Photolysis of Gas-Phase Atmospherically Relevant Monoterpene-Derived Organic Nitrates

Organic nitrates (ONs) can impact spatial distribution of reactive nitrogen species and ozone formation in the atmosphere. While photolysis of ONs is known to result in the release of NO₂ back to the atmosphere, the photolysis rate constants and mechanisms of monoterpene-derived ONs (MT-ONs) have not been well constrained. We investigated the gas-phase photolysis of three synthetic ONs derived from α-pinene, β-pinene, and d-limonene through chamber experiments. The measured photolysis rate constants ranged from (0.55 ± 0.10) × 10^-5 to (2.3 ± 0.80) × 10^-5 s^-1 under chamber black lights. When extrapolated to solar spectral photon flux at a solar zenith angle of 28.14° in summer, the photolysis rate constants were in the range of (4.1 ± 1.4) × 10^-5 to (14 ± 6.7) × 10^-5 s^-1 (corresponding to lifetimes of 2.0 ± 0.96 to 6.8 ± 2.4 h) and (1.7 ± 0.60) × 10^-5 to (8.3 ± 4.0) ×10^-5 s^-1 (3.3 ± 1.6 to 17 ± 6.0 h lifetimes) by using wavelength-dependent and average quantum yields, respectively. Photolysis mechanisms were proposed based on major products detected during photolysis. A zero-dimensional box model was further employed to simulate the photolysis of α-pinene-derived ON under ambient conditions. We found that more than 99% of α-pinene-derived ON can be converted to inorganic nitrogen within 12 h of irradiation and ozone was formed correspondingly. Together, these findings show that photolysis is an important atmospheric sink for MT-ONs and highlight their role in NO recycling and ozone chemistry.