PNNL

Abstract

The gas-phase reactions of nitrate radicals (NO3) with biogenic organic compounds are a major sink for these organics during night-time. These reactions form secondary organic aerosols, including organic nitrates thatcanundergolongrange transport, releasing NOx downwind. We report here studies of the reaction of NO3 with R-pinene at 1 atm in dry syntheticair(relativehumidity~3%)andat298Kusingatmospheric pressurechemicalionizationtriplequadrupolemassspectrometry (APCI-MS) to identify gaseous and particulate products. The emphasis is on the identification of individual organic nitrates in the particle phase that were obtained by passing the product mixture through a denuder to remove gas-phase reactants and products prior to entering the source region of the mass spectrometer. Filter extracts were also analyzed by GCMS and by APCI time-of-flight mass spectrometry (APCI-ToFMS) with methanol as the proton source. In addition to pinonaldehyde and pinonic acid, five organic nitrates were identified in the particles as well as in the gas phase: 3-oxopinane- 2-nitrate, 2-hydroxypinane-3-nitrate, pinonaldehyde-PAN, norpinonaldehyde-PAN, and (3-acetyl-2,2-dimethyl-3-nitrooxycyclobutyl) acetaldehyde. Furthermore, therewasanadditional firstgeneration organic nitrate product tentatively identified as a carbonyl hydroxynitrate with a molecular mass of 229. These studies suggest that a variety of organic nitrates would partition between the gas phase and particles in the atmosphere, and serve as a reservoir for NO.