Influence of nitrate radical on the oxidation of dimethyl sulfide in a polluted marine environment

Stark, Harald; Brown, Steven S.; Goldan, P. D.; Aldener, M.; Kuster, W. C.; Jakoubek, R.; Fehsenfeld, F. C.; Meagher, James F.; Bates, T. S.; Ravishankara, A. R.

doi:10.1029/2006jd007669

Cited by 38 publications

(38 citation statements)

References 76 publications

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“…2). Also, the average nighttime trend of WSOC g closely resembled the average diurnal profile of NO 3 observed in other studies (Stark et al, 2007). It is noteworthy that a reaction mechanism, presumably between biogenic VOCs and NO 3 , would produce significant WSOC g and yet little WSOC p relative to daytime production.…”

Section: Wsoc In Atlantasupporting

confidence: 81%

Gas/particle partitioning of water-soluble organic aerosol in Atlanta

et al. 2009

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Abstract. Gas and particle-phase organic carbon compounds soluble in water (e.g., WSOC) were measured simultaneously in Atlanta throughout the summer of 2007 to investigate gas/particle partitioning of ambient secondary organic aerosol (SOA). Previous studies have established that, in the absence of biomass burning, particulate WSOC (WSOC p ) is mainly from secondary organic aerosol (SOA) production. Comparisons between WSOC p , organic carbon (OC) and elemental carbon (EC) indicate that WSOC p was a nearly comprehensive measure of SOA in the Atlanta summertime. WSOC p and gas-phase WSOC (WSOC g ) concentrations both exhibited afternoon maxima, indicating that photochemistry was a major route for SOA formation. An additional nighttime maximum in the WSOC g concentration indicated a dark source for oxidized organic gases, but this was not accompanied by detectable increases in WSOC p . To study SOA formation mechanisms, WSOC gas/particle partitioning was investigated as a function of temperature, RH, NO x , O 3 , and organic aerosol mass concentration. No clear relationship was observed between temperature and partitioning, possibly due to a simultaneous effect from other temperature-dependent processes. For example, positive temperature effects on emissions of biogenic SOA precursors and photochemical SOA formation may have accounted for the observed similar proportional increases of WSOC p and WSOC g with temperature. Relative humidity data indicated a linear dependence between partitioning and predicted fine particle liquid water. Lower NO x concentrations were associated with greater partitioning to particles, but WSOC partitioning had no visible relation to O 3 or fine particle OC mass concentration. There was, however, a relationship between WSOC partitioning and the WSOC p concentration, Correspondence to: R. Weber (rweber@eas.gatech.edu) suggesting a compositional dependence between partitioning semi-volatile gases and the absorbing organic aerosol. Combined, the overall results suggest two dominant SOA formation processes in urban Atlanta during summer. One was the photochemical production of SOA from presumably biogenic precursors that increased with the onset of sunrise and peaked in the afternoon. The other, which showed no apparent diurnal pattern, involved the partitioning of semi-volatile gases to liquid water, followed by heterogeneous reactions. The co-emission of water vapor and biogenic VOCs from vegetation may link these processes.

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Section: Wsoc In Atlantasupporting

confidence: 81%

Gas/particle partitioning of water-soluble organic aerosol in Atlanta

et al. 2009

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“…Because OH production is UV dependent, it displays a clear seasonality with higher values during each hemispheric summer (28). Although DMS conversion into CCN also is influenced by nitrate radical DMS oxidation at nighttime (29) and by the presence of other aerosols, particularly over polluted regions, the central role of OH suggests that any coupling (or mismatch) between the seasonalities of DMS and OH could amplify (or buffer) the seasonal contribution of biogenic sulfur to CCN production.…”

Section: Resultsmentioning

confidence: 99%

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

Vallina

Simó

Manizza

2007

Proc. Natl. Acad. Sci. U.S.A.

