Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development

Yin, Fangdong; Grosjean, Daniel; Seinfeld, John H.

doi:10.1007/bf00053780

Cited by 336 publications

(295 citation statements)

References 104 publications

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“…These products are produced through reaction chains involving few branches and predominantly unidirectional radical abstraction and addition reactions (16). Given the high proportion of the ultimate sulfate product (NSS-SO 4 2− ) and the general similarity in the molecular structure of the reaction intermediates, it is inferred that the sulfur isotope composition of NSS-SO 4 2− will approximate that of oceanic DMS emissions.…”

Section: Conclusion and Implications For Marine Atmospherementioning

confidence: 99%

“…This sea-to-air exchange of DMS is mediated through turbulent diffusive processes in marine environments. Once released into the atmosphere, DMS is oxidized by odd nitrogen (NOx) and odd hydrogen (HOx) species through addition and abstraction reactions (16) to form DMSO, dimethyl sulfone (DMSO 2 ), sulfur dioxide (SO 2 ), non-seasalt sulfate (NSS-SO 4 2− ), and methanesulfonic acid (MSA). These products serve as sources for sulfuric acid, which has the potential to create new aerosols that can act as cloud condensation nuclei (CCN) (17).…”

mentioning

confidence: 99%

“…These products serve as sources for sulfuric acid, which has the potential to create new aerosols that can act as cloud condensation nuclei (CCN) (17). These CCN are thought to regulate cloud formation in the remote atmosphere and may have a significant impact on the Earth's cloud cover and albedo (15)(16)(17); however, many details of the connections between the biology, ocean chemistry, and atmospheric chemistry remain to be better understood (18).…”

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confidence: 99%

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

Oduro

Alstyne

Farquhar

2012

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

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Oceanic dimethylsulfoniopropionate (DMSP) is the precursor to dimethylsulfide (DMS), which plays a role in climate regulation through transformation to methanesulfonic acid (MSA) and nonseasalt 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. COO − ] is a secondary metabolite that is produced and stored in large amounts by marine macroalgae (1) and microalgae (2). This β-sulfonium compound is widespread among marine taxa but is particularly abundant within specific groups of phytoplankton, zooplankton, macroalgae, halophytic plants, macroinvertebrates, and fishes (3-5). DMSP plays important ecophysiological functions in marine algae by acting as an antioxidant (6), a cryoprotectant, an osmolyte, and a precursor to an activated defense system (3). It is also an important carbon and sulfur source for marine bacterioplankton (7).The synthesis of DMSP by algae has been reviewed previously (3,8). It starts with the assimilation of seawater sulfate into the cytoplasm. The sulfate is subsequently transported into the chloroplasts, where it is reduced to sulfide in the presence of glutathionine and then transformed into cysteine. Cysteine is used to synthesize methionine, which is then transformed into DMSP via one of three pathways that differ among taxonomic groups of plants and algae (9-12). Thus, the biosynthesis of DMSP ultimately depends on the activity of the sulfate assimilation pathway; however, little is known about how DMSP synthesis differs among algae from diverse origins, except that the whole molecule is derived from sulfur amino acids.DMSP and its cleavage product dimethylsulfide [DMS; (CH 3 ) 2 S] have attracted much research interest because of their possible role in climate regulation (13,14). Since the introduction of the Charlson, Lovelock, Andreae, Warren (CLAW) hypothesis, which argues for feedback between biological DMS production, Earth's solar radiation, and the regulation of global climate (15), there has been an increasing emphasis by environmental scientists on determining the strength of the sea-to-air biogeochemical sources of DMS. This sea-to-air exchange of DMS is mediated through turbu...

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Section: Conclusion and Implications For Marine Atmospherementioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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

Oduro

Alstyne

Farquhar

2012

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

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“…[39] Later, continuous measurements of DMS at Cape Grim demonstrated a strong seasonal cycle, with interannual variability that was matched in the sulfate aerosol. [40] The critical intermediate sulfur dioxide was hard to measure at Cape Grim, [41] but a modelling study encouraged the use of a novel technique [42] to monitor extremely low levels of sulfur dioxide, [43] showing that the most comprehensive modelling scheme for atmospheric sulfur available at the time [44,45] did an excellent job of reproducing the atmospheric sulfur cycle at Cape Grim in summer and demonstrated the influence of location (latitude), temperature, biology and photochemistry on the sulfur cycle. [43] Later work has shown that in some locations the OH radical is not the only oxidant and that halogen chemistry, in particular BrO, is probably involved in DMS oxidation.…”

