13% C; 9.68% H; 1.23% S; 4.96% O); products of tar hydrogenation with various phenol content; standard phenol mixture. It was found that quantitative determination of aromatic fraction content in coal conversion products and other phenol- and amine-containing complex mixtures, using NMR spectroscopy requires the addition of dimethylsulfide or acetone in order to suppress specific interactions of phenols (amines) with relaxants and obtain quantitative subspectra of Tertiary and Quaternary aromatic carbon atoms. 16 references.

Comparison of northern and central Greenland ice cores records of methanesulfonate covering the last glacial period

DEFF Research Database (Denmark)

Jonsell, U.; Hansson, M. E.; Siggaard-Andersen, M-L-

2007-01-01

Methanesulfonate (MS-) is measured in ice cores with the objective to obtain a proxy record of marine phytoplankton production of dimethylsulfide (DMS). We present a continuous MS- record covering the last glacial period from the North Greenland Ice Core Project (NGRIP) ice core and compare...... this record with the corresponding records previously presented from Greenland and, in particular, with the GISP2 ice core located 320 km south of NGRIP. Despite that the records have similar mean concentrations, their responses to climatic changes during the last glacial period are slightly different. NGRIP...... MS- concentrations were higher during the cold marine isotopic stages (MIS) 2 and 4 and lower during the warm MIS 5. This long-term trend in MS-, which is similar to the inverse of the corresponding trend in d 18O, is not detected in the GISP2 MS- record. A systematic response in MS- concentrations...

The influence of biogenic atmospheric sulfur compounds on climate

Energy Technology Data Exchange (ETDEWEB)

Georgii, H -W [University of Frankfurt am Main, Frankfurt am Main (Germany). Dept. of Meteorology and Geophysics

1993-09-01

The author reviews research so far into sulphur compounds occurring in the atmosphere, namely dimethylsulfide (DMS) and carbonyl sulphide (COS). He explains how the sulphate particles formed by oxidation of DMS with OH radicals act as cloud condensation nuclei which in turn leads to enhanced formation of precipitation. Increase of cloud droplet density leads also to an increase of cloud albedo. The hypothesis of carbonyl sulphide as a precursor for stratospheric sulphate particles is discussed, along with evidence of model calculations showing that the increase of COS flux in the stratosphere leads to an increase in density of stratospheric aerosols and to slight global cooling, particularly compensating for the warming caused by the greenhouse effect. Although the influence of biogenic sulphur gases on climate is still speculative due to lack of information of the source, strength and global trend of these gases, the author advocates they deserve special attention since they may contribute to the stabilization of our climate. 16 refs., 5 figs.

Identification and characterization of the HCl-DMS gas phase molecular complex via infrared spectroscopy and electronic structure calculations.

Science.gov (United States)

Bork, Nicolai; Du, Lin; Kjaergaard, Henrik G

2014-02-27

Models of atmospheric aerosol formation are dependent on accurate Gibbs free binding energies (ΔG°) of gaseous acids and bases, but for most acid–base pairs, only ab initio data are available. We report a combined experimental and theoretical study of the gaseous molecular complex of dimethylsulfide (DMS) and HCl. On the basis of infrared spectroscopy and anharmonic local mode calculations, we determine ΔG(295K)° to be between 6.2 and 11.1 kJ mol(–1). We test the performance of MP2 and five often used DFT functionals with respect to this result. M06-2X performs the best, but also the MP2 prediction is within the experimental range. We find that coupled cluster corrections to the electronic energy improves ΔG° estimates if and only if triple excitations are included. These estimates may be further improved by applying vibrational scaling factors to account for anharmonicity. Hereby, all but the PW91 based predictions are within the experimental range.

Do the organic sulfur compounds DMSP and DMS drive coral microbial associations?

Science.gov (United States)

Raina, Jean-Baptiste; Dinsdale, Elizabeth A; Willis, Bette L; Bourne, David G

2010-03-01

Dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) are key compounds in the global sulfur cycle. Moreover, DMS is particularly important in climate regulation owing to its role in cloud formation. Reef building corals are major contributors to the production of these two compounds and also form diverse and complex associations with bacteria, which are known to play a crucial role in the degradation of DMSP and DMS. Here, we highlight an extensive overlap between bacterial species implicated in DMSP/DMS degradation and those associated with corals, leading to the hypothesis that these two compounds play a major role in structuring coral-associated bacterial communities, with important consequences for coral health and the resilience of coral reefs. We also explore the publically available metagenome databases and show that genes implicated in DMSP metabolism are abundant in the viral component of coral-reef-derived metagenomes, indicating that viruses can act as a reservoir for such genes.

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

Science.gov (United States)

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

2012-06-05

Oceanic dimethylsulfoniopropionate (DMSP) is the precursor to dimethylsulfide (DMS), which plays a role in climate regulation through transformation to methanesulfonic acid (MSA) and non-seasalt sulfate (NSS-SO(4)(2-)) aerosols. Here, we report measurements of the abundance and sulfur isotope compositions of DMSP from one phytoplankton species (Prorocentrum minimum) and five intertidal macroalgal species (Ulva lactuca, Ulva linza, Ulvaria obscura, Ulva prolifera, and Polysiphonia hendryi) in marine waters. We show that the sulfur isotope compositions (δ(34)S) of DMSP are depleted in (34)S relative to the source seawater sulfate by ∼1-3‰ and are correlated with the observed intracellular content of methionine, suggesting a link to metabolic pathways of methionine production. We suggest that this variability of δ(34)S is transferred to atmospheric geochemical products of DMSP degradation (DMS, MSA, and NSS-SO(4)(2-)), carrying implications for the interpretation of variability in δ(34)S of MSA and NSS-SO(4)(2-) that links them to changes in growth conditions and populations of DMSP producers rather than to the contributions of DMS and non-DMS sources.

How phosphorus limitation can control climate-active gas sources and sinks

Science.gov (United States)

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

2017-06-01

Since the 1950's, anthropogenic activities have increased nutrient river loads to European coastal areas. Subsequent implementation of nutrient reduction policies have led to considerably reduction of phosphorus (P) loads from the mid-1980's, while nitrogen (N) loads were maintained, inducing a P limitation of phytoplankton growth in many eutrophied coastal areas such as the Southern Bight of the North Sea (SBNS). When dissolved inorganic phosphorus (DIP) is limiting, most phytoplankton organisms are able to indirectly acquire P from dissolved organic P (DOP). We investigate the impact of DOP use on phytoplankton production and atmospheric fluxes of CO2 and dimethylsulfide (DMS) in the SBNS from 1951 to 2007 using an extended version of the R-MIRO-BIOGAS model. This model includes a description of the ability of phytoplankton organisms to use DOP as a source of P. Results show that primary production can increase up to 30% due to DOP uptake under limiting DIP conditions. Consequently, simulated DMS emissions also increase proportionally while CO2 emissions to the atmosphere decrease, relative to the reference simulation without DOP uptake.

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

Directory of Open Access Journals (Sweden)

Alvaro Ortiz Pérez

2016-12-01

Full Text Available 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.

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

Science.gov (United States)

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.

The Influence of Air-Sea Fluxes on Atmospheric Aerosols During the Summer Monsoon Over the Tropical Indian Ocean

Science.gov (United States)

Zavarsky, Alex; Booge, Dennis; Fiehn, Alina; Krüger, Kirstin; Atlas, Elliot; Marandino, Christa

2018-01-01

During the summer monsoon, the western tropical Indian Ocean is predicted to be a hot spot for dimethylsulfide emissions, the major marine sulfur source to the atmosphere, and an important aerosol precursor. Other aerosol relevant fluxes, such as isoprene and sea spray, should also be enhanced, due to the steady strong winds during the monsoon. Marine air masses dominate the area during the summer monsoon, excluding the influence of continentally derived pollutants. During the SO234-2/235 cruise in the western tropical Indian Ocean from July to August 2014, directly measured eddy covariance DMS fluxes confirm that the area is a large source of sulfur to the atmosphere (cruise average 9.1 μmol m-2 d-1). The directly measured fluxes, as well as computed isoprene and sea spray fluxes, were combined with FLEXPART backward and forward trajectories to track the emissions in space and time. The fluxes show a significant positive correlation with aerosol data from the Terra and Suomi-NPP satellites, indicating a local influence of marine emissions on atmospheric aerosol numbers.

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

Directory of Open Access Journals (Sweden)

H. Bardouki

2003-01-01

Full Text Available 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

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

Science.gov (United States)

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

2016-09-08

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.

Is cloud seeding in coastal Antarctica linked to bromine and nitrate variability in snow?

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Antony, Runa; Thamban, Meloth; Krishnan, K P; Mahalinganathan, K, E-mail: runa@ncaor.or [National Centre for Antarctic and Ocean Research, Headland Sada, Vasco-da-Gama, Goa-403 804 (India)

2010-01-15

Considering the significance of methanesulfonate (MSA) in the sulfur cycle and global climate, we analyzed MSA and other ionic species in snow from the coastal Larsemann Hills, East Antarctica. MSA concentrations recorded were high (0.58 +- 0.7 {mu}M) with ice-cap regions showing significantly higher concentrations (df = 10, p < 0.001) than ice-free regions. High nutrient concentration in ice-cap snow appears to have favored algal growth (7.6 x 10{sup 2} cells l{sup -1}) with subsequent production of brominated compounds. The consequent elevated Br{sup -} (3.2 +- 2.2 {mu}M) in the ice-cap region could result in the release of Br atoms through photoactivated reactions on aerosols and the snow surface. Activated Br atoms in the atmosphere could react with ozone leading to BrO enhancement with subsequent dimethylsulfide (DMS) oxidation and production of sulfur aerosols. Since BrO based DMS oxidation is much faster than the OH/NO{sub 3} pathway, elevated Br{sup -} in ice-cap snow could contribute more than ice-free sites towards formation of cloud condensation nuclei at the expense of ozone.

