Subdaily variations of atmospheric dimethylsulfide, dimethylsulfoxide, methanesulfonate, and non-sea-salt sulfate aerosols in the atmospheric boundary layer at Dumont d'Urville (coastal Antarctica) during summer

A study of atmospheric dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) was conducted on a subdaily basis during austral summer months (450 samples from mid-December 1998 to late-February 1999) at Dumont d'Urville, a coastal Antarctic site (66° 40′S, 140° 01′E). In addition, subdaily aerosol samplings were analyzed for particulate methanesulfonate (MSA) and non-sea-salt sulfate (nssSO42−). During these summer months, DMS and DMSO levels fluctuated from 34 to 2923 pptv (mean of 290±305 pptv) and from 0.4 to 57 pptv (mean of 3.4±4.4 pptv), respectively. Mean MSA and non-sea-salt sulfate (nssSO42−) mixing ratios were close to 12.5±8.2 pptv and 68.1±35.0 pptv, respectively. In two occasions characterized by stable wind conditions and intense insolation, it was possible to examine the local photochemistry of DMS. During these events, DMSO levels tracked quite closely the solar flux and particulate MSA levels were enhanced during the afternoons. Photochemical calculations reproduce quite well observed diurnal variations of DMSO when we assume an 0.8 yield of DMSO from the DMS/OH addition channel and an heterogeneous loss rate of DMSO proportional to the OH radical concentration: 0.5×10−10 [OH] + 5.5x10−5 (in s−1). If correct, on a 24 hour average the heterogeneous loss of DMSO is estimated to be 2 times faster than the DMSO/OH gas phase oxidation in these regions. Very low levels of DMSO were found in the aerosol phase (less than 0.01 pptv), suggesting that an efficient oxidation of DMSO subsequently takes place onto the aerosol surface. The observed increase of MSA levels which takes place quasi-immediately after the noon DMSO maximum suggests that an heterogeneous oxidation of DMSO onto aerosols represents a more efficient pathway producing MSA compared to the gas phase DMSO/OH pathway. Since only a third of the total amount of DMSO lost can be explained by the observed enhancement of MSA levels, further studies investigating other species including methanesulfinic acid and dimethylsulfone (DMSO2) formed during the oxidation of DMS are here needed. When katabatic winds took place, bringing continental Antarctic air at the site, enrichments of DMSO relative to DMS and MSA relative to non-sea-salt sulfate levels were observed. That is in agreement with the hypothesis of an accumulation of DMSO and probably of gaseous MSA in the free Antarctic troposphere in relation to a less efficient heterogeneous loss rate of DMSO.