Abstract
Abstract. Oxidation flow reactors (OFRs) are an emerging tool for studying the formation and oxidative aging of organic aerosols and other applications. The majority of OFR studies to date have involved the generation of the hydroxyl radical (OH) to mimic daytime oxidative aging processes. In contrast, the use of the nitrate radical (NO3) in modern OFRs to mimic nighttime oxidative aging processes has been limited due to the complexity of conventional techniques that are used to generate NO3. Here, we present a new method that uses a laminar flow reactor (LFR) to continuously generate dinitrogen pentoxide (N2O5) in the gas phase at room temperature from the NO2 + O3 and NO2 + NO3 reactions. The N2O5 is then injected into a dark Potential Aerosol Mass (PAM) OFR and decomposes to generate NO3; hereafter, this method is referred to as “OFR-iN2O5” (where “i” stands for “injected”). To assess the applicability of the OFR-iN2O5 method towards different chemical systems, we present experimental and model characterization of the integrated NO3 exposure, NO3:O3, NO2:NO3, and NO2:O2 as a function of LFR and OFR conditions. These parameters were used to investigate the fate of representative organic peroxy radicals (RO2) and aromatic alkyl radicals generated from volatile organic compound (VOC) + NO3 reactions, and VOCs that are reactive towards both O3 and NO3. Finally, we demonstrate the OFR-iN2O5 method by generating and characterizing secondary organic aerosol from the β-pinene + NO3 reaction.
Highlights
The importance of nitrate radicals (NO3) as a nighttime oxidant is well established (Wayne et al, 1991; Brown and Stutz, 2012; Ng et al, 2017)
Atmospheric organic compounds that are reactive towards NO3 include isoprene and monoterpenes that are emitted from biogenic sources, phenols and methoxyphenols emitted from biomass burning, and polycyclic aromatic hydrocarbons (PAHs) emitted from combustion processes
We present experimental and model characterization of Oxidation flow reactors (OFRs)-iN2O5 as a function of laminar flow reactor (LFR) and OFR conditions, and we demonstrate the application of OFR-iN2O5 to generate and characterize secondary organic aerosol (SOA) from the β-pinene + NO3 reaction
Summary
The importance of nitrate radicals (NO3) as a nighttime oxidant is well established (Wayne et al, 1991; Brown and Stutz, 2012; Ng et al, 2017). Atmospheric organic compounds that are reactive towards NO3 include isoprene and monoterpenes that are emitted from biogenic sources (including urban vegetation), phenols and methoxyphenols emitted from biomass burning, and polycyclic aromatic hydrocarbons (PAHs) emitted from combustion processes. Lambe et al.: N2O5 and NO3 generation in a coupled LFR–OFR generates oxygenated volatile organic compounds (OVOCs) and/or secondary organic aerosol (SOA), including particulate organic nitrates or nitroaromatics. The importance of these sources and processes are likely to continue to increase for the foreseeable future due to climate change (Melaas et al, 2016; Short, 2017)
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