Decreases in Epoxide-Driven Secondary Organic Aerosol Production under Highly Acidic Conditions: The Importance of Acid-Base Equilibria.

Isoprene has the highest atmospheric emissions of any nonmethane hydrocarbon, and isoprene epoxydiols (IEPOX) are well-established oxidation products and the primary contributors forming isoprene-derived secondary organic aerosol (SOA). Highly acidic particles (pH 0-3) widespread across the lower troposphere enable acid-driven multiphase chemistry of IEPOX, such as epoxide ring-opening reactions forming methyltetrol sulfates through nucleophilic attack of sulfate (SO). Herein, we systematically demonstrate an unexpected decrease in SOA formation from IEPOX on highly acidic particles (pH < 1).

Acidity-Dependent Atmospheric Organosulfate Structures and Spectra: Exploration of Protonation State Effects via Raman and Infrared Spectroscopies Combined with Density Functional Theory.

Organosulfates formed from heterogeneous reactions of organic-derived oxidation products with sulfate ions can account for >15% of secondary organic aerosol (SOA) mass, primarily in submicron particles with long atmospheric lifetimes. However, fundamental understanding of organosulfate molecular structures is limited, particularly at atmospherically relevant acidities (pH = 0-6). Herein, for 2-methyltetrol sulfates (2-MTSs), an important group of isoprene-derived organosulfates, protonation state and vibrational modes were studied using Raman and infrared spectroscopy, as well as density functional theory (DFT) calculations of vibrational spectra for neutral (RO-SOH) and anionic/deprotonated (RO-SO) structures.

Impact of Environmental Conditions on Secondary Organic Aerosol Production from Photosensitized Humic Acid.

Recent studies have shown the potential of the photosensitizer chemistry of humic acid, as a proxy for humic-like substances in atmospheric aerosols, to contribute to secondary organic aerosol mass. The mechanism requires particle-phase humic acid to absorb solar radiation and become photoexcited, then directly or indirectly oxidize a volatile organic compound (VOC), resulting in a lower volatility product in the particle phase. We performed experiments in a photochemical chamber, with aerosol-phase humic acid as the photosensitizer and limonene as the VOC.