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The aqueous phase yield of alkyl nitrates from ROO + NO: Implications for photochemical production in seawater
Author(s) -
Dahl Elizabeth E.,
Saltzman Eric S.,
de Bruyn Warren J.
Publication year - 2003
Publication title -
geophysical research letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.007
H-Index - 273
eISSN - 1944-8007
pISSN - 0094-8276
DOI - 10.1029/2002gl016811
Subject(s) - alkyl , seawater , nitrate , yield (engineering) , aqueous solution , branching (polymer chemistry) , chemistry , aqueous two phase system , troposphere , irradiation , environmental chemistry , inorganic chemistry , photochemistry , organic chemistry , materials science , oceanography , climatology , geology , physics , nuclear physics , metallurgy
Alkyl nitrates have been observed in remote oceanic regions of the troposphere and in the surface ocean. The mechanism for their production in the oceans is not known. A likely source is the reaction of ROO + NO (where R is an alkyl group). Steady‐state laboratory experiments show that alkyl nitrates are produced in the aqueous phase via this reaction, with branching ratios of 0.23 ± 0.04, 0.67 ± 0.03, and 0.71 ± 0.04 for methyl, ethyl, and propyl nitrate respectively. The branching ratios in aqueous solution are significantly higher than in the gas phase. Irradiation of surface seawaters yield rates of alkyl nitrate production on the order of 10 −18 mol cm −3 s −1 , suggesting that the reaction of ROO and NO is an important source of alkyl nitrates in seawater.