Development and use of fluorescent 16S rRNA-targeted probes for the specific detection of Methylophaga species by in situ hybridization in marine sediments.

Science.gov (United States)

Janvier, Monique; Regnault, Béatrice; Grimont, Patrick

2003-09-01

Methylotrophic bacteria are widespread in nature. They may play an important role in the cycling of carbon and in the metabolism of dimethylsulfide in a marine environment. Bacteria belonging to the genus Methylophaga are a unique group of aerobic, halophilic, non-methane-utilizing methylotrophs. Two 16S rRNA-targeted oligonucleotide probes were developed for the specific detection of Methylophaga species, marine methylobacteria, by fluorescence in situ hybridization. Probe MPH-730 was highly specific for all members of the genus Methylophaga while probe MPHm-994 targeted exclusively M. marina. The application of these probes were demonstrated by the detection of Methylophaga species in enrichment cultures from various marine sediments. All isolates recovered were visualized by using the genus specific probe MPH-730. The results were confirmed by 16S rDNA sequencing which demonstrated that all selected isolates belong to Methylophaga. Five isolates could be detected by the M. marina-specific probe MPHm-994 and were confirmed by rRNA gene restriction pattern (ribotyping). With the development of these specific probes, fluorescence in situ hybridization shows that the genus Methylophaga is widespread in marine samples.

CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis

KAUST Repository

Galí, Martí

2016-11-14

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 m3 (mol quanta)-1). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m3 (mol quanta)-1. The largest AQY(330), up to 34 m3 (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.

Selective catalytic oxidation: a new catalytic approach to the desulfurization of natural gas and liquid petroleum gas for fuel cell reformer applications

Science.gov (United States)

Lampert, J.

In both natural gas and liquid petroleum gas (LPG), sulfur degrades the performance of the catalysts used in fuel reformers and fuel cells. In order to improve system performance, the sulfur must be removed to concentrations of less than 200 ppbv (in many applications to less than 20 ppbv) before the fuel reforming operation. Engelhard Corporation presents a unique approach to the desulfurization of natural gas and LPG. This new method catalytically converts the organic and inorganic sulfur species to sulfur oxides. The sulfur oxides are then adsorbed on a high capacity adsorbent. The sulfur compounds in the fuel are converted to sulfur oxides by combining the fuel with a small amount of air. The mixture is then heated from 250 to 270 °C, and contacted with a monolith supported sulfur tolerant catalyst at atmospheric pressure. When Engelhard Corporation demonstrated this catalytic approach in the laboratory, the result showed sulfur breakthrough to be less than 10 ppbv in the case of natural gas, and less than 150 ppbv for LPG. We used a simulated natural gas and LPG mixture, doped with a 50-170 ppmv sulfur compound containing equal concentrations of COS, ethylmercaptan, dimethylsulfide, methylethylsulfide and tetrahydrothiophene. There is no need for recycled H 2 as in the case for hydrodesulfurization.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

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

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

Davidovits, P. [Boston Coll., Chestnut Hill, MA (United States). Dept. of Chemistry; Worsnop, D.W.; Zahniser, M.S.; Kolb, C.E. [Aerodyne Research, Inc., Billerica, MA (United States). 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.

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

Energy Technology Data Exchange (ETDEWEB)

Davidovits, P. (Boston Coll., Chestnut Hill, MA (United States). Dept. of Chemistry); Worsnop, D.W.; Zahniser, M.S.; Kolb, C.E. (Aerodyne Research, Inc., Billerica, MA (United States). 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.

How phosphorus limitation can control climatic gas sources and sinks

Science.gov (United States)

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

2017-04-01

Since the 1950's, anthropogenic activities severely increased river nutrient loads in European coastal areas. Subsequent implementation of nutrient reduction policies have considerably reduced phosphorus (P) loads from mid-1980's, while nitrogen (N) loads were maintained, inducing a P limitation of phytoplankton growth in many eutrophied coastal areas such as the Southern Bight of the North Sea (SBNS). When dissolved inorganic phosphorous (DIP) is limiting, most phytoplankton organisms are able to indirectly acquire P from dissolved organic P (DOP). We investigate the impact of DOP use on the importance of phytoplankton production and atmospheric fluxes of CO2 and dimethylsulfide (DMS) in the SBNS from 1951 to 2007 using an extended version of the R-MIRO-BIOGAS model. This model includes a description of the ability of phytoplankton organisms to use DOP as a source of P. Results show that primary production can increase up to 70% due to DOP uptake in limiting DIP conditions. Consequently, simulated DMS emissions double while CO2 emissions to the atmosphere decrease, relative to the reference simulation without DOP uptake. At the end of the simulated period (late 2000's), the net direction of air-sea CO2 annual flux, changed from a source to a sink for atmospheric CO2 in response to use of DOP and increase of primary production.

Vertical variability of seawater DMS in the South Pacific Ocean and its implication for atmospheric and surface seawater DMS.

Science.gov (United States)

Lee, Gangwoong; Park, Jooyoung; Jang, Yuwoon; Lee, Meehye; Kim, Kyung-Ryul; Oh, Jae-Ryoung; Kim, Dongseon; Yi, Hi-Il; Kim, Tong-Yup

2010-02-01

Shipboard measurements of atmospheric dimethylsulfide (DMS) and sea surface water DMS were performed aboard the R/V Onnuri across the South Pacific from Santiago, Chile to Fiji in February 2000. Hydrographic profiles of DMS, dissolved dimethylsulfoniopropionate (DMSP(d)), and particulate DMSP(p) in the upper 200m were obtained at 16 stations along the track. Atmospheric and sea surface water DMS concentrations ranged from 3 to 442pptv and from 0.1 to 19.9nM, respectively; the mean values of 61pptv and 2.1nM, respectively, were comparable to those from previous studies in the South Pacific. The South Pacific Gyre was distinguished by longitudinal-vertical distributions of DMS, DMSP(d), and DMSP(p), which was thought to be associated with the characteristic modification of biological activities that occurs mainly due to significant change in water temperature. The averaged DMS maximum appeared at 40m depth, whereas DMSP(p) and DMSP(d) maxima coincided with that of dissolved oxygen content at 60-80m. The sea-to-air fluxes of DMS were estimated to be 0.4-11.3micromold(-1)m(-2) (mean=2.8micromold(-1)m(-2)). A fairly good correlation between atmospheric DMS and sea-to-air DMS flux indicated that atmospheric DMS concentration was more sensitive to change in physical parameters than its photochemical removal process or surface seawater DMS concentrations.

Role of the NO3 radicals in oxidation processes in the eastern Mediterranean troposphere during the MINOS campaign

Directory of Open Access Journals (Sweden)

M. Vrekoussis

2004-01-01

Full Text Available During the MINOS campaign (28 July-18 August 2001 the nitrate (NO3 radical was measured at Finokalia station, on the north coast of Crete in South-East Europe using a long path (10.4 km Differential Optical Absorption Spectroscopy instrument (DOAS. Hydroxyl (OH radical was also measured by a Chemical Ionization Mass-Spectrometer (Berresheim et al., 2003. These datasets represent the first simultaneous measurements of OH and NO3 radicals in the area. NO3 radical concentrations ranged from less than 3x107 up to 9x108 radicals· cm-3 with an average nighttime value of 1.1x108 radicals· cm-3. The observed NO3 mixing ratios are analyzed on the basis of the corresponding meteorological data and the volatile organic compound (VOC observations which were measured simultaneously at Finokalia station. The importance of the NO3 radical chemistry relatively to that of OH in the dimethylsulfide (DMS and nitrate cycles is also investigated. The observed NO3 levels regulate the nighttime variation of DMS. The loss of DMS by NO3 during night is about 75% of that by OH radical during day. NO3 and nitrogen pentoxide (N2O5 reactions account for about 21% of the total nitrate (HNO3(g+NO-3(g production.

Quantification of total and particulate dimethylsulfoniopropionate (DMSP) in five Bermudian coral species across a depth gradient

Science.gov (United States)

Yost, D. M.; Jones, R.; Rowe, C. L.; Mitchelmore, Carys Louise

2012-06-01

The symbiotic dinoflagellate microalgae of corals ( Symbiodinium spp.) contain high concentrations of dimethylsulfoniopropionate (DMSP), a multifunctional metabolite commonly found in many species of marine algae and dinoflagellates. A photoprotective antioxidant function for DMSP and its breakdown products has often been inferred in algae, but its role(s) in the coral-algal symbiosis remains elusive. To examine potential correlations between environmental and physiological parameters and DMSP, total DMSP (DMSPt, from the host coral and zooxanthellae), particulate DMSP (DMSPp, from the zooxanthellae only), coral surface area, and total protein, as well as zooxanthellae density, chlorophyll concentration, cell volume and genotype (i.e., clade) were measured in five coral species from the Diploria- Montastraea- Porites species complex in Bermuda along a depth gradient of 4, 12, 18, and 24 m. DMSPt concentrations were consistently greater than DMSPp concentrations in all species suggesting the possible translocation of DMSP from symbiont to host. D. labyrinthiformis was notably different from the other corals examined, showing DMSPp and DMSPt increases (per coral surface area or tissue biomass) with increasing water depth. However, overall, there were no consistent depth-related patterns in DMSPp and DMSPt concentrations. Further research, investigating dimethylsulfide (DMS), dimethylsulfoxide, and acrylate levels and DMSP-lyase activity in correlation with other biomarker endpoints that have been shown to be depth (i.e., temperature and light) responsive are needed to substantiate the significance of these findings.

