{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T02:50:33Z","timestamp":1791168633802,"version":"4.1.0"},"reference-count":44,"publisher":"American Association for the Advancement of Science (AAAS)","issue":"5347","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Science"],"published-print":{"date-parts":[[1998,1,2]]},"abstract":"<jats:p>Halogen atoms from the reactions of sea-salt particles may play a significant role in the marine boundary layer. Reactions of sodium chloride, the major component of sea-salt particles, with nitrogen oxides generate chlorine atom precursors. However, recent studies suggest there is an additional source of chlorine in the marine troposphere. This study shows that molecular chlorine is generated from the photolysis of ozone in the presence of sea-salt particles above their deliquescence point; this process may also occur in the ocean surface layer. Given the global distribution of ozone, this process may provide a global source of chlorine.<\/jats:p>","DOI":"10.1126\/science.279.5347.74","type":"journal-article","created":{"date-parts":[[2002,7,27]],"date-time":"2002-07-27T09:49:42Z","timestamp":1027763382000},"page":"74-76","source":"Crossref","is-referenced-by-count":286,"title":["Formation of Molecular Chlorine from the Photolysis of Ozone and Aqueous Sea-Salt Particles"],"prefix":"10.1126","volume":"279","author":[{"given":"K. W.","family":"Oum","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of California, Irvine, CA 92697\u20132025 USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"M. J.","family":"Lakin","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of California, Irvine, CA 92697\u20132025 USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"D. O.","family":"DeHaan","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of California, Irvine, CA 92697\u20132025 USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"T.","family":"Brauers","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of California, Irvine, CA 92697\u20132025 USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"B. J.","family":"Finlayson-Pitts","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of California, Irvine, CA 92697\u20132025 USA."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"221","reference":[{"key":"e_1_3_1_2_2","doi-asserted-by":"crossref","first-page":"14513","DOI":"10.1029\/92JD01373","volume":"97","author":"Cahill T. A.","year":"1992","unstructured":"Cahill T. A., Wilkinson K., Schnell R., J. Geophys. Res. 97, 14513 (1992).","journal-title":"J. Geophys. Res."},{"key":"e_1_3_1_3_2","doi-asserted-by":"crossref","unstructured":"B. J. Finlayson-Pitts Res. Chem. Intermed. 19 235 (1993).","DOI":"10.1163\/156856793X00091"},{"key":"e_1_3_1_4_2","doi-asserted-by":"crossref","first-page":"47","DOI":"10.1029\/94GB03103","volume":"9","author":"Graedel T. E.","year":"1995","unstructured":"Graedel T. E., Keene W. C., Global Biogeochem. Cycles 9, 47 (1995).","journal-title":"Global Biogeochem. Cycles"},{"key":"e_1_3_1_5_2","unstructured":"W. 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A., Shepson P. B., Hastie D. R., Barrie L. A., J. Geophys. Res. 102, 15999 (1997).","journal-title":"J. Geophys. Res."},{"key":"e_1_3_1_21_2","unstructured":"___ ibid. p. 16005."},{"key":"e_1_3_1_22_2","unstructured":"C. W. Spicer et al. in preparation."},{"key":"e_1_3_1_23_2","unstructured":"The internal surfaces of the rectangular metal chamber were coated with an inert halocarbon wax (Halocarbon Products Corporation Series 1500) to minimize wall reactions. The top of the chamber has quartz windows above which was mounted a series of lamps for carrying out photochemical reactions. We used four low-pressure mercury lamps (UVP XX-15S) with the major output at \u03bb = 254 nm."},{"key":"e_1_3_1_24_2","unstructured":"Two sets of White cell mirrors were mounted at opposite ends of the chamber for long-path FTIR and UV-visible spectrometry. The base path is 2 m with a total path length of 52 m used here for both FTIR and UV spectrometry."},{"key":"e_1_3_1_25_2","unstructured":"A sampling port was used to sample the gases into the API-MS for detection and measurement of halogen gases. The use of API-MS permits the unique and sensitive identification of Cl 2 Br 2 and BrCl in the negative-ion mode as a result of the generation of the parent ions Cl 2 \u2212 Br 2 \u2212 and BrCl \u2212 respectively by electron transfer from O 2 \u2212 and its clusters with water and O 2 at 1 atm. We isolated the parent ion using the first quadrupole. Scans based on the use of this quadrupole provide conventional mass spectra and are called Q1 scans. Ions exiting this first quadrupole can be collisionally dissociated in a gas collision cell and the fragment ions thus generated can be measured in the second quadrupole. Mass spectra generated by this approach are called MS-MS scans. This dual-selection process permits the unique identification of the halogens in complex mixtures."