Controlled nitric oxide production via O(1D)  + N2O reactions for use in oxidation flow reactor studies

Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O-3) is photolyzed at 254 nm to produce O(D-1) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O-3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(D-1) + N2O -> 2NO, followed by the reaction NO + O-3 -> NO2 + O-2. Laboratory measurements coupled with photochemical model simulations suggest that O(D-1) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and alpha-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.