Simulation of the diurnal variations of the oxygen isotope anomaly (Δ17O) of reactive atmospheric species
1Météo-France/CNRS, CNRM/GAME URA 1357, CEN, 38400 St Martin d'Hères, France
2Air Chemistry Department, Max-Planck Institute of Chemistry, P.O. Box 3060, 55020 Mainz, Germany
3CNRS/Université Joseph Fourier Grenoble 1, LGGE UMR 5183, St Martin d'Hères, France
Abstract. The isotope anomaly (Δ17O) of secondary atmospheric species such as nitrate (NO3−) or hydrogen peroxyde (H2O2) has potential to provide useful constrains on their formation pathways. Indeed, the Δ17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero Δ17O in the atmosphere. Interpreting variations of Δ17O in secondary species requires an in-depth understanding of the Δ17O of their precursors taking into account non-linear chemical regimes operating under various environmental settings.
We present results from numerical simulations carried out using the atmospheric chemistry box model (CAABA/MECCA) to explicitly compute the diurnal variations of the isotope anomaly of short-lived species such as NOx and HOx. Δ17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the classical mass-balance equation, through the implementation of various sets of hypotheses pertaining to the transfer of Δ17O during chemical reactions.
The model confirms that diurnal variations in Δ17O of NOx are well predicted by the photochemical steady-state relationship during the day, but that at night a different approach must be employed (i.e. "fossilization" of the Δ17O of NOx as soon as the photolytical lifetime of NOx drops below ca. 5 min). We quantify the diurnally-integrated isotopic signature (DIIS) of sources of atmospheric nitrate and H2O2 under the various environmental conditions analyzed, which is of particular relevance to larger-scale implementations of Δ17O where high computational costs cannot be afforded.