Significant non-linearity in nitrous oxide chamber data and its effect on calculated annual emissions

Abstract. Chambers are widely used to measure surface fluxes of nitrous oxide (N₂O). Usually linear regression is used to calculate the fluxes from the chamber data. Non-linearity in the chamber data can result in an underestimation of the flux. Non-linear regression models are available for these data, but are not commonly used. In this study we compared the fit of linear and non-linear regression models to determine significant non-linearity in the chamber data. We assessed the influence of this significant non-linearity on the annual fluxes.

For a two year dataset from an automatic chamber we calculated the fluxes with linear and non-linear regression methods. Based on the fit of the methods 32% of the data was defined significant non-linear. Significant non-linearity was not recognized by the goodness of fit of the linear regression alone. Using non-linear regression for these data and linear regression for the rest, increases the annual flux with 21% to 53% compared to the flux determined from linear regression alone.

We suggest that differences this large are due to leakage through the soil. Macropores or a coarse textured soil can add to fast leakage from the chamber. Yet, also for chambers without leakage non-linearity in the chamber data is unavoidable, due to feedback from the increasing concentration in the chamber. To prevent a possibly small, but systematic underestimation of the flux, we recommend comparing the fit of a linear regression model with a non-linear regression model. The non-linear regression model should be used if the fit is significantly better. Open questions are how macropores affect chamber measurements and how optimization of chamber design can prevent this.