Aroma analysis and quality control of food using highly sensitive analytical methods

International Nuclear Information System (INIS)

Mayr, D.

2003-02-01

This thesis deals with the development of quality control methods for food based on headspace measurements by Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) and with aroma analysis of food using PTR-MS and Gas Chromatography-Olfactometry (GC-O). An objective method was developed for the determination of a herb extract's quality; this quality was checked by a sensory analysis until now. The concentrations of the volatile organic compounds (VOCs) in the headspace of 81 different batches were measured by PTR-MS. Based on the sensory judgment of the customer, characteristic differences in the emissions of 'good' and 'bad' quality samples were identified and a method for the quality control of this herb extract was developed. This novel method enables the producing company to check and ensure that they are only selling high-quality products and therefore avoid complaints of the customer. Furthermore this method can be used for controlling, optimizing and automating the production process. VOCs emitted by meat were investigated using PTR-MS to develop a rapid, non-destructive and quantitative technique for determination of the microbial contamination of meat. Meat samples (beef, pork and poultry) that were wrapped into different kinds of packages (air and vacuum) were stored in at 4 o C for up to 13 days. The emitted VOCs were measured as a function of storage time and identified partly. The concentration of many of the measured VOCs, e.g. sulfur compounds like methanethiol, dimethylsulfide and dimethyldisulfide, largely increased over the storage time. There were big differences in the emissions of normal air- and vacuum-packed meat. VOCs typically emitted by air-packaged meat were methanethiol, dimethylsulfide and dimethyldisulfide, while ethanol and methanol were found in vacuum-packaged meat. A comparison of the PTR-MS results with those obtained by a bacteriological examination performed at the same time showed strong correlations (up to 99 %) between the

VOC amounts in ambient areas of a high-technology science park in Taiwan: their reciprocal correlations and impact on inhabitants.

Science.gov (United States)

Liu, Hsin-Wang; Wu, Bei-Zen; Nian, Hung-Chi; Chen, Hsing-Jung; Lo, Jiunn-Guang; Chiu, Kong-Hwa

2012-02-01

This study presents bihourly, seasonal, and yearly concentration changes in volatile organic compounds (VOCs) in the inlet and effluent water of the wastewater treatment plant (WWTP) of a high-technology science park (HTIP) in Taiwan, with the VOC amounts at different sites correlated geologically. This research adopted a combination of two systems, solid-phase microextraction with a gas chromatography/flame ionization detector and an assembly of purge and trap coupled with gas chromatography/mass spectrometry, to monitor polar and nonpolar VOCs in wastewater. This paper investigated the total VOCs, acetone, isopropyl alcohol (IPA), and dimethylsulfide (DMS) concentrations in real water samples collected in the ambient area of the HTIP. The major contents of VOCs measured in the effluent of the WWTP in the HTIP and the surrounding river region were DMS (14-176 ppb), acetone (5-95 ppb), and IPA (15-316 ppb). In comparison with the total VOCs in the inlet wastewater of the WWTP, no corresponding relationship for total VOC concentration in the wastewater was observed between the inlet water and effluent water of the WWTP. The peak VOC concentrations appeared in the third season, and the correlation of different VOC amounts reflects the production situation of the factories. In addition, VOC concentrations at different sites indicate that the Ke-Ya River is seemingly an effective channel for transporting wastewater to its final destination. The data are good indications for the management of environmental pollution near the HTIP.

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

Science.gov (United States)

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. Copyright © 2011 Elsevier B.V. All rights reserved.

Spatial variation of biogenic sulfur in the south Yellow Sea and the East China Sea during summer and its contribution to atmospheric sulfate aerosol.

Science.gov (United States)

Zhang, Sheng-Hui; Yang, Gui-Peng; Zhang, Hong-Hai; Yang, Jian

2014-08-01

Spatial distributions of biogenic sulfur compounds including dimethylsulfide (DMS), dissolved and particulate dimethylsulfoniopropionate (DMSPd and DMSPp) were investigated in the South Yellow Sea (SYS) and the East China Sea (ECS) in July 2011. The concentrations of DMS and DMSPp were significantly correlated with the levels of chlorophyll a in the surface water. Simultaneously, relatively high ratio values of DMSP/chlorophyll a and DMS/chlorophyll a occurred in the areas where the phytoplankton community was dominated by dinoflagellates. The DMSPp and chlorophyll a size-fractionation showed that larger nanoplankton (5-20 μm) was the most important producer of DMSPp in the study area. The vertical profiles of DMS and DMSP were characterized by a maximum at the upper layer and the bottom concentrations were also relatively higher compared with the overlying layer of the bottom. In addition, a positive linear correlation was observed between dissolved dimethylsulfoxide (DMSOd) and DMS concentrations in the surface waters. The sea-to-air fluxes of DMS in the study area were estimated to be from 0.03 to 102.35 μmol m(-2) d(-1) with a mean of 16.73 μmol m(-2) d(-1) and the contribution of biogenic non-sea-salt SO4(2-) (nss-SO4(2-)) to the measured total nss-SO4(2-) in the atmospheric aerosol over the study area varied from 1.42% to 30.98%, with an average of 8.2%. Copyright © 2014 Elsevier B.V. All rights reserved.

Agricultural Influences on Cache Valley, Utah Air Quality During a Wintertime Inversion Episode

Science.gov (United States)

Silva, P. J.

2017-12-01

Several of northern Utah's intermountain valleys are classified as non-attainment for fine particulate matter. Past data indicate that ammonium nitrate is the major contributor to fine particles and that the gas phase ammonia concentrations are among the highest in the United States. During the 2017 Utah Winter Fine Particulate Study, USDA brought a suite of online and real-time measurement methods to sample particulate matter and potential gaseous precursors from agricultural emissions in the Cache Valley. Instruments were co-located at the State of Utah monitoring site in Smithfield, Utah from January 21st through February 12th, 2017. A Scanning mobility particle sizer (SMPS) and aerodynamic particle sizer (APS) acquired size distributions of particles from 10 nm - 10 μm in 5-min intervals. A URG ambient ion monitor (AIM) gave hourly concentrations for gas and particulate ions and a Chromatotec Trsmedor gas chromatograph obtained 10 minute measurements of gaseous sulfur species. High ammonia concentrations were detected at the Smithfield site with concentrations above 100 ppb at times, indicating a significant influence from agriculture at the sampling site. Ammonia is not the only agricultural emission elevated in Cache Valley during winter, as reduced sulfur gas concentrations of up to 20 ppb were also detected. Dimethylsulfide was the major sulfur-containing gaseous species. Analysis indicates that particle growth and particle nucleation events were both observed by the SMPS. Relationships between gas and particulate concentrations and correlations between the two will be discussed.

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

Directory of Open Access Journals (Sweden)

J.-E. Tesdal

2016-09-01

Full Text Available 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.

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

Science.gov (United States)

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.

S-methylmethionine conversion to dimethylsulfoniopropionate: evidence for an unusual transamination reaction

International Nuclear Information System (INIS)

Rhodes, D.; Gage, D.A.; Cooper, A.J.L.; Hanson, A.D.

1997-01-01

Leaves of Wollastonia biflora (L.) DC. synthesize the osmoprotectant 3-dimethylsulfoniopropionate (DMSP) from methionine via S-methylmethionine (SMM) and 3-dimethylsulfoniopropionaldehyde (DMSP-ald); no other intermediates have been detected. To test whether the amino group of SMM is lost by transamination or deamination, [methyl-2H3, 15N]SMM was supplied to leaf discs, and 15N-labeling of amino acids was monitored, along with synthesis of [2H3]DMSP. After short incubations more 15N was incorporated into glutamate than into other amino acids, and the 15N abundance in glutamate exceeded that in the amide group of glutamine (Gln). This is more consistent with transamination than deamination, because deamination would be predicted to give greater labeling of Gln amide N due to reassimilation, via Gln synthetase, of the 15NH4+ released. This prediction was borne out by control experiments with 15NH4Cl. The transamination product of SMM, 4-dimethylsulfonio-2-oxobutyrate (DMSOB), is expected to be extremely unstable. This was confirmed by attempting to synthesize it enzymatically from SMM using L-amino acid oxidase or Gln transaminase K and from 4-methylthio-2-oxobutyrate using methionine S-methyltransferase. In each case, the reaction product decomposed rapidly, releasing dimethylsulfide. The conversion of SMM to DMSP-ald is therefore unlikely to involve a simple transamination that generates free DMSOB. Plausible alternatives are that DMSOB is channeled within a specialized transaminase-decarboxylase complex or that it exists only as the bound intermediate of a single enzyme catalyzing an unusual transamination-decarboxylation reaction

Ecological significance of compatible solute accumulation by micro-organisms: from single cells to global climate.

