OH-Initiated Photooxidation of Gas-Phase Atmospherically Relevant Monoterpene-Derived Organic Nitrates
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Monoterpene-derived organic nitrates (MT-ONs) can influence NO x recycling, secondary organic aerosol, and ozone formation. While OH-initiated photooxidation is considered a sink for MT-ONs, the rate constants and mechanisms remain poorly constrained. We investigate the gas phase photooxidation of three synthetic ONs derived from α-pinene, β-pinene, and d -limonene (3°_ApHN, 1°_BpHN, and 2°_LmHN) through chamber experiments. The photooxidation rate constants for MT-ONs range from (5.7 ± 0.5) to (11.0 ± 1.5) × 10 –11 cm 3 molecule –1 s –1, with corresponding lifetimes of 1.7–3.2 h under ambient OH concentrations. If we consider that products without a nitrooxy group (CHO) represent MT-ONs undergoing photooxidation to form NO x or nitric acid, our measurements suggest that up to 85%, 49%, and 23% of 3°_ApHN, 2°_LmHN, and 1°_BpHN, respectively, contribute to NO x recycling. The prevalence of CHO products is influenced by the molecular structure of MT-ONs and different peroxy radical chemistry. These results are different from prior studies that suggest that photooxidation leads to the complete degradation of MT-ONs into NO x or nitric acid. We propose photooxidation mechanisms, highlighting both OH addition and H abstraction as important processes. This study provides fundamental data to evaluate the contributions of MT-ON photooxidation to NO x recycling and offers new insights into the broader implications of ON chemistry in the atmosphere.
Institutions: Georgia Institute of Technology, Hunan University
Language: English
Subfield: Atmospheric Science
Field: Earth and Planetary Sciences
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: G1515116883, MRI: Acquisition of Instrumentation for Real-Time Molecular Level Measurement of Atmospheric Gas- and Particle-Phase Compounds, CAREER: Integrated Laboratory and Field Studies of Organic Nitrates from BVOC + NO3: Formation, Processing, and Fates, G6123861678, G6388939114, G6671297155, G7121102501, G7694396965, G8040891726
OpenAlex ID: W7117124572