General Mechanism for Sulfate Radical Addition to Olefinic Volatile Organic Compounds in Secondary Organic Aerosol
- 21 January 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Environmental Science & Technology
- Vol. 55 (3), 1456-1465
- https://doi.org/10.1021/acs.est.0c05256
Abstract
Previous laboratory studies have suggested that sulfate radical addition to olefinic biogenic volatile organic compounds (BVOCs) is a potential formation mechanism for some organosulfates detected in ambient secondary organic aerosol (SOA). However, these studies propose conflicting reaction products, possibly because laboratory dissolved oxygen levels did not accurately reflect atmospheric conditions. Additionally, these studies used analytical methods that could not definitively identify and quantify the structurally specific products. Here, we describe a method that allows for the study of the reaction of sulfate radicals and several olefinic precursors, including allyl alcohol (AA), methyl vinyl ketone (MVK), 2-methyl-3-buten-2-ol (MBO), and methacrolein (MA), with careful control of dissolved oxygen levels and using the isomer-specific nuclear magnetic resonance (NMR) method to definitively identify and quantify the reaction products. Specific mechanisms for each olefinic precursor were developed, as well as a generalized mechanism that can be used to predict the sulfate radical reaction pathways for any olefin. The product yield results indicate that this mechanism is dominated by carbon backbone fragmentation pathways: 61, 83, 79, and 100% for AA, MVK, MBO, and MA, respectively. Several of the observed organosulfate products have also been detected in field observations of SOA, which indicates the potential relevance of this mechanism in the atmosphere.Keywords
Funding Information
- Division of Biological Infrastructure (1427949)
- Division of Atmospheric and Geospace Sciences (1559319, 1841019)
This publication has 39 references indexed in Scilit:
- PM2.5 chemistry, organosulfates, and secondary organic aerosol during the 2017 Lake Michigan Ozone StudyAtmospheric Environment, 2020
- Organosulfates in Atlanta, Georgia: anthropogenic influences on biogenic secondary organic aerosol formationAtmospheric Chemistry and Physics, 2019
- Source apportionment of organic carbon in Centreville, AL using organosulfates in organic tracer-based positive matrix factorizationAtmospheric Environment, 2018
- Qualitative and quantitative analysis of atmospheric organosulfates in Centreville, AlabamaAtmospheric Chemistry and Physics, 2017
- “What We Breathe Impacts Our Health: Improving Understanding of the Link between Air Pollution and Health”Published by American Chemical Society (ACS) ,2016
- Contribution of Organosulfur Compounds to Organic Aerosol MassEnvironmental Science & Technology, 2012
- Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphereAtmospheric Environment, 2008
- Health Effects of Fine Particulate Air Pollution: Lines that ConnectJournal of the Air & Waste Management Association, 2006
- Organic aerosol and global climate modelling: a reviewAtmospheric Chemistry and Physics, 2005
- An Association between Air Pollution and Mortality in Six U.S. CitiesThe New England Journal of Medicine, 1993