Science.gov (United States)

Welsh, D T

2000-07-01

The osmoadaptation of most micro-organisms involves the accumulation of K(+) ions and one or more of a restricted range of low molecular mass organic solutes, collectively termed 'compatible solutes'. These solutes are accumulated to high intracellular concentrations, in order to balance the osmotic pressure of the growth medium and maintain cell turgor pressure, which provides the driving force for cell extension growth. In this review, I discuss the alternative roles which compatible solutes may also play as intracellular reserves of carbon, energy and nitrogen, and as more general stress metabolites involved in protection of cells against other environmental stresses including heat, desiccation and freezing. Thus, the evolutionary selection for the accumulation of a specific compatible solute may not depend solely upon its function during osmoadaptation, but also upon the secondary benefits its accumulation provides, such as increased tolerance of other environmental stresses prevalent in the organism's niche or even anti-herbivory or dispersal functions in the case of dimethylsulfoniopropionate (DMSP). In the second part of the review, I discuss the ecological consequences of the release of compatible solutes to the environment, where they can provide sources of compatible solutes, carbon, nitrogen and energy for other members of the micro-flora. Finally, at the global scale the metabolism of specific compatible solutes (betaines and DMSP) in brackish water, marine and hypersaline environments may influence global climate, due to the production of the trace gases, methane and dimethylsulfide (DMS) and in the case of DMS, also couple the marine and terrestrial sulfur cycles.

Selective oxidation with nanoporous silica supported sensitizers: An environment friendly process using air and visible light

Energy Technology Data Exchange (ETDEWEB)

Saint-Cricq, Philippe; Pigot, Thierry; Blanc, Sylvie [Institut des Sciences Analytiques et de Physicochimie pour l' Environnement et les Materiaux, Universite de Pau et des Pays de l' Adour, Helioparc-2 Av. du President Angot, F-64053 Pau Cedex 09 (France); Lacombe, Sylvie, E-mail: sylvie.lacombe@univ-pau.fr [Institut des Sciences Analytiques et de Physicochimie pour l' Environnement et les Materiaux, Universite de Pau et des Pays de l' Adour, Helioparc-2 Av. du President Angot, F-64053 Pau Cedex 09 (France)

2012-04-15

Highlights: Black-Right-Pointing-Pointer Photo-sensitizers were covalently grafted on silica matrices. Black-Right-Pointing-Pointer Grafted powdered silica was characterized by diffuse reflectance and emission spectroscopy. Black-Right-Pointing-Pointer Selective solvent-free photo-oxygenation was carried out with air under visible light. Black-Right-Pointing-Pointer Singlet generation and reactivity at the gas-solid interface was demonstrated. - Abstract: Transparent and porous silica xerogels containing various grafted photosensitizers (PSs) such as anthraquinone derivatives, Neutral Red, Acridine Yellow and a laboratory-made dicyano aromatics (DBTP) were prepared. In most cases, the xerogels were shown to be mainly microporous by porosimetry. The PSs were characterized in the powdered monoliths (form, aggregation, concentration) by electronic spectroscopy which also proved to be a useful tool for monitoring the material evolution after irradiation. These nanoporous xerogels were used as microreactors for gas/solid solvent-free photo-oxygenation of dimethylsulfide (DMS) using visible light and air as the sole reactant. All these PSs containing monoliths were efficient for gas-solid DMS oxidation, leading to sulfoxide and sulfone in varying ratios. As these polar oxidation products remained strongly adsorbed on the silica matrix, the gaseous flow at the outlet of the reactor was totally free of sulfide and odorless. The best results in term of yield and initial rate of degradation of DMS were obtained with DBTP containing xerogels. Moreover, as these materials were reusable without loss of efficiency and sensitizer photobleaching after a washing regeneration step, the concept of recyclable sensitizing materials was approved, opening the way to green process.

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

International Nuclear Information System (INIS)

Kiene, R.P.; Oremland, R.S.; Catena, A.; Miller, L.G.; Capone, A.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 ∼2-3=M levels as [ 14 C]DMS, metabolism by sediments resulted in a 14 CH 4 / 14 CO 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 14 CO 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 [ 14 C]-DMS to yield a 14 CH 4 / 14 CO 2 ratio of ∼ 2.8

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.

Science.gov (United States)

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.

Formation and growth of sulfur derived particles in the marine environment

Energy Technology Data Exchange (ETDEWEB)

Kerminen, V M; Wexler, A; Hillamo, R [Finnish Meteorological Inst., Helsinki (Finland). Air Quality Dept.

1996-12-31

Aerosol particles modify the Earth`s radiation balance directly by scattering and absorbing solar radiation, and indirectly via their influence on cloud properties. The indirect climate forcing due to aerosols probably dominates over that of the direct forcing over global scale, and is induced primary by sulfate originating from both natural and anthropogenic sources. A large portion of the global sulfur flux is due to dimethylsulfide (DMS) released from the ocean surface, where it is produced in large quantities by various biogenic processes. DMS is believed to be the primary particulate precursor over vast oceanic regions, hence having a potential to modify aerosol climatic effects over a major portion of the Earth`s surface. The connection between marine DMS emissions and the resulting climate forcing involves several steps still not properly quantified. Among the open questions related to this system, perhaps the most critical ones are when and where the DMS-derived particles are formed in the atmosphere, and how these particles grow into sizes where they are able to alter cloud properties, such as cloud albedos, lifetimes and precipitation efficiencies, that are relevant to climate. In this work, production and growth of sulfur particles has been examined using a simple, yet realistic model that simulates the processes taking place in a remote marine boundary layer. The specific questions examined include: (1) what is the role of boundary layer dynamics in affecting the condensation nuclei (CN) and cloud condensation nuclei (CCN) production in this system, (2) what are the factors controlling the growth of fresh CN into CCN, and (3) how does the presence of boundary layer clouds interact with CN/CCN production

Occurrence and Turnover of Biogenic Sulfur in the Bering Sea During Summer

Science.gov (United States)

Li, Cheng-Xuan; Wang, Bao-Dong; Yang, Gui-Peng; Wang, Zi-Cheng; Chen, Jian-Fang; Lyu, Yang

2017-11-01

The horizontal/geographical variations in dissolved dimethylsulfide (DMS), its precursor dimethylsulfoniopropionate (DMSPd and DMSPp), and chlorophyll a (Chl a), as well as the oceanographic parameters influencing the concentrations of dimethylated sulfur compounds, were investigated in the Bering Sea from July to August 2012. Similar to Chl a, the surface DMS and DMSPp levels, as well as DMS(P) production and consumption rates, exhibited a declining gradient from the central basin to the continental shelf, with high-value areas appearing in the central basin, the slope regions, and Anadyr Strait but a low-value area occurring on the outer-middle continental shelf. Considerably high values of DMS and DMSP were measured in the saline Bering Sea Basin Deep Water (>2,000 m) located at the southwest of the Bering Basin because of the release of resuspension in 2,000 m depth and the DMSP production from endogenous benthic bacteria and cyanobacteria population. Chl a was positively correlated with DMSPp and DMS in the surface waters and the upper water of the basin, whereas significant negative correlations were found between DMS and nutrients (dissolved inorganic nitrogen [DIN], phosphorus, and silicate) in the inner shelf of the Bering Sea. DMS microbial consumption was approximately 6.26 times faster than the DMS sea-air exchange, demonstrating that the major loss of DMS in the surface water occurred through biological consumption relative to evasion into the atmosphere. Average sea-to-air DMS fluxes were estimated to be 4.66 μmol/(m2·d), and consequently oceanic biogenic DMS emission had a dominant contribution to the sulfur budget over the observational area.

Formation and growth of sulfur derived particles in the marine environment

Energy Technology Data Exchange (ETDEWEB)

Kerminen, V.M.; Wexler, A.; Hillamo, R. [Finnish Meteorological Inst., Helsinki (Finland). Air Quality Dept.

1995-12-31

Aerosol particles modify the Earth`s radiation balance directly by scattering and absorbing solar radiation, and indirectly via their influence on cloud properties. The indirect climate forcing due to aerosols probably dominates over that of the direct forcing over global scale, and is induced primary by sulfate originating from both natural and anthropogenic sources. A large portion of the global sulfur flux is due to dimethylsulfide (DMS) released from the ocean surface, where it is produced in large quantities by various biogenic processes. DMS is believed to be the primary particulate precursor over vast oceanic regions, hence having a potential to modify aerosol climatic effects over a major portion of the Earth`s surface. The connection between marine DMS emissions and the resulting climate forcing involves several steps still not properly quantified. Among the open questions related to this system, perhaps the most critical ones are when and where the DMS-derived particles are formed in the atmosphere, and how these particles grow into sizes where they are able to alter cloud properties, such as cloud albedos, lifetimes and precipitation efficiencies, that are relevant to climate. In this work, production and growth of sulfur particles has been examined using a simple, yet realistic model that simulates the processes taking place in a remote marine boundary layer. The specific questions examined include: (1) what is the role of boundary layer dynamics in affecting the condensation nuclei (CN) and cloud condensation nuclei (CCN) production in this system, (2) what are the factors controlling the growth of fresh CN into CCN, and (3) how does the presence of boundary layer clouds interact with CN/CCN production

Methanethiol Concentrations and Sea-Air Fluxes in the Subarctic NE Pacific Ocean

Science.gov (United States)

Kiene, R. P.; Williams, T. E.; Esson, K.; Tortell, P. D.; Dacey, J. W. H.

