| Title: | Radical oxidation of methyl vinyl ketone and methacrolein in aqueous droplets: Characterization of organosulfates and atmospheric implications |
| Author(s): | Wach P; Spolnik G; Rudzinski KJ; Skotak K; Claeys M; Danikiewicz W; Szmigielski R; |
| Address: | "Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland. Electronic address: pwach@ichf.edu.pl. Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland. Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland. Institute of Environmental Protection-National Research Institute, ul. Krucza 5/11D, 00-548 Warszawa, Poland. Department of Pharmaceutical Sciences, University of Antwerp, BE 2610 Antwerp, Belgium. Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland. Electronic address: ralf@ichf.edu.pl" |
| DOI: | 10.1016/j.chemosphere.2018.09.026 |
| ISSN/ISBN: | 1879-1298 (Electronic) 0045-6535 (Linking) |
| Abstract: | "In-cloud processing of volatile organic compounds is one of the significant routes leading to secondary organic aerosol (SOA) in the lower troposphere. In this study, we demonstrate that two atmospherically relevant alpha,beta-unsaturated carbonyls, i.e., but-3-en-2-on (methyl vinyl ketone, MVK) and 2-methylopropenal (methacrolein, MACR), undergo sulfate radical-induced transformations in dilute aqueous systems under photochemical conditions to form organosulfates previously identified in ambient aerosols and SOA generated in smog chambers. The photooxidation was performed under sun irradiation in unbuffered aqueous solutions containing carbonyl precursors at a concentration of 0.2?ª+mmol and peroxydisulfate as a source of sulfate radicals (SO(4)(-)) at a concentration of 0.95?ª+mmol. UV-vis analysis of solutions showed the fast decay of unsaturated carbonyl precursors in the presence of sulfate radicals. The observation confirms the capacity of sulfate radicals to transform the organic compounds into SOA components in atmospheric waters. Detailed interpretation of high-resolution negative ion electrospray ionization tandem mass spectra allowed to assign molecular structures to multiple aqueous organosulfate products, including an abundant isoprene-derived organosulfate C(4)H(8)SO(7) detected at m/z 199. The results highlight the solar aqueous-phase reactions as a potentially significant route for biogenic SOA production in clouds at locations where isoprene oxidation occurs. A recent modelling study suggests that such processes could likely contribute to 20-30?ª+Tg?ª+year(-1) production of SOA, referred to as aqSOA, which is a non-negligible addition to the still underestimated budget of atmospheric aerosol" |
| Keywords: | Acrolein/*analogs & derivatives/chemistry Air Pollutants/analysis/*chemistry Butanones/*chemistry Oxidation-Reduction Water/analysis/*chemistry Aqueous photochemistry Methacrolein Methyl vinyl ketone Organosulfates Secondary organic aerosol Sulfate radica; |
| Notes: | "MedlineWach, Paulina Spolnik, Grzegorz Rudzinski, Krzysztof J Skotak, Krzysztof Claeys, Magda Danikiewicz, Witold Szmigielski, Rafal eng England 2018/09/25 Chemosphere. 2019 Jan; 214:1-9. doi: 10.1016/j.chemosphere.2018.09.026. Epub 2018 Sep 7" |
