| Title: | Suppression of the phenolic SOA formation in the presence of electrolytic inorganic seed |
| Address: | "Department of Environmental Engineering Sciences, University of Florida, Gainesville, FL 32611, USA. Department of Environmental Engineering Sciences, University of Florida, Gainesville, FL 32611, USA. Electronic address: mjang@ufl.edu" |
| DOI: | 10.1016/j.scitotenv.2022.158082 |
| ISSN/ISBN: | 1879-1026 (Electronic) 0048-9697 (Linking) |
| Abstract: | "Phenolic compounds are largely attributed to wildfire gases and rapidly react with atmospheric oxidants to form persistent phenoxy free radicals, which influence atmospheric chemistry and secondary organic aerosol (SOA) formation. In this study, phenol or o-cresol was photochemically oxidized under various conditions (NO(x) levels, humidity, and seed conditions) in an outdoor photochemical reactor. Unexpectedly, SOA growth of both phenols was suppressed in the presence of salted aqueous aerosol compared to non-seed SOA. This discovery is different from the typical SOA formation of aromatic or biogenic hydrocarbons, which show noticeably higher SOA yields via organic aqueous reactions. Phenol, o-cresol, and their phenolic products (e.g., catechols) are absorbed in aqueous aerosol and form phenoxy radicals via heterogeneous reactions under sunlight. The resulting phenoxy radicals are redistributed between the gas and particle phases. Gaseous phenoxy radicals quickly react with ozone to form phenyl peroxide radicals and regenerated through a NO(x) cycle to retard phenol oxidation and SOA formation. The explicit oxidation mechanisms of phenol or o-cresol in the absence of aqueous phase were derived including the Master Chemical Mechanism (MCM v3.3.1) and the path for peroxy radical adducts originating from the addition of an OH radical to phenols to form low volatility products (e.g., multi-hydroxy aromatics). The resulting gas mechanisms of phenol or o-cresol were, then, applied to the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model to predict SOA formation via multiphase partitioning of organics and aerosol-phase oligomerization. The model well simulated chamber-generated phenolic SOA in absence of wet-inorganic seed, but significantly overestimated SOA mass in presence of wet seed. This study suggests that heterogeneous chemistry to form phenoxy radicals needs to be included to improve SOA prediction from phenols. The suppression of atmospheric oxidation due to phenoxy radicals in wet inorganic aerosol can explain the low SOA formation during wildfire episodes" |
| Keywords: | Aerosols/analysis *Air Pollutants/chemistry Catechols Cresols Free Radicals Oxidants Oxidation-Reduction *Ozone Peroxides Phenol Cresol Photooxidation Soa; |
| Notes: | "MedlineChoi, Jiwon Jang, Myoseon eng Netherlands 2022/08/20 Sci Total Environ. 2022 Dec 10; 851(Pt 1):158082. doi: 10.1016/j.scitotenv.2022.158082. Epub 2022 Aug 17" |
