The reactive partitioning of cis and trans β-IEPOX was investigated on hydrated inorganic seed particles, without the addition of acids. No organic aerosol (OA) formation was observed on dry ammonium sulfate (AS); however, prompt and efficient OA growth was observed for the cis and trans β-IEPOX on AS seeds at liquid water contents of 40–75% of the total particle mass. OA formation from IEPOX is a kinetically limited process, thus the OA growth continues if there is a reservoir of gas-phase IEPOX. There appears to be no differences, within error, in the OA growth or composition attributable to the cis / trans isomeric structures. Reactive uptake of IEPOX onto hydrated AS seeds with added base (NaOH) also produced high OA loadings, suggesting the pH dependence for OA formation from IEPOX is weak for AS particles. No OA formation, after particle drying, was observed on seed particles where Na+ was substituted for NH4+. The Henry's Law partitioning of IEPOX was measured on NaCl particles (ionic strength ~9 M) to be 3 × 107 M atm−1 (−50 / +100%). A small quantity of OA was produced when NH4+ was present in the particles, but the chloride (Cl-) anion was substituted for sulfate (SO42-), possibly suggesting differences in nucleophilic strength of the anions. Online time-of-flight aerosol mass spectrometry and offline filter analysis provide evidence of oxygenated hydrocarbons, organosulfates, and amines in the particle organic composition. The results are consistent with weak correlations between IEPOX-derived OA and particle acidity or liquid water observed in field studies, as the chemical system is nucleophile-limited and not limited in water or catalyst activity.
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Long-term observational constraints of organic aerosol dependence on inorganic species in the southeast US
Abstract. Organic aerosol (OA), with a large biogenic fraction in the summertime southeast US, adversely impacts air quality and human health. Stringent airquality controls have recently reduced anthropogenic pollutants including sulfate, whose impact on OA remains unclear. Three filter measurementnetworks provide long-term constraints on the sensitivity of OA to changes in inorganic species, including sulfate and ammonia. The 2000–2013summertime OA decreases by 1.7 % yr−1–1.9 % yr−1 with little month-to-month variability, while sulfatedeclines rapidly with significant monthly difference in the early 2000s. In contrast, modeled OA from a chemical-transport model (GEOS-Chem) decreasesby 4.9 % yr−1 with much larger monthly variability, largely due to the predominant role of acid-catalyzed reactive uptake ofepoxydiols (IEPOX) onto sulfate. The overestimated modeled OA dependence on sulfate can be improved by implementing a coating effect and assumingconstant aerosol acidity, suggesting the needs to revisit IEPOX reactive uptake in current models. Our work highlights the importance of secondaryOA formation pathways that are weakly dependent on inorganic aerosol in a region that is heavily influenced by both biogenic and anthropogenicemissions.
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- Award ID(s):
- 1822664
- PAR ID:
- 10288741
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 20
- Issue:
- 21
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 13091 to 13107
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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