Abstract
The products of the 254 nm photolysis of ppm levels of DMDS have been studied as a function of the O2 partial pressure at 760 Torr (N2 + O2) and 298±2 K. The major sulfur containing compounds detected were SO2 and CH3SO3H (methane sulfonic acid, MSA) and the major carbon containing compounds were CO, HCHO, CH3OH and CH3OOH (methyl hydroperoxide). Within the experimental error limits the observed sulfur and carbon balances were approximately 100%. CH3OOH has been observed for the first time in such a photooxidation system. Its observation provides evidence for the formation of CH3 radicals by the further oxidation of the CH3S radicals formed in the primary photolysis step.
From the behavior of the DMDS photolysis products as a function of the O2 partial pressure, O3 concentration and added OH radical source it is postulated that the further reactions of CH3SOH (methyl sulfenic acid), formed in the reaction OH + CH3SCCH3 → CH3SOH + CH3S, are the main source of MSA in the 254 nm photolysis of DMDS.
Some of the possible implications of the results of this study for the degradation mechanisms of other atmospherically important organic sulfur compounds, in particular DMS, are briefly considered.
Similar content being viewed by others
References
Andreae, M. O., 1986, The ocean as a source of atmospheric sulfur compounds, in P. Buat-Menard (ed.),The Role of Air-Sea Exchange in Geochemical Cycling, D. Reidel, Dordrecht, pp. 331–362.
Atkinson, R., Baulch, D. L., Cox, R. A., Hampson, R. F., Jr., Kerr, J. A., and Troe, J., 1992, Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement IV,J. Phys. Chem. Ref. Data 21, 1125–1568.
Bates, T. S., Cline, J. D., Gammon, R. H., and Kelly-Hansen, S. R., 1987, Regional and seasonal variations in the flux of oceanic dimethylsulfide to the atmosphere,J. Geophys. Res. 92, 2930–2938.
Balla, R. J. and Heicklen, J., 1985, Oxidation of sulfur compounds III: The photolysis of (CH3S)2 in the presence of O2,J. Photochem. 29, 297–310.
Balla, R. J. and Heicklen, J., 1984, Oxidation of sulfur compounds I: The photolysis of CH3SH and (CH3S)2 in the presence of NO,J. Canad. J. Chem. 62, 162–170.
Balla, R. J., Nelson, H. H., and McDonald, J. R., 1986, Kinetics of the reaction of CH3S with NO, NO2, and O2,Chem. Phys. 109, 101–107.
Barnes, I., Becker, K. H., and Patroescu, J., 1993, Chemistry of radical intermediates in the tropospheric oxidation of DMS and isoprene, Paper presented at the LAB-VOC/FIELDVOC Meeting, June 4 and 5, Le Dourdy, Loctudy, Bretagne, France.
Barnes, I., Bastian, V., Becker, K. H., and Niki, H., 1987, FTIR spectroscopic studies of the CH3S + NO2 reaction under atmospheric conditions,Chem. Phys. Lett. 140, 451–457.
Barnes, I., Bastian, V., and Becker, K. H., 1988, Kinetics and mechanism of the reaction of OH radicals with dimethyl sulfide,Int. J. Chem. Kinet. 20, 415–431.
Black, G. and Jusinski, L. E., 1986, Laser-induced fluorescence studies of the CH3S radical,J. Chem. Soc. 82, 2143–2151.
Dominé, F., Murrells, T. P., and Howard, C. J., 1990, Kinetics of the reactions of NO2 with CH3S, CH3SO, CH3SS, and CH3SSO at 297 K and 1 torr,J. Phys. Chem. 94, 5839–5847.
Dominé, F., Ravishankara, A. R., and Howard, C. J., 1992, Kinetics and mechanisms of the reactions of CH3S, CH3SO, CH3SS with O3 at 300 K and low pressure,J. Phys. Chem. 96, 2171–2178.
Graham, D. M., Mieville, R. L., and Sivertz, C., 1964, Photo-initiated reactions of thiols and olefins I. The thiyl radical catalysed isomerization of butene-2 and 1,1-ethylene-d2,Can. J. Chem. 42, 2239–2249.