2017-12-01

Exchange of volatile organic sulfur from the ocean to the atmosphere impacts the global sulfur cycle and the climate system and is thought to occur mainly via the gas dimethylsulfide (DMS). DMS is produced during degradation of the abundant phytoplankton osmolyte dimethylsulfoniopropionate (DMSP) but bacteria can also convert dissolved DMSP into the sulfur gas methanethiol (MeSH). MeSH has been difficult to measure in seawater because of its high chemical and biological reactivity and, thus, information on MeSH concentrations, distribution and sea-air fluxes is limited. We measured MeSH in the northeast subarctic Pacific Ocean in July 2016, along transects with strong phytoplankton abundance gradients. Water samples obtained with Niskin bottles were analyzed for MeSH by purge-and-trap gas chromatography. Depth profiles showed that MeSH concentrations were high near the surface and declined with depth. Surface waters (5 m depth) had an average MeSH concentration of 0.75 nM with concentrations reaching up to 3nM. MeSH concentrations were correlated (r = 0.47) with microbial turnover of dissolved DMSP which ranged up to 236 nM per day. MeSH was also correlated with total DMSP (r = 0.93) and dissolved DMS (r = 0.63), supporting the conclusion that DMSP was a major precursor of MeSH. Surface water MeSH:DMS concentration ratios averaged 0.19 and ranged up to 0.50 indicating that MeSH was a significant fraction of the volatile sulfur pool in surface waters. Sea-air fluxes of MeSH averaged 15% of the combined DMS+MeSH flux, therefore MeSH contributed an important fraction of the sulfur emitted to the atmosphere from the subarctic NE Pacific Ocean.

Droplet number uncertainties associated with CCN: an assessment using observations and a global model adjoint

Directory of Open Access Journals (Sweden)

R. H. Moore

2013-04-01

Full Text Available We use the Global Modelling Initiative (GMI chemical transport model with a cloud droplet parameterisation adjoint to quantify the sensitivity of cloud droplet number concentration to uncertainties in predicting CCN concentrations. Published CCN closure uncertainties for six different sets of simplifying compositional and mixing state assumptions are used as proxies for modelled CCN uncertainty arising from application of those scenarios. It is found that cloud droplet number concentrations (Nd are fairly insensitive to the number concentration (Na of aerosol which act as CCN over the continents (∂lnNd/∂lnNa ~10–30%, but the sensitivities exceed 70% in pristine regions such as the Alaskan Arctic and remote oceans. This means that CCN concentration uncertainties of 4–71% translate into only 1–23% uncertainty in cloud droplet number, on average. Since most of the anthropogenic indirect forcing is concentrated over the continents, this work shows that the application of Köhler theory and attendant simplifying assumptions in models is not a major source of uncertainty in predicting cloud droplet number or anthropogenic aerosol indirect forcing for the liquid, stratiform clouds simulated in these models. However, it does highlight the sensitivity of some remote areas to pollution brought into the region via long-range transport (e.g., biomass burning or from seasonal biogenic sources (e.g., phytoplankton as a source of dimethylsulfide in the southern oceans. Since these transient processes are not captured well by the climatological emissions inventories employed by current large-scale models, the uncertainties in aerosol-cloud interactions during these events could be much larger than those uncovered here. This finding motivates additional measurements in these pristine regions, for which few observations exist, to quantify the impact (and associated uncertainty of transient aerosol processes on cloud properties.

An updated climatology of surface dimethlysulfide concentrations and emission fluxes in the global ocean

Science.gov (United States)

Lana, A.; Bell, T. G.; Simó, R.; Vallina, S. M.; Ballabrera-Poy, J.; Kettle, A. J.; Dachs, J.; Bopp, L.; Saltzman, E. S.; Stefels, J.; Johnson, J. E.; Liss, P. S.

2011-03-01

The potentially significant role of the biogenic trace gas dimethylsulfide (DMS) in determining the Earth's radiation budget makes it necessary to accurately reproduce seawater DMS distribution and quantify its global flux across the sea/air interface. Following a threefold increase of data (from 15,000 to over 47,000) in the global surface ocean DMS database over the last decade, new global monthly climatologies of surface ocean DMS concentration and sea-to-air emission flux are presented as updates of those constructed 10 years ago. Interpolation/extrapolation techniques were applied to project the discrete concentration data onto a first guess field based on Longhurst's biogeographic provinces. Further objective analysis allowed us to obtain the final monthly maps. The new climatology projects DMS concentrations typically in the range of 1-7 nM, with higher levels occurring in the high latitudes, and with a general trend toward increasing concentration in summer. The increased size and distribution of the observations in the DMS database have produced in the new climatology substantially lower DMS concentrations in the polar latitudes and generally higher DMS concentrations in regions that were severely undersampled 10 years ago, such as the southern Indian Ocean. Using the new DMS concentration climatology in conjunction with state-of-the-art parameterizations for the sea/air gas transfer velocity and climatological wind fields, we estimate that 28.1 (17.6-34.4) Tg of sulfur are transferred from the oceans into the atmosphere annually in the form of DMS. This represents a global emission increase of 17% with respect to the equivalent calculation using the previous climatology. This new DMS climatology represents a valuable tool for atmospheric chemistry, climate, and Earth System models.

Biochemical, Kinetic, and Spectroscopic Characterization of Ruegeria pomeroyi DddW--A Mononuclear Iron-Dependent DMSP Lyase.

Directory of Open Access Journals (Sweden)

Adam E Brummett

Full Text Available The osmolyte dimethylsulfoniopropionate (DMSP is a key nutrient in marine environments and its catabolism by bacteria through enzymes known as DMSP lyases generates dimethylsulfide (DMS, a gas of importance in climate regulation, the sulfur cycle, and signaling to higher organisms. Despite the environmental significance of DMSP lyases, little is known about how they function at the mechanistic level. In this study we biochemically characterize DddW, a DMSP lyase from the model roseobacter Ruegeria pomeroyi DSS-3. DddW is a 16.9 kDa enzyme that contains a C-terminal cupin domain and liberates acrylate, a proton, and DMS from the DMSP substrate. Our studies show that as-purified DddW is a metalloenzyme, like the DddQ and DddP DMSP lyases, but contains an iron cofactor. The metal cofactor is essential for DddW DMSP lyase activity since addition of the metal chelator EDTA abolishes its enzymatic activity, as do substitution mutations of key metal-binding residues in the cupin motif (His81, His83, Glu87, and His121. Measurements of metal binding affinity and catalytic activity indicate that Fe(II is most likely the preferred catalytic metal ion with a nanomolar binding affinity. Stoichiometry studies suggest DddW requires one Fe(II per monomer. Electronic absorption and electron paramagnetic resonance (EPR studies show an interaction between NO and Fe(II-DddW, with NO binding to the EPR silent Fe(II site giving rise to an EPR active species (g = 4.29, 3.95, 2.00. The change in the rhombicity of the EPR signal is observed in the presence of DMSP, indicating that substrate binds to the iron site without displacing bound NO. This work provides insight into the mechanism of DMSP cleavage catalyzed by DddW.

Modeling natural emissions in the Community Multiscale Air Quality (CMAQ Model–I: building an emissions data base

Directory of Open Access Journals (Sweden)

S. F. Mueller

2010-05-01

Full Text Available A natural emissions inventory for the continental United States and surrounding territories is needed in order to use the US Environmental Protection Agency Community Multiscale Air Quality (CMAQ Model for simulating natural air quality. The CMAQ air modeling system (including the Sparse Matrix Operator Kernel Emissions (SMOKE emissions processing system currently estimates non-methane volatile organic compound (NMVOC emissions from biogenic sources, nitrogen oxide (NOx emissions from soils, ammonia from animals, several types of particulate and reactive gas emissions from fires, as well as sea salt emissions. However, there are several emission categories that are not commonly treated by the standard CMAQ Model system. Most notable among these are nitrogen oxide emissions from lightning, reduced sulfur emissions from oceans, geothermal features and other continental sources, windblown dust particulate, and reactive chlorine gas emissions linked with sea salt chloride. A review of past emissions modeling work and existing global emissions data bases provides information and data necessary for preparing a more complete natural emissions data base for CMAQ applications. A model-ready natural emissions data base is developed to complement the anthropogenic emissions inventory used by the VISTAS Regional Planning Organization in its work analyzing regional haze based on the year 2002. This new data base covers a modeling domain that includes the continental United States plus large portions of Canada, Mexico and surrounding oceans. Comparing July 2002 source data reveals that natural emissions account for 16% of total gaseous sulfur (sulfur dioxide, dimethylsulfide and hydrogen sulfide, 44% of total NOx, 80% of reactive carbonaceous gases (NMVOCs and carbon monoxide, 28% of ammonia, 96% of total chlorine (hydrochloric acid, nitryl chloride and sea salt chloride, and 84% of fine particles (i.e., those smaller than 2.5 μm in size released into the

Wind Speed and Sea State Dependencies of Air-Sea Gas Transfer: Results From the High Wind Speed Gas Exchange Study (HiWinGS)

Science.gov (United States)

Blomquist, B. W.; Brumer, S. E.; Fairall, C. W.; Huebert, B. J.; Zappa, C. J.; Brooks, I. M.; Yang, M.; Bariteau, L.; Prytherch, J.; Hare, J. E.; Czerski, H.; Matei, A.; Pascal, R. W.

2017-10-01

A variety of physical mechanisms are jointly responsible for facilitating air-sea gas transfer through turbulent processes at the atmosphere-ocean interface. The nature and relative importance of these mechanisms evolves with increasing wind speed. Theoretical and modeling approaches are advancing, but the limited quantity of observational data at high wind speeds hinders the assessment of these efforts. The HiWinGS project successfully measured gas transfer coefficients (k660) with coincident wave statistics under conditions with hourly mean wind speeds up to 24 m s-1 and significant wave heights to 8 m. Measurements of k660 for carbon dioxide (CO2) and dimethylsulfide (DMS) show an increasing trend with respect to 10 m neutral wind speed (U10N), following a power law relationship of the form: k660 CO2˜U10N1.68 and k660 dms˜U10N1.33. Among seven high wind speed events, CO2 transfer responded to the intensity of wave breaking, which depended on both wind speed and sea state in a complex manner, with k660 CO2 increasing as the wind sea approaches full development. A similar response is not observed for DMS. These results confirm the importance of breaking waves and bubble injection mechanisms in facilitating CO2 transfer. A modified version of the Coupled Ocean-Atmosphere Response Experiment Gas transfer algorithm (COAREG ver. 3.5), incorporating a sea state-dependent calculation of bubble-mediated transfer, successfully reproduces the mean trend in observed k660 with wind speed for both gases. Significant suppression of gas transfer by large waves was not observed during HiWinGS, in contrast to results from two prior field programs.

