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Abstract. We present a novel photolytic source of gas-phase NO3 suitable for use in atmospheric chemistry studies that has several advantages over traditional sources that utilize NO2 + O3 reactions and/or thermal dissociation of dinitrogen pentoxide (N2O5). The method generates NO3 via irradiation of aerated aqueous solutions of ceric ammonium nitrate (CAN, (NH4)2Ce(NO3)6) and nitric acid (HNO3) or sodium nitrate (NaNO3). We present experimental and model characterization of the NO3 formation potential of irradiated CAN / HNO3 and CAN / NaNO3 mixtures containing [CAN] = 10−3 to 1.0 M, [HNO3] = 1.0 to 6.0 M, [NaNO3] = 1.0 to 4.8 M, photon fluxes (I) ranging from 6.9 × 1014 to 1.0 × 1016 photons cm−2 s−1, and irradiation wavelengths ranging from 254 to 421 nm. NO3 mixing ratios ranging from parts per billion to parts per million by volume were achieved using this method. At the CAN solubility limit, maximum [NO3] was achieved using [HNO3] ≈ 3.0 to 6.0 M and UVA radiation (λmax = 369 nm) in CAN / HNO3 mixtures or [NaNO3] ≥ 1.0 M and UVC radiation (λmax = 254 nm) in CAN / NaNO3 mixtures. Other reactive nitrogen (NO2, N2O4, N2O5, N2O6, HNO2, HNO3, HNO4) and reactive oxygen (HO2, H2O2) species obtained from the irradiation of ceric nitrate mixtures were measured using a NOx analyzer and an iodide-adduct high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS). To assess the applicability of the method for studies of NO3-initiated oxidative aging processes, we generated and measured the chemical composition of oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) from the β-pinene + NO3 reaction using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the HR-ToF-CIMS.
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Molecular Insights into Chemical Reactions at Aqueous Aerosol Interfaces
Atmospheric aerosols facilitate reactions between ambient gases and dissolved species. Here, we review our efforts to interrogate the uptake of these gases and the mechanisms of their reactions both theoretically and experimentally. We highlight the fascinating behavior of N2O5 in solutions ranging from pure water to complex mixtures, chosen because its aerosol-mediated reactions significantly impact global ozone, hydroxyl, and methane concentrations. As a hydrophobic, weakly soluble, and highly reactive species, N2O5 is a sensitive probe of the chemical and physical properties of aerosol interfaces. We employ contemporary theory to disentangle the fate of N2O5 as it approaches pure and salty water, starting with adsorption and ending with hydrolysis to HNO3, chlorination to ClNO2, or evaporation. Flow reactor and gas-liquid scattering experiments probe even greater complexity as added ions, organic molecules, and surfactants alter the interfacial composition and reaction rates. Together, we reveal a new perspective on multiphase chemistry in the atmosphere.
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- Award ID(s):
- 1801971
- PAR ID:
- 10555722
- Publisher / Repository:
- Annual Review of Physical Chemistry
- Date Published:
- Journal Name:
- Annual Review of Physical Chemistry
- Volume:
- 75
- Issue:
- 1
- ISSN:
- 0066-426X
- Page Range / eLocation ID:
- 111 to 135
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1146/annurev-physchem-083122-121620
