Nocturnal survival of isoprene linked to formation of upper tropospheric organic aerosol.

Isoprene is emitted mainly by terrestrial vegetation and is the dominant volatile organic compound (VOC) in Earth's atmosphere. It plays key roles in determining the oxidizing capacity of the troposphere and the formation of organic aerosol. Daytime infrared satellite observations of isoprene reported here broadly agree with emission inventories, but we found substantial differences in the locations and magnitudes of isoprene hotspots, consistent with a recent study. The corresponding nighttime infrared observations reveal unexpected hotspots over tropical South America, the Congo basin, and Southeast Asia. We used an atmospheric chemistry model to link these nighttime isoprene measurements to low-NOx regions with high biogenic VOC emissions; at sunrise the remaining isoprene can lead to the production of epoxydiols and subsequently to the widespread seasonal production of organic aerosol in the tropical upper troposphere.

Experimental and theoretical study of aqueous cis-pinonic acid photolysis.

Direct aqueous photolysis of cis-pinonic acid (PA; 2-(3-acetyl-2,2-dimethylcyclobutyl)acetic acid; CAS Registry No. 473-72-3) by 280-400 nm radiation was investigated. The photolysis resulted in Norrish type II isomerization of PA leading to 3-isopropenyl-6-oxoheptanoic acid (CAS Registry No. 4436-82-2), also known as limononic acid, as the major product, confirmed by (1)H and (13)C NMR analysis, chemical ionization mass spectrometry, and electrospray ionization mass spectrometry. Several minor products resulting from Norrish type I splitting of PA were also detected. The molar extinction coefficients of aqueous PA were measured and used to calculate the photolysis quantum yield of aqueous PA as 0.5 ± 0.3 (effective average value over the 280-400 nm range). The gas-phase photolysis quantum yield of 0.53 ± 0.06 for PA methyl ester (PAMe; CAS Registry No. 16978-11-3) was also measured for comparison. These results indicate that photolysis of PA is not significantly suppressed by the presence of water. This fact was confirmed by photodissociation dynamics simulations of bare PA and of PAMe hydrated with one or five water molecules using on-the-fly dynamics simulations on a semiempirical potential energy surface. The calculations correctly predicted the occurrence of both Norrish type I and Norrish type II photolysis pathways, both driven by the dynamics on the lowest triplet excited state of PA and PAMe. The rate of removal of PA by direct aqueous photolysis in cloudwater and in aerosol water was calculated for a range of solar zenith angles and compared with rates of other removal processes such as gas-phase oxidation by OH, aqueous-phase oxidation by OH, and gas-phase photolysis. Although the direct photolysis mechanism was not the most significant sink for PA in cloud and fog droplets, direct photolysis can be expected to contribute to removal of PA and more soluble/less volatile biogenic oxidation products in wet particulate matter.