The aqueous phase yield of alkyl nitrates from ROO+NO: Implications for photochemical production in seawater

[1] 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.