Gradient flux measurements of sea–air DMS transfer during the Surface Ocean Aerosol Production (SOAP experiment

Directory of Open Access Journals (Sweden)

M. J. Smith

2018-04-01

Full Text Available Direct measurements of marine dimethylsulfide (DMS fluxes are sparse, particularly in the Southern Ocean. The Surface Ocean Aerosol Production (SOAP voyage in February–March 2012 examined the distribution and flux of DMS in a biologically active frontal system in the southwest Pacific Ocean. Three distinct phytoplankton blooms were studied with oceanic DMS concentrations as high as 25 nmol L−1. Measurements of DMS fluxes were made using two independent methods: the eddy covariance (EC technique using atmospheric pressure chemical ionization–mass spectrometry (API-CIMS and the gradient flux (GF technique from an autonomous catamaran platform. Catamaran flux measurements are relatively unaffected by airflow distortion and are made close to the water surface, where gas gradients are largest. Flux measurements were complemented by near-surface hydrographic measurements to elucidate physical factors influencing DMS emission. Individual DMS fluxes derived by EC showed significant scatter and, at times, consistent departures from the Coupled Ocean–Atmosphere Response Experiment gas transfer algorithm (COAREG. A direct comparison between the two flux methods was carried out to separate instrumental effects from environmental effects and showed good agreement with a regression slope of 0.96 (r2 = 0.89. A period of abnormal downward atmospheric heat flux enhanced near-surface ocean stratification and reduced turbulent exchange, during which GF and EC transfer velocities showed good agreement but modelled COAREG values were significantly higher. The transfer velocity derived from near-surface ocean turbulence measurements on a spar buoy compared well with the COAREG model in general but showed less variation. This first direct comparison between EC and GF fluxes of DMS provides confidence in compilation of flux estimates from both techniques, as well as in the stable periods when the observations are not well predicted by the COAREG

Dynamics of dimethylsulphoniopropionate and dimethylsulphide under different CO2 concentrations during a mesocosm experiment

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C. LeQuéré

2008-03-01

Full Text Available The potential impact of seawater acidification on the concentrations of dimethylsulfide (DMS and dimethylsulfoniopropionate (DMSP, and the activity of the enzyme DMSP-lyase was investigated during a pelagic ecosystem CO2 enrichment experiment (PeECE III in spring 2005. Natural phytoplankton blooms were studied for 24 days under present, double and triple partial pressures of CO2 (pCO2; pH=8.3, 8.0, 7.8 in triplicate 25 m3 enclosures. The results indicate similar DMSP concentrations and DMSP-lyase activity (DLA patterns for all treatments. Hence, DMSP and DLA do not seem to have been affected by the CO2 treatment. In contrast, DMS concentrations showed small but statistically significant differences in the temporal development of the low versus the high CO2 treatments. The low pCO2 enclosures had higher DMS concentrations during the first 10 days, after which the levels decreased earlier and more rapidly than in the other treatments. Integrated over the whole study period, DMS concentrations were not significantly different from those of the double and triple pCO2 treatments. Pigment and flow-cytometric data indicate that phytoplanktonic populations were generally similar between the treatments, suggesting a certain resilience of the marine ecosystem under study to the induced pH changes, which is reflected in DMSP and DLA. However, there were significant differences in bacterial community structure and the abundance of one group of viruses infecting nanoeukaryotic algae. The amount of DMS accumulated per total DMSP or chlorophyll-a differed significantly between the present and future scenarios, suggesting that the pathways for DMS production or bacterial DMS consumption were affected by seawater pH. A comparison with previous work (PeECE II suggests that DMS concentrations do not respond consistently to pelagic ecosystem CO2 enrichment experiments.

Gradient flux measurements of sea-air DMS transfer during the Surface Ocean Aerosol Production (SOAP) experiment

Science.gov (United States)

Smith, Murray J.; Walker, Carolyn F.; Bell, Thomas G.; Harvey, Mike J.; Saltzman, Eric S.; Law, Cliff S.

2018-04-01

Direct measurements of marine dimethylsulfide (DMS) fluxes are sparse, particularly in the Southern Ocean. The Surface Ocean Aerosol Production (SOAP) voyage in February-March 2012 examined the distribution and flux of DMS in a biologically active frontal system in the southwest Pacific Ocean. Three distinct phytoplankton blooms were studied with oceanic DMS concentrations as high as 25 nmol L-1. Measurements of DMS fluxes were made using two independent methods: the eddy covariance (EC) technique using atmospheric pressure chemical ionization-mass spectrometry (API-CIMS) and the gradient flux (GF) technique from an autonomous catamaran platform. Catamaran flux measurements are relatively unaffected by airflow distortion and are made close to the water surface, where gas gradients are largest. Flux measurements were complemented by near-surface hydrographic measurements to elucidate physical factors influencing DMS emission. Individual DMS fluxes derived by EC showed significant scatter and, at times, consistent departures from the Coupled Ocean-Atmosphere Response Experiment gas transfer algorithm (COAREG). A direct comparison between the two flux methods was carried out to separate instrumental effects from environmental effects and showed good agreement with a regression slope of 0.96 (r2 = 0.89). A period of abnormal downward atmospheric heat flux enhanced near-surface ocean stratification and reduced turbulent exchange, during which GF and EC transfer velocities showed good agreement but modelled COAREG values were significantly higher. The transfer velocity derived from near-surface ocean turbulence measurements on a spar buoy compared well with the COAREG model in general but showed less variation. This first direct comparison between EC and GF fluxes of DMS provides confidence in compilation of flux estimates from both techniques, as well as in the stable periods when the observations are not well predicted by the COAREG model.

Modeling natural emissions in the Community Multiscale Air Quality (CMAQ) Model-I: building an emissions data base

Science.gov (United States)

Smith, S. N.; Mueller, S. F.

2010-05-01

A natural emissions inventory for the continental United States and surrounding territories is needed in order to use the US Environmental Protection Agency Community Multiscale Air Quality (CMAQ) Model for simulating natural air quality. The CMAQ air modeling system (including the Sparse Matrix Operator Kernel Emissions (SMOKE) emissions processing system) currently estimates non-methane volatile organic compound (NMVOC) emissions from biogenic sources, nitrogen oxide (NOx) emissions from soils, ammonia from animals, several types of particulate and reactive gas emissions from fires, as well as sea salt emissions. However, there are several emission categories that are not commonly treated by the standard CMAQ Model system. Most notable among these are nitrogen oxide emissions from lightning, reduced sulfur emissions from oceans, geothermal features and other continental sources, windblown dust particulate, and reactive chlorine gas emissions linked with sea salt chloride. A review of past emissions modeling work and existing global emissions data bases provides information and data necessary for preparing a more complete natural emissions data base for CMAQ applications. A model-ready natural emissions data base is developed to complement the anthropogenic emissions inventory used by the VISTAS Regional Planning Organization in its work analyzing regional haze based on the year 2002. This new data base covers a modeling domain that includes the continental United States plus large portions of Canada, Mexico and surrounding oceans. Comparing July 2002 source data reveals that natural emissions account for 16% of total gaseous sulfur (sulfur dioxide, dimethylsulfide and hydrogen sulfide), 44% of total NOx, 80% of reactive carbonaceous gases (NMVOCs and carbon monoxide), 28% of ammonia, 96% of total chlorine (hydrochloric acid, nitryl chloride and sea salt chloride), and 84% of fine particles (i.e., those smaller than 2.5 μm in size) released into the atmosphere

Modeling natural emissions in the Community Multiscale Air Quality (CMAQ) model - Part 1: Building an emissions data base

Science.gov (United States)

Smith, S. N.; Mueller, S. F.

2010-01-01

A natural emissions inventory for the continental United States and surrounding territories is needed in order to use the US Environmental Protection Agency Community Multiscale Air Quality (CMAQ) Model for simulating natural air quality. The CMAQ air modeling system (including the Sparse Matrix Operator Kernel Emissions (SMOKE) emissions processing system) currently estimates volatile organic compound (VOC) emissions from biogenic sources, nitrogen oxide (NOx) emissions from soils, ammonia from animals, several types of particulate and reactive gas emissions from fires, as well as windblown dust and sea salt emissions. However, there are several emission categories that are not commonly treated by the standard CMAQ Model system. Most notable among these are nitrogen oxide emissions from lightning, reduced sulfur emissions from oceans, geothermal features and other continental sources, and reactive chlorine gas emissions linked with sea salt chloride. A review of past emissions modeling work and existing global emissions data bases provides information and data necessary for preparing a more complete natural emissions data base for CMAQ applications. A model-ready natural emissions data base is developed to complement the anthropogenic emissions inventory used by the VISTAS Regional Planning Organization in its work analyzing regional haze based on the year 2002. This new data base covers a modeling domain that includes the continental United States plus large portions of Canada, Mexico and surrounding oceans. Comparing July 2002 source data reveals that natural emissions account for 16% of total gaseous sulfur (sulfur dioxide, dimethylsulfide and hydrogen sulfide), 44% of total NOx, 80% of reactive carbonaceous gases (VOCs and carbon monoxide), 28% of ammonia, 96% of total chlorine (hydrochloric acid, nitryl chloride and sea salt chloride), and 84% of fine particles (i.e., those smaller than 2.5 μm in size) released into the atmosphere. The seasonality and

Effects of increased solar ultraviolet radiation on biogeochemical cycles

International Nuclear Information System (INIS)

Zepp, R.G.; Callaghan, T.V.; Erickson, D.J.

