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 (SO42-). Herein, we systematically demonstrate an unexpected decrease in SOA formation from IEPOX on highly acidic particles (pH < 1). While IEPOX-SOA formation is commonly assumed to increase at low pH when more [H+] is available to protonate epoxides, we observe maximum SOA formation at pH 1 and less SOA formation at pH 0.0 and 0.4. This is attributed to limited availability of SO42- at pH values below the acid dissociation constant (pKa) of SO42- and bisulfate (HSO4-). The nucleophilicity of HSO4- is 100× lower than SO42-, decreasing SOA formation and shifting particulate products from low-volatility organosulfates to higher-volatility polyols. Current model parameterizations predicting SOA yields for IEPOX-SOA do not properly account for the SO42-/HSO4- equilibrium, leading to overpredictions of SOA formation at low pH. Accounting for this underexplored acidity-dependent behavior is critical for accurately predicting SOA concentrations and resolving SOA impacts on air quality.

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-SO3H) and anionic/deprotonated (RO-SO3-) structures. The calculated sulfate group vibrations differ for the two protonation states due to their different sulfur-oxygen bond orders (1 or 2 versus 12/3 for the neutral and deprotonated forms, respectively). Only vibrations at 1060 and 1041 cm-1, which are associated with symmetric S-O stretches of the 2-MTS anion, were observed experimentally with Raman, while sulfate group vibrations for the neutral form (∼900, 1200, and 1400 cm-1) were not observed. Additional calculations of organosulfates formed from other SOA-precursor gases (α-pinene, ß-caryophyllene, and toluene) identified similar symmetric vibrations between 1000 and 1100 cm-1 for RO-SO3-, consistent with corresponding organosulfates formed during laboratory experiments. These results suggest that organosulfates are primarily deprotonated at atmospheric pH values, which have further implications for aerosol acidity, heterogeneous reactions, and continuing chemistry in atmospheric aerosols.

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. In the presence of 26 ppb limonene and under atmospherically relevant UV-visible irradiation levels, there is no significant change in particle diameter. Calculations show that SOA production via this pathway is highly sensitive to VOC precursor concentrations. Under the assumption that HULIS is equally or less reactive than the humic acid used in these experiments, the results suggest that the photosensitizer chemistry of HULIS in ambient atmospheric aerosols is unlikely to be a significant source of secondary organic aerosol mass.