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The solar radiation dose in the oceanic upper mixed layer (SRD) has recently been identified as the main climatic force driving global dimethylsulfide (DMS) dynamics and seasonality. Because DMS is suggested to exert a cooling effect on the earth radiative budget through its involvement in the formation and optical properties of tropospheric clouds over the ocean, a positive relationship between DMS and the SRD supports the occurrence of a negative feedback between the oceanic biosphere and climate, as postulated 20 years ago. Such a natural feedback might partly counteract anthropogenic global warming through a shoaling of the mixed layer depth (MLD) and a consequent increase of the SRD and DMS concentrations and emission. By applying two globally derived DMS diagnostic models to global fields of MLD and chlorophyll simulated with an Ocean General Circulation Model coupled to a biogeochemistry model for a 50% increase of atmospheric CO2 and an unperturbed control run, we have estimated the response of the DMS-producing pelagic ocean to global warming. Our results show a net global increase in surface DMS concentrations, especially in summer. This increase, however, is so weak (globally 1.2%) that it can hardly be relevant as compared with the radiative forcing of the increase of greenhouse gases. This contrasts with the seasonal variability of DMS (1000 -2000% summer-to-winter ratio). We suggest that the ''plankton-DMS-clouds-earth albedo feedback'' hypothesis is less strong a long-term thermostatic system than a seasonal mechanism that contributes to regulate the solar radiation doses reaching the earth's biosphere. mixed layer depth ͉ solar radiation dose ͉ global modeling O cean-emitted dimethylsulfide (DMS) has been suggested to play a climatic role by contributing to cloud droplet condensation and thereby to cloud albedo. As such a climate-active compound, DMS was proposed as a candidate to partially counteract human-induced global warming (GW) through a global biogeochemical feedback between oceanic biosphere and climate, the so-called ''CLAW hypothesis'' (1). To quantitatively assess the feasibility and magnitude of this potential long-term climatestabilizing response, it is important to understand which are the main factors that drive DMS dynamics: if we can estimate how they are changing due to GW, we should be able to predict the DMS response. Early works pointed to the mutual interaction of several factors (i.e., phytoplankton community structure, zooplankton grazing, bacterial activity, etc.), over which the mixed layer depth (MLD) seems to have some kind of regulatory influence (2, 3). However, more recent studies have strongly suggested that solar radiation is the key factor regarding DMS dynamics, notably through its stress effects on phytoplankton and inhibitory effects on heterotrophic bacterioplankton (4-8). One suggestion is that the enzymatic cleavage of dimethylsulfoniopropionate (DMSP) into DMS in phytoplankton is part of an antioxidant system that protects the cell from endogenous, hazard...

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“…The two most important oxidants of DMS in the atmosphere are thought to be the OH and NO 3 radicals (Barnes et al, 2006) (Reactions R6 and R7). Because of its photochemical source, OH is thought to be the more important oxidant during the day in tropical regions, while NO 3 becomes more important at night, at high latitudes, and in more polluted air masses (Stark et al, 2007). Certain halogenated compounds, e.g.…”

Section: Dimethyl Sulfide (Dms)mentioning

confidence: 99%

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide

et al. 2015

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Abstract. Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO 2 and NO 2 in the atmosphere; however the significance of this chemistry for SO 2 processing (affecting sulfate aerosol) and NO 2 processing (affecting NO x levels) depends critically upon the fate of the SCIs with respect to reaction with water and decomposition. Here, we have investigated the removal of SO 2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO 2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene-derived SCIs with H 2 O. Under excess SO 2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (±0.03). The observed SO 2 removal kinetics are consistent with a relative rate constant, k(SCI + H 2 O) / k(SCI + SO 2 ), of 3.1 (±0.5) × 10 −5 for isoprene-derived SCIs. The relative rate constant for k(SCI decomposition) / k(SCI+SO 2 ) is 3.0 (±3.2) × 10 11 cm −3 . Uncertainties are ±2σ and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprenederived SCIs are unlikely to make a substantial contribution to gas-phase SO 2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO 2 removal in the isopreneozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCIs and dimethyl sulfide (DMS); the observed SO 2 removal kinetics are consistent with a relative rate constant, k(SCI + DMS) / k(SCI + SO 2 ), of 3.5 (±1.8). This result suggests that SCIs may contribute to the oxidation of DMS in the atmosphere and that this process could therefore influence new particle formation in regions impacted by emissions of unsaturated hydrocarbons and DMS.

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Influence of nitrate radical on the oxidation of dimethyl sulfide in a polluted marine environment

Cited by 38 publications

References 76 publications

Gas/particle partitioning of water-soluble organic aerosol in Atlanta

Gas/particle partitioning of water-soluble organic aerosol in Atlanta

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

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide

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Influence of nitrate radical on the oxidation of dimethyl sulfide in a polluted marine environment

Cited by 38 publications

References 76 publications

Gas/particle partitioning of water-soluble organic aerosol in Atlanta

Gas/particle partitioning of water-soluble organic aerosol in Atlanta

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

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO&lt;sub&gt;2&lt;/sub&gt;, H&lt;sub&gt;2&lt;/sub&gt;O and dimethyl sulfide

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Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide