Hal B. MARING Robert A. DucE** ** Graduate School of Oceanography, University of Rhode Island, Narragansett, RI 02882, U. S. A. 1) J. E. Lovelock, R.

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1 Hal B. MARING Robert A. DucE** ** Graduate School of Oceanography, University of Rhode Island, Narragansett, RI 02882, U. S. A. 1) J. E. Lovelock, R. J. Maggs, R. A. Rasmussen, Nature, 273, 452(1972). 2) M. 0. Andreae, H. Raemdonck, A Global View, Science, 221, 744(1983). 3) T. S. Bates, J. D. Cline, R. H. Gammon, R. Kelly- Hamsen, J. Geophys. Res., 92, 2930(1987). 4) H. Berresheim, ibid., 92, 13245(1987). 5) D. J. Erickson III, S. J. Ghan, J. E. Penner, ibid., 95, 7543(1990). 6) E. S. Saltzman, D. L. Savoie, R. G. Zika, J. M. Prospero, ibid., 88, 10897(1983). 7) S. Hatakeyama, M. Okuda, H. Akimoto, Geophys. Res. Lett., 9, 583(1982). 8) E. S. Saltzman, D. L. Savoie, J. M. Prospero, R. G. Zika, J. Atmos. Chem., 4, 227(1986).

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3 a) Samples were collected on the route of Antarctic Exploration ship "SHIRASE" b) Samples were collected on the ship "SEIYOMARU".. 0..A...1'- 11/ /5 15 3/5 15 Date Fig. 2 Concentrations of SO42- and Na + and ratio of SO42-/Na in the marine atmosphere on the route of Antarctic Exploration ship "SHIRASE", from November 1988 to March ) W. R. Barnard, M. O. Andreae, R. Iverson, Cont. Shelf. Res., 3, 103(1984).

4 11) A. J. Hynes, P. H. Wine, D. H. Semmes, J. Phys. Chem., 90, 4148(1986). 12) J. Dignon, J. Hameed, JAPC A, 39, 180(1989). 13) P. S. Liss, P. G. Slater, Nature, 247, 181(1974).

5 F M A M J J A S 0 N D J Fig. 4 Concentrations of SO2, nss-so42- (non sea salt sulfare), and MSA (methane sulfonic acid) in the marine atmosphere in Bermuda, ) J. W. H. Dacey, S. G. Wakeham, Brian L. Howes, Geophys. Res. Lett., 11, 991(1984). 15) M. O. Andreae, "The Ocean as a Source of Atmos - pheric Sulfur Compounds, in the Role of Air-Sea Exchange in Geochemical Cycling", edited by P. Buat Menard, pp , D. Reidel, Hingham, Mass (1986). 16) C. F. Cullis, M. M. Hirschler, Atmos. Environ., 14, 1263(1980).

6 Special Articles on Global and Regional Environment and Chemistry Concentrations of Sulfur Compounds (MSA, 502 and nss-so42-) in the Marine Atmosphere and Estimation of Biogenic Sulfur Emission From the Sea Shigeru TANAKA, Motohiro MACHIDA, Yoshikazu HASHIMOTO*, Hal B. MARING and Robert A. DucE" * Department of Applied Chemistry, Faculty of Science and Technology, Keio University; Hiyoshi, Kohoku-ku, Yokohama-shi, 223 Japan ** Graduate School of Oceanography, University of Rhode Island; Narragansett, RI U. S. A. Sulfur compounds (methane sulfonic acid (MSA), SO2 and non sea salt sulfate (nss-so 42-)) i n the marine atmosphere were investigated at the cource of the Antarctic Exploration ship "Shirase" over the North Pa cific Ocean, the Indian Ocean and the Anlarctic Ocean at Oahu Island over the North Pacific Ocean and at Bermuda Island over the North Atlantic Ocean. In any marine atmosphere, an existence of MSA was confirmed. Therefore, it was found that dimethyl sulfide (DMS) as a precursor of MSA was emitted globally from sea water to atmosphere. Moreover, a high concentration of MSA in Bermuda was observed during early summer when marine phytoplankton propagated. It suggestes that MSA is biogenic product. From this work, the mean concentrations in the unpolluted open sea atmosphere were fig/m3 for MSA, 0. 4 pern3 for nss-so42- (non seasalt sulfate), ppb for SO2. On the base of these measured concentrations, the global emission of biogenic sulfur compounds from sea water to atmosphere is estimated to be about 50 TgS/y. This value is comparable to 40% of the sulfur emission (126 x 1012 gs/y) from anthropogenic sources.

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