文献类型：期刊文献

英文题名：The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

作者：Mueller, Jean-Francois[1];Liu, Zhen[2,3];Vinh Son Nguyen[2];Stavrakou, Trissevgeni[1];Harvey, Jeremy N.[2];Peeters, Jozef[2]

机构：[1]Royal Belgian Inst Space Aeron, Atmospher Composit Dept, Ave Circulaire 3, B-1180 Brussels, Belgium;[2]Univ Leuven, Dept Chem, B-3001 Heverlee, Belgium;[3]East China Univ Sci & Technol, State Key Lab Chem Engn, Meilong Rd 130, Shanghai 200237, Peoples R China

年份：2016

卷号：7

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000385630100001)】；

基金：This work received support from project PRODEX ACROSAT of the European Space Agency funded by the Belgian Science Policy Office (Belspo). It was also sponsored in part by Belspo under contract SD/CS/05A (project BIOSOA) in the frame of the Science for Sustainable Development programme, and by the Office of China Postdoctoral Council (No. 20140061) through the International Postdoctoral Exchange Fellowship Program. We acknowledge the free use of merged data sets from NASA tropospheric chemistry campaigns. We thank Maite Bauwens for her assistance with data management.

语种：英文

摘要：Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of similar to 30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions.