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ABSTRACT: Isoprene, the most abundant nonmethane volatile organic compound in the atmosphere, undergoes photochemical reactions with hydroxyl radical (•OH), a major sink for isoprene, leading to the formation of secondary organic aerosol (SOA). Using a Vocus Chemical Ionization Mass Spectrometer with ammonium-adduct ions (Vocus NH4+ CIMS), this study used the positive ion mode to quantify the yields and time-dependent reactiveuptake of oxidized volatile organic compounds (OVOCs) produced from •OH-initiated oxidation of isoprene under dry conditions. Molar gas-phase yields of key oxidation products were constrained using sensitivities derived from a voltage scan of the front and back end of the Vocus ion−molecule reactor region. Carefully designed chamber experiments measured uptake coefficients (γ) for key isoprene-derived oxidation products onto acidic sulfate particles. The γ values for both C5H10O3 isomers (IEPOX/ISOPOOH) and C5H8O4, another epoxy species from isoprene photo-oxidation, rapidly decreased as the SOA coating thickness increased, demonstrating a self-limiting effect. Despite ISOPOOH/IEPOX contributing around 80% to total reactive uptake, other oxidation products from isoprene photooxidation were estimated to contribute 20% of the total SOA formation. These findings highlight the importance for future models to consider the self-limiting effects of ISOPOOH/IEPOX and SOA formation through non-IEPOX pathways.
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Identifying a Missing Link: Confirmation of the Structure and Origin of 4-hydroperoxy-3-methylbut-2-enal (4-HPALD) with an Authentic Standard
Isoprene (C5H8) is the largest non-methane volatile organic compound emitted into the atmosphere. Isoprene reacts rapidly with ambient hydroxyl radicals (OH) and subsequent addition of O2 results in the formation alkyl peroxy (RO2) radicals. The fate of the initially formed RO2 radicals has been the focus of continuing theoretical and experimental research. Under pristine conditions where bimolecular reactions of RO2 are limited, the thermodynamically favored RO2 undergoes an intramolecular H-shift followed by reaction with O2 and elimination of HO2 to yield 4-hydroperoxy aldehyde (4-HPALD, C5H8O3), predicted to account for up to 13% of first-generation isoprene photochemical oxidation products. Mass spectrometric evidence has been reported for 4-HPALD, but lack of an authentic standard has precluded definitive confirmation of both the structure of 4-HPALD and its origin as a first-generation product of OH oxidation of isoprene. We report the synthesis and characterization of 4-HPALD and establish that it is a major product of isoprene oxidation. Synthetic 4-HPALD is isolated as the peroxyhemiacetal. As expected for the 4-hydroperoxy aldehyde, 1H NMR spectra show no evidence for equilibration with the carbonyl form, even in protic solvents, and gas-phase chemical analysis by CIMS also shows only a single form. OH oxidation of isoprene in an oxidation flow reactor coupled to an ion mobility source with an HR-CIMS detector unequivocally demonstrates 4-HPALD (and likely also 1-HPALD) as isoprene oxidation products. Although HPALDs have been discounted as significant contributors to SOA, oxidation of 4-HPALD in a potential aerosol mass (PAM) reactor in the presence of ozone and OH indicates 4-HPALD rapidly undergoes autooxidation reactions forming low-volatility particulate products. We have confirmed highly oxygenated compounds with compositions C5H8O6 and C5H10O6 likely from OH oxidation, and C5H10O7 and C5H10O8 compounds likely products of ozonolysis. The PAM oxidation experiment further demonstrates that the highly oxygenated, low-volatility products efficiently nucleate particles.
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- Award ID(s):
- 2001027
- PAR ID:
- 10392022
- Date Published:
- Journal Name:
- AAAR 40th Annual Conference
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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