1995-01-01

microorganisms. The marine sulfur cycle may be affected by UV-B radiation resulting in possible changes in the sea-to-air emissions of COS and dimethylsulfide, two gases that are degraded to sulfate aerosols in the stratosphere and troposphere, respectively

Relative importance of methylotrophic methanogenesis in sediments of the Western Mediterranean Sea

Science.gov (United States)

Zhuang, Guang-Chao; Heuer, Verena B.; Lazar, Cassandre S.; Goldhammer, Tobias; Wendt, Jenny; Samarkin, Vladimir A.; Elvert, Marcus; Teske, Andreas P.; Joye, Samantha B.; Hinrichs, Kai-Uwe

2018-03-01

Microbial production of methane is an important terminal metabolic process during organic matter degradation in marine sediments. It is generally acknowledged that hydrogenotrophic and acetoclastic methanogenesis constitute the dominant pathways of methane production; the importance of methanogenesis from methylated compounds remains poorly understood. We conducted various biogeochemical and molecular genetic analyses to characterize substrate availability, rates of methanogenesis, and methanogen community composition, and further evaluated the contribution of different substrates and pathways for methane production in deltaic surface and subsurface sediments of the Western Mediterranean Sea. Major substrates representing three methanogenic pathways, including H2, acetate, and methanol, trimethylamine (TMA), and dimethylsulfide (DMS), were detected in the pore waters and sediments, and exhibited variability over depth and between sites. In accompanying incubation experiments, methanogenesis rates from various 14C labeled substrates varied as well, suggesting that environmental factors, such as sulfate concentration and organic matter quality, could significantly influence the relative importance of individual pathway. In particular, methylotrophic and hydrogenotrophic methanogenesis contributed to the presence of micromolar methane concentrations in the sulfate reduction zone, with methanogenesis from methanol accounting for up to 98% of the total methane production in the topmost surface sediment. In the sulfate-depleted zone, hydrogenotrophic methanogenesis was the dominant methanogenic pathway (67-98%), and enhanced methane production from acetate was observed in organic-rich sediment (up to 31%). Methyl coenzyme M reductase gene (mcrA) analysis revealed that the composition of methanogenic communities was generally consistent with the distribution of methanogenic activity from different substrates. This study provides the first quantitative assessment of

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

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Filipiak Wojciech

2012-06-01

Full Text Available Abstract 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

Analysis of factors affecting volatile compound formation in roasted pumpkin seeds with selected ion flow tube-mass spectrometry (SIFT-MS) and sensory analysis.

Science.gov (United States)

Bowman, T; Barringer, S

2012-01-01

Pumpkin (Cucurbita pepo and maxima) seeds are uniquely flavored and commonly consumed as a healthy roasted snack. The objective was to determine dominant volatiles in raw and roasted pumpkin seeds, and the effect of seed coat, moisture content, fatty acid ratio, total lipids, reducing sugars, and harvest year on volatile formation. Sensory was conducted to evaluate overall liking of seed variety and texture. Seed processing included extraction from the fruit, dehydration, and roasting (150 °C). Oil extraction was done using soxhlet, fatty acid profile using Gas Chromatography Flame Ionization Detector, and reducing sugars using 3,5-dinitrosalicylic acid and UV-spectroscopy. Headspace analysis of seeds was performed by selected ion flow tube-mass spectrometry (SIFT-MS). Volatiles dominating in raw pumpkin seeds were lipid aldehydes, ethyl acetate, 2,3-butandione, and dimethylsulfide. Compounds contributing to roasted aroma include alkylpyrazines and Strecker and lipid aldehydes. Overall, hull-less seeds had higher volatile lipid aldehydes and Strecker aldehydes. Seeds dehydrated to a moisture content of 6.5% before roasting had higher initial and final volatile concentrations than seeds starting at 50% moisture. Higher oil content resulted in higher lipid aldehyde formation during roasting with a moderate correlation between free fatty acid ratio and corresponding lipid aldehyde. Harvest year (2009 compared with 2010) had a significant impact on volatile formation in hull-less seeds, but not as much as variety differences. No significant correlation was found between reducing sugars and volatile formation. Sensory showed that hull-less seeds were liked significantly more than hulled seeds. Elucidation of aromatic flavor development during roasting with SIFT-MS provides information on flavor release and offers better control during processing. Knowledge of volatiles in raw and roasted pumpkin seeds and effects of seed coat, moisture content, seed composition, and

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

Energy Technology Data Exchange (ETDEWEB)

Seager, S.; Bains, W.; Hu, R. [Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139 (United States)

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

Model study of multiphase DMS oxidation with a focus on halogens

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R. von Glasow

2004-01-01

Full Text Available We studied the oxidation of dimethylsulfide (DMS in the marine boundary layer (MBL with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV* (=SO2,aq+HSO3-+SO32- with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA to non-sea salt sulfate (nss-SO42- production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

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

Science.gov (United States)

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

Potential for a biogenic influence on cloud microphysics over the ocean: a correlation study with satellite-derived data

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A. Lana

2012-09-01

Full Text Available Aerosols have a large potential to influence climate through their effects on the microphysics and optical properties of clouds and, hence, on the Earth's radiation budget. Aerosol–cloud interactions have been intensively studied in polluted air, but the possibility that the marine biosphere plays an important role in regulating cloud brightness in the pristine oceanic atmosphere remains largely unexplored. We used 9 yr of global satellite data and ocean climatologies to derive parameterizations of the temporal variability of (a production fluxes of sulfur aerosols formed by the oxidation of the biogenic gas dimethylsulfide emitted from the sea surface; (b production fluxes of secondary organic aerosols from biogenic organic volatiles; (c emission fluxes of biogenic primary organic aerosols ejected by wind action on sea surface; and (d emission fluxes of sea salt also lifted by the wind upon bubble bursting. Series of global monthly estimates of these fluxes were correlated to series of potential cloud condensation nuclei (CCN numbers derived from satellite (MODIS. More detailed comparisons among weekly series of estimated fluxes and satellite-derived cloud droplet effective radius (r_e data were conducted at locations spread among polluted and clean regions of the oceanic atmosphere. The outcome of the statistical analysis was that positive correlation to CCN numbers and negative correlation to r_e were common at mid and high latitude for sulfur and organic secondary aerosols, indicating both might be important in seeding cloud droplet activation. Conversely, primary aerosols (organic and sea salt showed widespread positive correlations to CCN only at low latitudes. Correlations to r_e were more variable, non-significant or positive, suggesting that, despite contributing to large shares of the marine aerosol mass, primary aerosols are not widespread major drivers of the variability of cloud

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

Science.gov (United States)

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

Plankton origin of particulate dimethylsulfoniopropionate in a Mediterranean oligotrophic coastal and shallow ecosystem

Science.gov (United States)

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

2009-03-01

We report here dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) levels as a function of plankton communities and abiotic factors over a 12-month cycle in the Mediterranean oligotrophic coastal and shallow ecosystem of Niel Bay (N.W. Mediterranean Sea, France). Total particulate DMSP (DMSP p) and DMS concentrations were highly seasonal, peaking during a spring (April) bloom at 8.9 nM and 73.9 nM, respectively. Significant positive correlations were found between total DMSP p concentration and the abundance or biomass of the dinoflagellate Prorocentrum compressum (Spearman's rank correlation test: r = 0.704; p = 0.011). Similarly, DMS concentrations peaked during the development of blooms of P. compressum and Gymnodinium sp. There seemed to be a positive relationship between the chlorophyll a to pheopigment ratio and DMS concentrations, suggesting that DMS was released during phytoplankton growth. High DMS levels recorded in the shallow Niel Bay may also result from the activity of benthic macroalgae, and/or macrophytes such as Posidonia spp., or the resuspension of sulfur species accumulating in sediments. The fractionation of particulate DMSP into three size classes (>90 μm, 5-90 μm and 0.2-5 μm) revealed that 5-90 μm DMSP-containing particles made the greatest contribution to the total DMSP p pool (annual mean contribution = 62%), with a maximal contribution in April (96%). This size class consisted mainly of dinoflagellates (annual mean contribution = 68%), with P. compressum and Gymnodinium sp. the predominant species, together accounting for up to 44% of the phytoplankton present. The positive correlation between DMSP concentration in the 5-90 μm size class and the abundance of P. compressum (Spearman's rank correlation test: r = 0.648; p = 0.023) suggests that this phytoplankton species would be the major DMSP producer in Niel Bay. The DMSP collected in the >90 μm fraction was principally associated with zooplankton organisms, dominated by

Potential aromatic compounds as markers to differentiate between Tuber melanosporum and Tuber indicum truffles.

