Unexpected quenching effect on new particle formation from the atmospheric reaction of methanol with SO3

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Liu , L , Zhong , J , Vehkamäki , H , Kurten , T , Du , L , Zhang , X , Francisco , J S & Zeng , X C 2019 , ' Unexpected quenching effect on new particle formation from the atmospheric reaction of methanol with SO3 ' , Proceedings of the National Academy of Sciences of the United States of America , vol. 116 , no. 50 , pp. 24966-24971 . https://doi.org/10.1073/pnas.1915459116

Title: Unexpected quenching effect on new particle formation from the atmospheric reaction of methanol with SO3
Author: Liu, Ling; Zhong, Jie; Vehkamäki, Hanna; Kurten, Theo; Du, Lin; Zhang, Xiuhui; Francisco, Joseph S.; Zeng, Xiao Cheng
Contributor: University of Helsinki, Institute for Atmospheric and Earth System Research (INAR)
University of Helsinki, Department of Chemistry
Date: 2019-12-10
Language: eng
Number of pages: 6
Belongs to series: Proceedings of the National Academy of Sciences of the United States of America
ISSN: 0027-8424
URI: http://hdl.handle.net/10138/324863
Abstract: Despite the high abundance in the atmosphere, alcohols in general and methanol in particular are believed to play a small role in atmospheric new particle formation (NPF) largely due to the weak binding abilities of alcohols with the major nucleation precursors, e.g., sulfuric acid (SA) and dimethylamine (DMA). Herein, we identify a catalytic reaction that was previously overlooked, namely, the reaction between methanol and SO3, catalyzed by SA, DMA, or water. We found that alcohols can have unexpected quenching effects on the NPF process, particularly in dry and highly polluted regions with high concentrations of alcohols. Specifically, the catalytic reaction between methanol and SO3 can convert methanol into a less-volatile species-methyl hydrogen sulfate (MHS). The latter was initially thought to be a good nucleation agent for NPF. However, our simulation results suggest that the formation of MHS consumes an appreciable amount of atmospheric SO3, disfavoring further reactions of SO3 with H2O. Indeed, we found that MHS formation can cause a reduction of SA concentration up to 87%, whereas the nucleation ability of MHS toward new particles is not as good as that of SA. Hence, a high abundance of methanol in the atmosphere can lower the particle nucleation rate by as much as two orders of magnitude. Such a quenching effect suggests that the recently identified catalytic reactions between alcohols and SO3 need to be considered in atmospheric modeling in order to predict SA concentration from SO2, while also account for their potentially negative effect on NPF.
Subject: atmospheric aerosol
alcohols
SO3
catalytic reactions
nucleation precursors
VOLATILE ORGANIC-COMPOUNDS
SULFURIC-ACID
DIMETHYL SULFATE
HYDROGEN SULFATE
INTERMEDIATE
KINETICS
CLUSTERS
NANOPARTICLES
TROPOSPHERE
NUCLEATION
116 Chemical sciences
114 Physical sciences
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