Diurnal variations in oxygen and nitrogen isotopes of atmospheric nitrogen dioxide and nitrate: implications for tracing NOx oxidation pathways and emission sources - INSU - Institut national des sciences de l'Univers
Article Dans Une Revue Atmospheric Chemistry and Physics Année : 2024

Diurnal variations in oxygen and nitrogen isotopes of atmospheric nitrogen dioxide and nitrate: implications for tracing NOx oxidation pathways and emission sources

Résumé

The oxygen (∆17O) and nitrogen (δ15N) isotopic compositions of atmospheric nitrate (NO− 3 ) are widely used as tracers of its formation pathways, precursor (nitrogen oxides (NOx ) ≡ nitric oxide (NO) + nitrogen dioxide (NO2)) emission sources, and physico-chemical processing. However, the lack of obser- vations on the multi-isotopic composition of NO2 perpetuates significant uncertainties regarding the quantitative links between the isotopic composition of NOx and NO− 3 , which ultimately may bias inferences about NO− 3 formation processes and the distribution of sources, particularly in winter urban atmospheres. We report here on the first simultaneous atmospheric observations of ∆17O and δ15N in NO2 (n = 16) and NO− 3 (n = 14). The measurements were carried out at sub-daily (∼ 3 h) resolution over 2 non-consecutive days in an Alpine city in February 2021. A strong diurnal signal is observed in both NO2 and NO− 3 multi-isotopic composition. ∆17O of NO2 and NO− 3 ranges from 19.6 ‰ to 40.8 ‰ and from 18.3 ‰ to 28.1 ‰, respectively. During the day and night, the variability in ∆17O(NO2) is mainly driven by the oxidation of NO by ozone, with a substan- tial contribution from peroxy radicals in the morning. NO− 3 mass balance equations, constrained by observed ∆17O(NO2), suggest that during the first day of sampling, most of the NO− 3 was formed locally from the oxi- dation of NO2 by hydroxyl radicals by day and via heterogeneous hydrolysis of dinitrogen pentoxide at night. For the second day, calculated and observed ∆17O(NO− 3 ) do not match, particularly daytime values; the possible effects on ∆17O(NO− 3 ) of a Saharan dust event that occurred during this sampling period and of winter boundary layer dynamics are discussed. δ15N of NO2 and NO− 3 ranges from −10.0 ‰ to 19.7 ‰ and from −4.2 ‰ to 14.9 ‰, respectively. Consistent with theoretical predictions of N isotope fractionation, the observed variability in δ15N(NO2) is explained by significant post-emission equilibrium N fractionation. After accounting for this effect, vehicle exhaust is found to be the primary source of NOx emissions at the sampling site. δ15N(NO− 3 ) is closely linked to δ15N(NO2) variability, bringing further support to relatively fast and local NOx processing. Uncertainties in current N fractionation factors during NO2 to NO− 3 conversion are underlined. Overall, this detailed investigation highlights the potential and necessity of simultaneously using ∆17O and δ15N in NO2 and NO− 3 in order to better constrain quantitative inferences about the sources and formation chemistry of NO− 3 in urban environments in winter.
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insu-04095457 , version 1 (11-05-2023)
insu-04095457 , version 2 (31-01-2024)

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Sarah Albertin, Joël Savarino, Slimane Bekki, Albane Barbero, Roberto Grilli, et al.. Diurnal variations in oxygen and nitrogen isotopes of atmospheric nitrogen dioxide and nitrate: implications for tracing NOx oxidation pathways and emission sources. Atmospheric Chemistry and Physics, 2024, 24 (2), pp.1361-1388. ⟨10.5194/acp-24-1361-2024⟩. ⟨insu-04095457v2⟩
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