Science.gov (United States)

Culleré, Laura; Ferreira, Vicente; Venturini, María E; Marco, Pedro; Blanco, Domingo

2013-11-01

The Tuber indicum (Chinese truffle) and Tuber melanosporum (Black truffle) species are morphologically very similar but their aromas are very different. The black truffle aroma is much more intense and complex, and it is consequently appreciated more gastronomically. This work tries to determine whether the differences between the aromatic compounds of both species are sufficiently significant so as to apply them to fraud detection. An olfactometric evaluation (GC-O) of T. indicum was carried out for the first time. Eight important odorants were identified. In order of aromatic significance, these were: 1-octen-3-one and 1-octen-3-ol, followed by two ethyl esters (ethyl isobutyrate and ethyl 2-methylbutyrate), 3-methyl-1-butanol, isopropyl acetate, and finally the two sulfides dimethyldisulfide (DMDS) and dimethylsulfide (DMS). A comparison of this aromatic profile with that of T. melanosporum revealed the following differences: T. indicum stood out for the significant aromatic contribution of 1-octen-3-one and 1-octen-3-ol (with modified frequencies (MF%) of 82% and 69%, respectively), while in the case of T. melanosporum both had modified frequencies of less than 30%. Ethyl isobutyrate, ethyl 2-methylbutyrate and isopropyl acetate were also significantly higher, while DMS and DMDS had low MF (30-40%) compared to T. melanosporum (>70%). The volatile profiles of both species were also studied by means of headspace solid-phase microextraction (HS-SPME-GC-MS). This showed that the family of C8 compounds (3-octanone, octanal, 1-octen-3-one, 3-octanol and 1-octen-3-ol) is present in T. indicum at much higher levels. The presence of 1-octen-3-ol was higher by a factor of about 100, while 1-octen-3-one was detected in T. indicum only (there was no chromatographic signal in T. melanosporum). As well as showing the greatest chromatographic differences, these two compounds were also the most powerful from the aromatic viewpoint in the T. indicum olfactometry. Therefore

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

Science.gov (United States)

Cloern, James E.

1996-05-01

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

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

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

Pollution Levels in Fog at the Chilean Coast

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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.

Inorganic bromine in the marine boundary layer: a critical review

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R. Sander

2003-01-01

to produce atomic 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.

Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides: 1. Direct observations of the formation of the OH-DMS adduct-pressure dependence of the forward rate of addition and development of a predictive expression at low temperature.

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Williams, M B; Campuzano-Jost, P; Cossairt, B M; Hynes, A J; Pounds, A J

2007-01-11

A pulsed laser photolysis-pulsed laser-induced fluorescence (PLP-PLIF) system was employed to study the kinetics and mechanisms of reactions (1) OH + h6-DMS --> products and (2) OH + d6-DMS --> products. We report direct observations of the rate coefficients for the formation and dissociation of the h6-OHDMS and d6-OHDMS adducts over the pressure range 50-650 Torr and between 240 and 245 K, together with measurements of the oxygen dependence of the effective rate coefficients for reactions 1 and 2 under similar conditions. The effective rate coefficients increased as a function of O2 concentration reaching their limiting values in each case. The values of the adduct formation rate, obtained from the O2 dependencies, were in excellent agreement with values determined from direct observation of adduct equilibration in N2. OH regeneration is insignificant. The rate coefficients for the formation of the adduct isotopomers showed slight differences in their falloff behavior and do not approach the high-pressure limit in either case. The equilibrium constants obtained show no dependence on isotopomer and are in good agreement with previous work. A "second-law" analysis of the temperature dependence of the equilibrium constant gives an adduct bond strength (DeltaH degrees =-10.9 +/- 1.0 kcal mol(-1)), also in good agreement with previously reported values. Using the entropy calculated from the ab initio vibrational frequencies, we obtain a "third-law" value for the reaction enthalpy at 240 K, DeltaH(240K) degrees = -10.5 kcal mol(-1) in good agreement with the other approach. The rate coefficient for the reactions of the adducts with O2 was obtained from an analysis of the O2 dependence and was determined to be 6.3 +/- 1.2 x 10(-13) cm3 molecule(-1) s(-1), with no dependence on pressure or isotopomer. The pressure and temperature dependence for all of the elementary processes in the initial steps of the dimethylsulfide (DMS) oxidation mechanism have been characterized in

Overview and preliminary results of the Surface Ocean Aerosol Production (SOAP campaign

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C. S. Law

2017-11-01

Full Text Available Establishing the relationship between marine boundary layer (MBL aerosols and surface water biogeochemistry is required to understand aerosol and cloud production processes over the remote ocean and represent them more accurately in earth system models and global climate projections. This was addressed by the SOAP (Surface Ocean Aerosol Production campaign, which examined air–sea interaction over biologically productive frontal waters east of New Zealand. This overview details the objectives, regional context, sampling strategy and provisional findings of a pilot study, PreSOAP, in austral summer 2011 and the following SOAP voyage in late austral summer 2012. Both voyages characterized surface water and MBL composition in three phytoplankton blooms of differing species composition and biogeochemistry, with significant regional correlation observed between chlorophyll a and DMSsw. Surface seawater dimethylsulfide (DMSsw and associated air–sea DMS flux showed spatial variation during the SOAP voyage, with maxima of 25 nmol L−1 and 100 µmol m−2 d−1, respectively, recorded in a dinoflagellate bloom. Inclusion of SOAP data in a regional DMSsw compilation indicates that the current climatological mean is an underestimate for this region of the southwest Pacific. Estimation of the DMS gas transfer velocity (kDMS by independent techniques of eddy covariance and gradient flux showed good agreement, although both exhibited periodic deviations from model estimates. Flux anomalies were related to surface warming and sea surface microlayer enrichment and also reflected the heterogeneous distribution of DMSsw and the associated flux footprint. Other aerosol precursors measured included the halides and various volatile organic carbon compounds, with first measurements of the short-lived gases glyoxal and methylglyoxal in pristine Southern Ocean marine air indicating an unidentified local source. The application of a real-time clean sector

Modeling natural emissions in the Community Multiscale Air Quality (CMAQ model – Part 2: Modifications for simulating natural emissions

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S. F. Mueller

2011-01-01

Full Text Available The Community Multiscale Air Quality (CMAQ model version 4.6 has been revised with regard to the representation of chlorine (HCl, ClNO₂ and sulfur (dimethylsulfide, or DMS, and H₂S, and evaluated against observations and earlier published models. Chemistry parameterizations were based on published reaction kinetic data and a recently developed cloud chemistry model that includes heterogeneous reactions of organic sulfur compounds. Evaluation of the revised model was conducted using a recently enhanced data base of natural emissions that includes ocean and continental sources of DMS, H₂S, chlorinated gases and lightning NO_x for the continental United States and surrounding regions. Results using 2002 meteorology and emissions indicated that most simulated "natural" (plus background chemical and aerosol species exhibit the expected seasonal variations at the surface. Ozone exhibits a winter and early spring maximum consistent with ozone data and an earlier published model. Ozone distributions reflect the influences of atmospheric dynamics and pollutant background levels imposed on the CMAQ simulation by boundary conditions derived from a global model. A series of model experiments reveals that the consideration of gas-phase organic sulfur chemistry leads to sulfate aerosol increases over most of the continental United States. Cloud chemistry parameterization changes result in widespread decreases in SO₂ across the modeling domain and both increases and decreases in sulfate. Most cloud-mediated sulfate increases occurred mainly over the Pacific Ocean (up to about 0.1 μg m⁻³ but also over and downwind from the Gulf of Mexico (including parts of the eastern US. Geographic variations in simulated SO₂ and sulfate are due to the link between DMS/H₂S and their byproduct SO₂, the heterogeneity of cloud cover and precipitation (precipitating clouds act as

Investigations of Methane Production in Hypersaline Environments

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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

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

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D. Lowe

2015-02-01

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.

Temperature, productivity and sediment characteristics as drivers of seasonal and spatial variations of dissolved methane in the near-shore coastal areas (Belgian coastal zone, North Sea)

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Borges, Alberto V.; Speeckaert, Gaëlle; Champenois, Willy; Scranton, Mary I.; Gypens, Nathalie

2017-04-01

The open ocean is a modest source of CH4 to the atmosphere compared to other natural and anthropogenic CH4 emissions. Coastal regions are more intense sources of CH4 to the atmosphere than open oceanic waters, in particular estuarine zones. The CH4 emission to the atmosphere from coastal areas is sustained by riverine inputs and methanogenesis in the sediments due to high organic matter (OM) deposition. Additionally, natural gas seeps are sources of CH4 to bottom waters leading to high dissolved CH4 concentrations in bottom waters (from tenths of nmol L-1 up to several µmol L-1). We report a data set of dissolved CH4 concentrations obtained at nine fixed stations in the Belgian coastal zone (Southern North Sea), during one yearly cycle, with a bi-monthly frequency in spring, and a monthly frequency during the rest of the year. This is a coastal area with multiple possible sources of CH4 such as from rivers and gassy sediments, and where intense phytoplankton blooms are dominated by the high dimethylsulfoniopropionate (DMSP) producing micro-algae Phaeocystis globosa, leading to DMSP and dimethylsulfide (DMS) concentrations. Furthermore, the BCZ is a site of important OM sedimentation and accumulation unlike the rest of the North Sea. Spatial variations of dissolved CH4 concentrations were very marked with a minimum yearly average of 9 nmol L-1 in one of the most off-shore stations and maximum yearly average of 139 nmol L-1 at one of the most near-shore stations. The spatial variations of dissolved CH4 concentrations were related to the organic matter (OM) content of sediments, although the highest concentrations seemed to also be related to inputs of CH4 from gassy sediments associated to submerged peat. In the near-shore stations with fine sand or muddy sediments with a high OM content, the seasonal cycle of dissolved CH4 concentration closely followed the seasonal cycle of water temperature, suggesting the control of methanogenesis by temperature in these OM

Tropospheric Aerosols

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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 �

PERSPECTIVE: Snow matters in the polar regions

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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