Abstract
Abstract. Nitrogen oxides, classified as NOx (nitric oxide (NO) + nitrogen dioxide (NO2)) and NOy (NOx+ NO3, N2O5 HNO3, + HNO4+ HONO + Peroxyacetyl nitrate (PAN) + organic nitrates + any oxidized N compound), are important trace gases in the troposphere, which play an important role in the formation of ozone, particulate matter (PM), and secondary organic aerosols (SOA). There remain many uncertainties in the origin and fate of atmospheric N compounds including the understanding of NOy cycling, NOx emission budgets, unresolved issues within the heterogeneous uptake coefficients of N2O5, and the formation of organic nitrates in urban forests, to name a few. A potential tool to resolve some of these uncertainties are using natural abundance N isotopes in NOy compounds. Here we have developed a photochemical mechanism used to simulate tropospheric photochemistry to include 15N compounds and reactions as a means to simulate δ15N values in NOy compounds. The 16 N compounds and 96 reactions involving N used in the Regional Atmospheric Chemistry Mechanism (RACM) were replicated using 15N in a new mechanism called iNRACM. The 192 N reactions in iNRACM were tested to see if isotope effects were relevant with respect to significantly changing the δ15N values (±1 ‰) of NOx, HONO, and/or HNO3. The isotope fractionation factors (α) for relevant reactions were assigned based on recent experimental or calculated values. Each relevant reaction in the iNRACM mechanism was tested individually and in concert in order to assess the controlling reactions. The controlling reactions and their diurnal importance are discussed. A comparison between iNRACM predictions and observed δ15N NO3- in particulate matter from Tucson, Arizona, suggests the model, and isotope fractionation factors incorporated into it, are accurately capturing the isotope effects occurring during the photochemistry of NOy. The implication is that measurements of δ15N in NOy compounds may be a new way of tracing in situ N chemistry and a means of assessing NOx emission budgets.
Highlights
Nitrogen oxides are an integral part of atmospheric chemistry, controlling the oxidation state of the troposphere, influencing aerosol formation, altering the pH of rainwater, and facilitating the movement of nitrogen through the N cycle
The second is the examination of the relevant isotope effects occurring during nighttime chemistry (EIE and kinetic isotope effects (KIEs)) and their effect on NOx, HONO, and HNO3 δ15N values
This tests how changes in photochemical oxidation pathways result in differences in the δ15N values of NOx, HONO, and HNO3
Summary
Nitrogen oxides are an integral part of atmospheric chemistry, controlling the oxidation state of the troposphere, influencing aerosol formation, altering the pH of rainwater, and facilitating the movement of nitrogen through the N cycle. NOx facilitates the cleansing of the atmosphere through the production of O3 and OHx (OH + HO2), which together define the troposphere’s oxidation state (Bloss et al, 2005; Lelieveld et al, 2008; Prinn, 2003) These oxidants play an important role in the formation of particulate matter (PM) (Bauer et al, 2007; Pye et al, 2010), forming secondary organic aerosols (SOA) via VOC oxidation (Hoyle et al, 2011; Shrivastava et al, 2017). Understanding NOy sources and their chemistry is important for an array of scientific disciplines and evaluating their social, economic, and cultural impact on the environment
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