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

Abstract. 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 2 ), sulfuric (H 2 SO 4 ) and methanesulfonic acids (MSA) and particulate sulfate (SO 4 2- ) and methanesulfonate (MS - ) have been performed during the campaign. Dimethylsulfide (DMS) levels ranged from 2.9 to 136 pmol·mol -1 (mean value of 21.7 pmol·mol -1 ) and showed a clear diurnal variation with daytime maximum. During nighttime DMS levels fall close or below the detection limit of 2 pmol·mol -1 . Concurrent measurements of OH and NO 3 radicals during the campaign indicate that NO 3 levels can explain most of the observed diurnal variation of DMS. Dimethylsulfoxide (DMSO) ranged between 0.02 and 10.1 pmol·mol -1 (mean value of 1.7 pmol·mol -1 ) and presents a diurnal variation similar to that of DMS. SO 2 levels ranged from 220 to 2970 pmol·mol -1 (mean value of 1030 pmol·mol -1 ), while nss-SO 4 2- and MS - ranged from 330 to 7100 pmol·mol -1 , (mean value of 1440 pmol·mol -1 ) and 1.1 to 37.5 pmol·mol -1 (mean value of 11.5 pmol·mol -1 ) respectively. Of particular interest are the measurements of gaseous MSA and H 2 SO 4 . MSA ranged from below the detection limit (3x10 4 ) to 3.7x10 7 molecules cm -3 , whereas H 2 SO 4 ranged between 1x10 5 and 9.0x10 7 molecules cm -3 . The measured H 2 SO 4 maxima are among the highest reported in literature and can be attributed to high insolation, absence of precipitation and increased SO 2 levels in the area. From the concurrent SO 2 , OH, and H 2 SO 4 measurements a sticking coefficient of 0.52±0.28 was calculated for H 2 SO 4 . 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 - levels. Heterogeneous reactions of DMSO on aerosols should be considered to explain the observed levels of MS - .

[1]  D. Worsnop,et al.  Online mass spectrometric aerosol measurements during the MINOS campaign (Crete, August 2001) , 2003 .

[2]  J. Lelieveld,et al.  Ground-based PTR-MS measurements of reactive organic compounds during the MINOS campaign in Crete, July-August 2001 , 2003 .

[3]  J. Lelieveld,et al.  Role of the NO 3 radicals in oxidation processes in the eastern Mediterranean troposphere during the MINOS campaign , 2003 .

[4]  N. Mihalopoulos,et al.  OH in the coastal boundary layer of Crete during MINOS: Measurements and relationship with ozone photolysis , 2003 .

[5]  T. Cokacar,et al.  Influence of Black Sea and local biogenic activity on the seasonal variation of aerosol sulfur species in the eastern Mediterranean atmosphere , 2002 .

[6]  H. Hansson,et al.  Gas‐aerosol relationships of H2SO4, MSA, and OH: Observations in the coastal marine boundary layer at Mace Head, Ireland , 2002 .

[7]  N. Mihalopoulos,et al.  Kinetics and mechanism of the oxidation of dimethylsulfoxide (DMSO) and methanesulfinate (MSI−) by OH radicals in aqueous medium , 2002 .

[8]  C. Moulin,et al.  Aerosol sources and their contribution to the chemical composition of aerosols in the Eastern Mediterranean Sea during summertime , 2002 .

[9]  N. Mihalopoulos,et al.  Sulfur budget above the Eastern Mediterranean: relative contribution of anthropogenic and biogenic sources , 2002 .

[10]  Nikos Mihalopoulos,et al.  Seasonal variation of dimethylsulfide in the gas phase and of methanesulfonate and non-sea-salt sulfate in the aerosols phase in the Eastern Mediterranean atmosphere , 2002 .

[11]  C. Genthon,et al.  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 , 2001 .

[12]  N. Mihalopoulos,et al.  Short-Term Variability of Atmospheric DMS and Its Oxidation Products at Amsterdam Island during Summer Time , 2001 .

[13]  A. Bandy,et al.  Airborne observations of DMSO, DMS, and OH at marine tropical latitudes , 2001 .

[14]  Christian Plass-Dülmer,et al.  Chemical ionization mass spectrometer for long-term measurements of atmospheric OH and H2SO4 , 2000 .

[15]  M. Kanakidou,et al.  Diurnal and seasonal variation of atmospheric dimethylsulfoxide at Amsterdam Island in the southern Indian Ocean , 2000 .

[16]  N. Mihalopoulos,et al.  Carboxylic acids in gas and particulate phase above the Atlantic Ocean , 2000 .

[17]  Kostas Tsigaridis,et al.  Temporal variations of surface regional background ozone over Crete Island in the southeast Mediterranean , 2000 .

[18]  P. Crutzen,et al.  Kinetics and Products of the Reactions BrO + DMS and Br + DMS at 298 K , 1999 .

[19]  D. Lenschow,et al.  Dimethyl sulfide oxidation in the equatorial Pacific: Comparison of model simulations with field observations for DMS, SO2, H2SO4(g), MSA(g), MS and NSS , 1999 .

[20]  B. Huebert,et al.  Observations of H2SO4 and MSA during PEM-Tropics-A , 1999 .

[21]  C. N. Hewitt,et al.  Dimethylsulfide and its oxidation products at two sites in Brittany (France) , 1999 .

[22]  S. Urbanski,et al.  Mechanistic and Kinetic Study of the Gas-Phase Reaction of Hydroxyl Radical with Dimethyl Sulfoxide , 1998 .

