Comparison of methods for the determination of NO-O3-NO2 fluxes and chemical interactions over a bare soil

Tropospheric ozone (O-3) is a known greenhouse gas responsible for impacts on human and animal health and ecosystem functioning. In addition, O-3 plays an important role in tropospheric chemistry, together with nitrogen oxides. The determination of surface-atmosphere exchange fluxes of these trace gases is a prerequisite to establish their atmospheric budget and evaluate their impact onto the biosphere. In this study, O-3, nitric oxide (NO) and nitrogen dioxide (NO2) fluxes were measured using the aerodynamic gradient method over a bare soil in an agricultural field. Ozone and NO fluxes were also measured using eddy-covariance and automatic chambers, respectively. The aerodynamic gradient measurement system, composed of fast response sensors, was capable to measure significant differences in NO and O-3 mixing ratios between heights. However, due to local advection, NO2 mixing ratios were highly non-stationary and NO2 fluxes were, therefore, not significantly different from zero. The chemical reactions between O-3, NO and NO2 led to little ozone flux divergence between the surface and the measurement height (less than 1% of the flux on average), whereas the NO flux divergence was about 10% on average. The use of fast response sensors allowed reducing the flux uncertainty. The aerodynamic gradient and the eddy-covariance methods gave comparable O-3 fluxes. The chamber NO fluxes were down to 70% lower than the aerodynamic gradient fluxes, probably because of either the spatial heterogeneity of the soil NO emissions or the perturbation due to the chamber itself.