Grosjean, D. and Lewis, R., 1982, Atmospheric photooxidation of methyl sulfide,Geophys. Res. Lett. 9, 1203–1206.
Grosjean, D., 1984, Photooxidation of methyl sulfide, ethyl sulfide, and methanethiol,Environ. Sci. Technol. 19, 1059–1065.
Hatakeyama, S. and Akimoto, H., 1983, Reactions of OH radicals with methanethiol, dimethyl sulfide and dimethyl disulfide in air,J. Phys. Chem. 87, 2387–2395.
Hynes, A. J. and Wine, P. H., 1987, Kinetics of the OH + CH3SH reaction under atmospheric conditions,J. Phys. Chem. 91, 3672–3676.
Lightfoot, P. D., Cox, R. A., Crowley, J. N., Destriau, M., Hayman, G. D., Jenkin, M. E., Moortgat, G. K., and Zabel, F., 1992, Organic peroxy radicals: Kinetics, Spectroscopy and tropospheric chemistry,Atmos. Chem. 26A(10, 1805–1961.
Martinet, A., 1989, Etudes cinétiques sous conditions atmosphériques simulées, de réactions élémentaires intervenant dans la photooxydation de précurseurs d'acidité en milieu marin, PhD Thesis, Université Paris VII.
Mihalopoulos, N., Barnes, I., and Becker, K. H., 1991, Infrared absorption spectra and integrated band intensities for gaseous methanesulphonic acid (MSA),Atmos. Environ. 26A, 807–812.
Niki, H., Maker, P. D., Savage, C. M., and Breitenbach, L. P., 1983, An FTIR study of the mechanism for the reaction HO + CH3SCH3,Int. J. Chem. Kinet. 15, 647–654.
Plane, J., 1989, Gas-phase atmospheric oxidation of biogenic sulfur compounds: A review, in E. S. Saltzman and W. J. Cooper (eds.),Biogenic Sulfur in the Environment, American Chemical Society Symposium Series 393, Washington, D.C., pp. 404–423.
Turnipseed, A. A., Barone, S. B., and Ravishankara, A. R., 1993, Reactions of CH3S and CH3SOO with O3, NO2, and NO,J. Phys. Chem. 97, 5926–5934.
Turnipseed, A. A., Barone, S. B., and Ravishankara, A. R., 1992, Observation of CH3S addition to O2 in the gas phase,J. Phys. Chem. 96, 7502–7505.
Tycholiz, D. R. and Knight, A. R., 1973, Reactions of thiyl radicals, IX. Sensitized photolysis of methyl sulfide. Pressure dependence of methylthiyl radicals,J. Am. Chem. Soc. 95, 1726–1731.
Tyndall, G. S. and Ravishankara, A. R., 1989a, Kinetics and mechanisms of the reactions of CH3S radicals with O2 and NO2 at 298 K,J. Phys. Chem. 93, 2426.
Tyndall, G. S. and Ravishankara, A. R., 1989b, Kinetics of the reaction of CH3S with O3 at 298 K,J. Phys. Chem. 93, 4707–4710.
Tyndall, G. S. and Ravishankara, A. R., 1991, Atmospheric oxidation of reduced sulfur species,Int. J. Chem. Kinet. 23, 483–527.
Yin, F., Grosjean, D., and Seinfeld, J. H., 1986, Analysis of atmospheric photooxidation mechanisms for organosulfur compounds,J. Geophys. Res. 91, 14,417–14,438.
Yin, F., Grosjean, D., and Seinfeld, J. H.: 1990a, Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development,J. Atmos. Chem. 11, 309–364.
Yin, F., Grosjean, D., and Seinfeld, J. H., 1990b, Photooxidation of dimethyl sulfide and dimethyl disulfide. II: Mechanism evaluation,J. Atmos. Chem. 11, 365–399.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Barnes, I., Becker, K.H. & Mihalopoulos, N. An FTIR product study of the photooxidation of dimethyl disulfide. J Atmos Chem 18, 267–289 (1994). https://doi.org/10.1007/BF00696783
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00696783