[23]  D. Lenschow,et al.  DMS oxidation in the Antarctic marine boundary layer: Comparison of model simulations and held observations of DMS, DMSO, DMSO2, H2SO4(g), MSA(g), and MSA(p) , 1998 .

[24]  R. P. Thorn,et al.  Measurements of dimethyl sulfide, dimethyl sulfoxide, dimethyl sulfone, and aerosol ions at Palmer Station, Antarctica , 1998 .

[25]  A. Jefferson,et al.  OH photochemistry and methane sulfonic acid formation in the coastal Antarctic boundary layer , 1998 .

[26]  H. Berresheim,et al.  Sulfur Chemistry in the Antarctic Troposphere Experiment: An overview of project SCATE , 1998 .

[27]  P. Ziemann,et al.  Measurements of the H2SO4 mass accommodation coefficient onto polydisperse aerosol , 1997 .

[28]  P. Bousquet,et al.  Tropospheric aerosol ionic composition in the Eastern Mediterranean region , 1997 .

[29]  A. Jefferson,et al.  Selected ion chemical ionization mass spectrometric measurement of OH , 1997 .

[30]  Nadine D. Spitz,et al.  Atmospheric sulfur over the east Mediterranean region , 1996 .

[31]  S. Mora,et al.  Atmospheric dimethylsulfide and sulfur species in aerosol and rainwater at a coastal site in New Zealand , 1996 .

[32]  B. Huebert,et al.  Production and loss of methanesulfonate and non-sea salt sulfate in the equatorial Pacific marine boundary layer , 1996 .

[33]  A. Wexler,et al.  Enhanced formation and development of sulfate particles due to marine boundary layer circulation , 1995 .

[34]  G. Ayers,et al.  Dimethylsulfide in marine air at Cape Grim, 41°S , 1995 .

[35]  Y. Chen.  [The change of serum alpha 1-antitrypsin level in patients with spontaneous pneumothorax]. , 1995, Zhonghua jie he he hu xi za zhi = Zhonghua jiehe he huxi zazhi = Chinese journal of tuberculosis and respiratory diseases.

[36]  M. Zahniser,et al.  Uptake of gas phase sulfur species methanesulfonic acid, dimethylsulfoxide, and dimethyl sulfone by aqueous surfaces , 1994 .

[37]  Yin‐Nan Lee,et al.  Aqueous reaction kinetics of ozone and dimethylsulfide and its atmospheric implications , 1994 .

[38]  D. Tanner,et al.  Measurement of the gas phase concentration of H2SO4 and methane sulfonic acid and estimates of H2SO4 production and loss in the atmosphere , 1993 .

[39]  M. Molina,et al.  Chemical kinetics and photochemical data for use in stratospheric modeling , 1992 .

[40]  J. Putaud,et al.  Field study of dimethylsulfide oxibation in the boundary layer: Variations of dimethylsulfide, methanesulfonic acid, sulfur dioxide, non-sea-salt sulfate and aitken nuclei at a coastal site , 1992 .

[41]  I. Barnes,et al.  Kinetic studies of the reactions of IO, BrO, and ClO with dimethylsulfide , 1991 .

[42]  N. Mihalopoulos,et al.  Seasonal variation of atmospheric dimethylsulfide at Amsterdam Island in the southern Indian Ocean , 1990 .

[43]  I. Barnes,et al.  Fourier Transform IR Studies of the Reactions of Dimethyl Sulfoxide with OH, NO3, and Cl Radicals , 1989 .

[44]  S. Warren,et al.  Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate , 1987, Nature.

[45]  P. Wine,et al.  Kinetics and mechanism of hydroxyl reactions with organic sulfides , 1986 .

[46]  W. R. Cofer,et al.  Improved aqueous scrubber for collection of soluble atmospheric trace gases. , 1985, Environmental science & technology.

[47]  H. Akimoto,et al.  Formation of sulfur dioxide and methanesulfonic acid in the photooxidation of dimethyl sulfide in the air , 1982 .

[48]  N. Jensen,et al.  Atmospheric gas-phase reactions of dimethylsulphoxide and dimethylsulphone with OH and NO3 radicals, Cl atoms and ozone , 2000 .

[49]  H. Bingemer,et al.  Biogenic sulphate generation in the Mediterranean Sea and its contribution to the sulphate anomaly in the aerosol over Israel and the Eastern Mediterranean , 2000 .

[50]  N. Mihalopoulos,et al.  A new technique for sampling and analysis of atmospheric dimethylsulfoxide (DMSO) , 2000 .

[51]  Ian Barnes,et al.  FT-IR product study of the photo-oxidation of dimethyl sulfide: Temperature and O2 partial pressure dependence , 1999 .

[52]  Ian Barnes,et al.  FT-IR product study of the OH-initiated oxidation of DMS in the presence of NOx , 1998 .

[53]  P. Wine,et al.  The atmospheric chemistry of dimethylsulfoxide (DMSO) kinetics and mechanism of the OH+DMSO reaction , 1996 .

[54]  H. Singh,et al.  Composition, chemistry, and climate of the atmosphere , 1995 .

[55]  A. Watson,et al.  Methanesulphonic acid, dimethyl sulphoxide and dimethyl sulphone in aerosols , 1990 .

[56]  P. Buat-Ménard.  The role of air-sea exchange in geochemical cycling , 1986 .

[57]  N. Fuchs,et al.  HIGH-DISPERSED AEROSOLS , 1971 .

[58]  C. Junge.  Sulfur in the atmosphere , 1960 .