Section: The Devil Is In the Detailmentioning

confidence: 99%

The CLAW hypothesis: a review of the major developments

2007

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Environmental context. Understanding the role of clouds in the warming and the cooling of the planet and how that role alters in a warming world is one of the biggest uncertainties climate change researchers face. Important in this regard is the influence on cloud properties of cloud condensation nuclei, the tiny atmospheric particles necessary for the nucleation of every single cloud droplet. The anthropogenic contribution to cloud condensation nuclei is known to be large in some regions through knowledge of pollutant emissions; however, the natural processes that regulate cloud condensation nuclei over large parts of the globe are less well understood. The CLAW hypothesis provides a mechanism by which plankton may modify climate through the atmospheric sulfur cycle via the provision of sulfate cloud condensation nuclei. The CLAW hypothesis was published over 20 years ago and has stimulated a great deal of research.Abstract. The CLAW hypothesis has for 20 years provided the intriguing prospect of oceanic and atmospheric systems exhibiting in an intimately coupled way a capacity to react to changing climate in a manner that opposes the change. A great number of quality scientific papers has resulted, many confirming details of specific links between oceanic phytoplankton and dimethylsulfide (DMS) emission to the atmosphere, the importance of DMS oxidation products in regulation of marine atmospheric cloud condensation nucleus (CCN) populations, and a concomitant influence on marine stratocumulus cloud properties. However, despite various links in the proposed phytoplankton-DMS-CCN-cloud albedo climate feedback loop being affirmed, there has been no overall scientific synthesis capable of adequately testing the hypothesis at a global scale. Moreover, significant gaps and contradictions remain, such as a lack of quantitative understanding of new particle formation processes in the marine atmospheric boundary layer, and of the extent to which dynamical, rather than microphysical, cloud feedbacks exist. Nevertheless, considerable progress has been made in understanding 'Earth System Science' involving the integration of ocean and atmospheric systems inherent in the CLAW hypothesis. We present here a short review of this progress since the publication of the CLAW hypothesis.

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“…It is generally accepted that MSA is produced from the OH addition to DMS, in a mechanism highly dependent on temperature and O 2 partial pressure. On the other hand, the presence of MSIA in the atmospheric decomposition of DMS was proposed by Yin et al, 10 as a second-generation product of the DMS oxidation. However, the mechanism and the yields of MSIA formation were reasons of great discussions in the literature.…”

Section: Introductionmentioning

confidence: 98%

Theoretical determination of the properties of Methanesulfinic and Methanesulfonic acids

Carvalho¹,

Silva²,

Resende³

2011

J. Braz. Chem. Soc.

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As propriedades estruturais, espectroscópicas e termodinâmicas de duas espécies de enxofre de interesse atmosférico, ácidos metanosulfínico (CH 3 S(O)OH, MSIA) e metanosulfônico (CH 3 S(O) 2 OH, MSA) foram determinadas no nível de CCSD(T)/CBS (coupled-cluster with single and double and perturbative triple excitations/complete basis set) de teoria. Duas conformações foram encontradas para o ácido metanosulfínico e o valor médio determinado para a entalpia de formação foi -337,2 kJ mol -1 . Para o ácido metanosulfônico, o resultado para a entalpia de formação foi 566,2 kJ mol -1 . Escolhendo cuidadosamente as reações químicas e considerando a existência de duas conformações de MSIA, esta investigação reporta os valores mais precisos de DH f disponíveis até agora para estas espécies.The structural, spectroscopic and thermochemical properties of two sulfur species of atmospheric interest, methanesulfinic (CH 3 S(O)OH, MSIA) and methanesulfonic (CH 3 S(O) 2 OH, MSA) acids, were determined at the CCSD(T)/CBS (coupled-cluster with single and double and perturbative triple excitations/complete basis set) level of theory. Two stable conformers were found to the methanesulfinic acid, and the determined average value for the enthalpy of formation (DH f ) was -337.2 kJ mol -1 . For methanesulfonic acid, the determined enthalpy of formation was 566.2 kJ mol -1 . By carefully choosing of the chemical reactions and considering the existence of two MSIA conformers, this investigation reports the most accurate DH f values available to date for these species. Keywords: dimethyl sulfide, enthalpy of formation, CCSD(T)/CBS theory IntroductionDimethyl sulfide (DMS), generated in the ocean by phytoplankton, is an important natural source of sulfur in the atmosphere. 1 The main final products of its atmospheric decomposition are sulfuric acid and sulfate ions, which are key species in the climate regulation, due to the fact that they are precursors of aerosols. Sulfur aerosols act in the global warming producing a negative radiative forcing, dispersing the solar radiation and increasing the albedo. 2 Besides, due to the low gas pressure and polarity, these species can act as cloud condensation nuclei (CCN), condensing water molecules. 3,4 Several experimental and theoretical investigations of the oxidation of DMS in gas phase were conducted 5-7 and studies for OH-initiated reaction had revealed methanesulfonic acid (CH 3 S(O) 2 OH, MSA) 8 and methanesulfinic acid (CH 3 S(O) OH, MSIA) 9 as two key intermediates. In general, there are some difficulties in the characterization of the products, and the values of product yields reported can differ significantly. It is generally accepted that MSA is produced from the OH addition to DMS, in a mechanism highly dependent on temperature and O 2 partial pressure. On the other hand, the presence of MSIA in the atmospheric decomposition of DMS was proposed by Yin et al., 10 as a second-generation product of the DMS oxidation. However, the mechanism and the yields of MSIA formation were reasons of ...

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Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development

Cited by 336 publications

References 104 publications

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

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

The CLAW hypothesis: a review of the major developments

Theoretical determination of the properties of Methanesulfinic and Methanesulfonic acids

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