CH3CH2SCH3þOH radicals: temperature-dependent rate coefficient andproduct identification under atmospheric pressure of air.

GABRIELA OKSDATH MANSILLA;ALICIA PEÑEÑORY;MICHAELA ALBU;IAN BARNES; PETER WIESEN; MARIA A. TERUEL

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

JOHN WILEY & SONS LTD

Año: 2010 vol. 23 p. 925 - 930

0894-3230

It is well established that sulfur-containing organic compounds play an important role in atmospheric chemistry. Dimethyl sulfide (CH3SCH3: DMS), produced in the oceans by the biological activity of phytoplankton and volatilized to the atmosphere, is considered to be the dominant natural source of sulfur released to the atmosphere.[1] The main gas-phase degradation process of DMS in the troposphere is chemical oxidation initiated by OH radicals during the day and by NO3 radicals at night. These processes lead to the formation of sulfur-containing species, such as sulfuric and methane sulfonic acids, which can significantly contribute to the acidity of the atmosphere.[2–5] It has been postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. processes lead to the formation of sulfur-containing species, such as sulfuric and methane sulfonic acids, which can significantly contribute to the acidity of the atmosphere.[2–5] It has been postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. DMS in the troposphere is chemical oxidation initiated by OH radicals during the day and by NO3 radicals at night. These processes lead to the formation of sulfur-containing species, such as sulfuric and methane sulfonic acids, which can significantly contribute to the acidity of the atmosphere.[2–5] It has been postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. processes lead to the formation of sulfur-containing species, such as sulfuric and methane sulfonic acids, which can significantly contribute to the acidity of the atmosphere.[2–5] It has been postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. activity of phytoplankton and volatilized to the atmosphere, is considered to be the dominant natural source of sulfur released to the atmosphere.[1] The main gas-phase degradation process of DMS in the troposphere is chemical oxidation initiated by OH radicals during the day and by NO3 radicals at night. These processes lead to the formation of sulfur-containing species, such as sulfuric and methane sulfonic acids, which can significantly contribute to the acidity of the atmosphere.[2–5] It has been postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. postulated that emissions of DMS from the oceans may have a significant influence on the Earth’s radiation budget and possibly in climate regulation due to the formation of CCN (cloud condensation nuclei) from the oxidation of SO2 formed in the photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. photo-oxidation of DMS.[6–10] In this sense, it is necessary to determine rate coefficients for the reactions of organic sulfur compounds with tropospheric oxidants like OH and NO3 radicals and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. and Cl atoms, as well as the degradation pathways under atmospheric conditions. This information allows an assessment of the persistence, fate, and possible environmental effects of sulfides in the atmosphere. de