},{"key":"e_1_3_1_26_2","unstructured":"D. O. DeHaan and B. J. Finlayson-Pitts J. Phys. Chem. in press."},{"key":"e_1_3_1_27_2","doi-asserted-by":"crossref","first-page":"656","DOI":"10.1039\/tf9575300656","volume":"53","author":"Taube H.","year":"1957","unstructured":"Taube H., Trans. Faraday Soc. 53, 656 (1957).","journal-title":"Trans. Faraday Soc."},{"key":"e_1_3_1_28_2","doi-asserted-by":"crossref","unstructured":"G. R. Peyton and W. H. Glaze Environ. Sci. Technol. 22 761 (1988).","DOI":"10.1021\/es00172a003"},{"key":"e_1_3_1_29_2","doi-asserted-by":"crossref","unstructured":"M. D. Gurol and A. Akata AIChE J. 42 3283 (1996).","DOI":"10.1002\/aic.690421128"},{"key":"e_1_3_1_30_2","doi-asserted-by":"crossref","unstructured":"G. G. Jayson B. J. Parsons A. J. Swallow J. Chem. Soc. Faraday Trans. 1 69 1597 (1973).","DOI":"10.1039\/f19736901597"},{"key":"e_1_3_1_31_2","doi-asserted-by":"crossref","first-page":"861","DOI":"10.1002\/bbpc.19860901007","volume":"90","author":"Wagner I.","year":"1986","unstructured":"Wagner I., Karth\u00e4user J., Strehlow H., Ber. Bunsenges. Phys. Chem. 90, 861 (1986).","journal-title":"Ber. Bunsenges. Phys. Chem."},{"key":"e_1_3_1_32_2","unstructured":"The rate constant for the dissociation at room temperature is k 9b = 6.1 \u00d7 10 9 s \u20131 ; that for reaction 10 is k 10 = 2.1 \u00d7 10 10 liter mol \u22121 s \u22121 (29). At a pH of 7 the lifetime of HOCl \u2013 with respect to dissociation is 0.2 ns compared to 0.5 ms for reaction 10 with H + . Thus reaction 10 is the rate-determining step which is still relatively fast on the time scale of our experiments."},{"key":"e_1_3_1_33_2","unstructured":"There is experimental evidence for this in these studies because peak Cl 2 concentrations decreased as the initial O 3 concentration decreased."},{"key":"e_1_3_1_34_2","unstructured":"C. D. O'Dowd and"},{"key":"e_1_3_1_34_3","doi-asserted-by":"crossref","first-page":"1137","DOI":"10.1029\/92JD02302","volume":"98","author":"Smith M. H.","year":"1993","unstructured":"Smith M. H., J. Geophys. Res. 98, 1137 (1993).","journal-title":"J. Geophys. Res."},{"key":"e_1_3_1_35_2","first-page":"3819","volume":"102","author":"Gong S. L.","year":"1997","unstructured":"Gong S. L., et al., ibid. 102, 3819 (1997).","journal-title":"ibid."},{"key":"e_1_3_1_36_2","unstructured":"C. D. O'Dowd"},{"key":"e_1_3_1_36_3","doi-asserted-by":"crossref","first-page":"73","DOI":"10.1016\/S1352-2310(96)00106-9","volume":"31","author":"Smith M. 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Photobiol."},{"key":"e_1_3_1_40_2","doi-asserted-by":"crossref","unstructured":"R. Atkinson J. Phys. Chem. Ref. Data 26 215 (1997).","DOI":"10.1525\/9780520311824-027"},{"key":"e_1_3_1_41_2","doi-asserted-by":"crossref","unstructured":"U. von Gunten and J. Hoign\u00e9 Environ. Sci. Technol. 28 1234 (1994).","DOI":"10.1021\/es00056a009"},{"key":"e_1_3_1_42_2","unstructured":"The molar ratio of Br \u2212 to Cl \u2212 in the aerosol is 1:660."},{"key":"e_1_3_1_43_2","unstructured":"The concept design and construction of the aerosol apparatus was carried out in collaboration with J. C. Hemminger F. S. Rowland and D. W. Toohey and was supported by NSF (grant ATM-9512181) and the University of California Irvine. We are also grateful to NSF (grant ATM-9741817) especially J. L. Moyers and the U.S. Department of Energy (grant DE-FG-03-94ER61899) for support. We thank P. Poyner L. Moritz and J. Meyer for assistance with the chamber design and construction J. N. Pitts Jr. J. Stutz E. G. Chapman C. M. Berkowitz and W. C. Keene for helpful discussions and C. W. Spicer for advice on API-MS and for providing the annual denuder."}],"container-title":["Science"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.science.org\/doi\/pdf\/10.1126\/science.279.5347.74","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,1,13]],"date-time":"2024-01-13T04:55:24Z","timestamp":1705121724000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.science.org\/doi\/10.1126\/science.279.5347.74"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[1998,1,2]]},"references-count":44,"journal-issue":{"issue":"5347","published-print":{"date-parts":[[1998,1,2]]}},"alternative-id":["10.1126\/science.279.5347.74"],"URL":"https:\/\/doi.org\/10.1126\/science.279.5347.74","relation":{},"ISSN":["0036-8075","1095-9203"],"issn-type":[{"value":"0036-8075","type":"print"},{"value":"1095-9203","type":"electronic"}],"subject":[],"published":{"date-parts":[[1998,1,2]]}}}