Quantifying atmospheric nitrate formation pathways based on a global model of the oxygen isotopic composition (δ17O) of atmospheric nitrate

Abstract

The oxygen isotopic composition (δ17O) of atmospheric nitrate is a function of the relative abundance of atmospheric oxidants (O 3, ROx=OH+HO2+RO2) and the formation pathway of nitrate from its precursor NOx (=NO+NO2). Coupled observations and modeling of nitrate δ17O can be used to quantify the relative importance of chemical formation pathways leading to nitrate formation and reduce uncertainties in the budget of reactive nitrogen chemistry in the atmosphere. We present the first global model of atmospheric nitrate δ17O and compare with available observations. The largest uncertainty for calculations of nitrate δ17O is the unconstrained variability in the δ17O value of tropospheric ozone. The model shows the best agreement with a global compilation of observations when assuming a δ17O value of tropospheric ozone equal to 35 % and preferential oxidation of NOx by the terminal oxygen atoms of ozone. Calculated values of annual-mean nitrate δ17O in the lowest model layer (0-200m above the surface) vary from 7% in the tropics to 41% in the polar-regions. The global, annual-mean tropospheric inorganic nitrate burden is dominated by nitrate formation via NO2+OH (76%), followed by N5O2 hydrolysis (18%) and NO2+DMS/HC (4%). Calculated nitrate δ17O is sensitive to the relative importance of each nitrate formation pathway, suggesting that observations of nitrate δ17O can be used to quantify the importance of individual reactions (e.g. N2O5 hydrolysis) leading to nitrate formation if the δ17O value of ozone is known. © 2009 Author(s).