Gaseous (DMS, MSA, SO<sub>2</sub>, H<sub>2</sub>SO<sub>4</sub> and DMSO) and particulate (sulfate and methanesulfonate) sulfur species over the northeastern coast of Crete

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 o...

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Bibliographic Details
Main Authors: H. Bardouki, H. Berresheim, M. Vrekoussis, J. Sciare, G. Kouvarakis, K. Oikonomou, J. Schneider, N. Mihalopoulos
Format: Article
Language:English
Published: Copernicus Publications 2003-01-01
Series:Atmospheric Chemistry and Physics
Online Access:http://www.atmos-chem-phys.net/3/1871/2003/acp-3-1871-2003.pdf
Description
Summary: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 (SO<sub>2</sub>), sulfuric (H<sub>2</sub>SO<sub>4</sub>) and methanesulfonic acids (MSA) and particulate sulfate (SO<sub>4</sub><sup>2-</sup>) and methanesulfonate (MS<sup>-</sup>) have been performed during the campaign.<br> <br> Dimethylsulfide (DMS) levels ranged from 2.9 to 136 pmol·mol<sup>-1</sup> (mean value of 21.7 pmol·mol<sup>-1</sup>) and showed a clear diurnal variation with daytime maximum. During nighttime DMS levels fall close or below the detection limit of 2 pmol·mol<sup>-1</sup>. Concurrent measurements of OH and NO<sub>3</sub> radicals during the campaign indicate that NO<sub>3</sub> levels can explain most of the observed diurnal variation of DMS. Dimethylsulfoxide (DMSO) ranged between 0.02 and 10.1 pmol·mol<sup>-1</sup> (mean value of 1.7 pmol·mol<sup>-1</sup>) and presents a diurnal variation similar to that of DMS. SO<sub>2</sub> levels ranged from 220 to 2970 pmol·mol<sup>-1</sup> (mean value of 1030 pmol·mol<sup>-1</sup>), while nss-SO<sub>4</sub><sup>2-</sup> and MS<sup>-</sup> ranged from 330 to 7100 pmol·mol<sup>-1</sup>, (mean value of 1440 pmol·mol<sup>-1</sup>) and 1.1 to 37.5 pmol·mol<sup>-1</sup> (mean value of 11.5 pmol·mol<sup>-1</sup>) respectively.<br> <br> Of particular interest are the measurements of gaseous MSA and H<sub>2</sub>SO<sub>4</sub>. MSA ranged from below the detection limit (3x10<sup>4</sup>) to 3.7x10<sup>7</sup> molecules cm<sup>-3</sup>, whereas H<sub>2</sub>SO<sub>4</sub> ranged between 1x10<sup>5</sup> and 9.0x10<sup>7</sup> molecules cm<sup>-3</sup>. The measured H<sub>2</sub>SO<sub>4</sub> maxima are among the highest reported in literature and can be attributed to high insolation, absence of precipitation and increased SO<sub>2</sub> levels in the area. From the concurrent SO<sub>2</sub>, OH, and H<sub>2</sub>SO<sub>4</sub> measurements a sticking coefficient of 0.52±0.28 was calculated for H<sub>2</sub>SO<sub>4</sub>. 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 yield implies that gaseous MSA levels can not account for the observed MS<sup>-</sup> levels. Heterogeneous reactions of DMSO on aerosols should be considered to explain the observed levels of MS<sup>-</sup>.
ISSN:1680-7316
1680-7324