Direct measurement of dissolved dinitrogen to refine reactive modelling of denitrification in agricultural soils

Nitrogen fertilizers used in agriculture often cause nitrate leaching towards shallow groundwater, especially in lowland areas where soil permeability, ploughing, clay content, and the flat topography minimizes surface runoff. The introduction of good agricultural practices to reduce the nitrate amount entering the groundwater system is crucial to ameliorate the kinetic control on nitrate denitrification capacity. With this aim, a series of anaerobic mesocosms, consisting of loamy and clay soils and nitrate rich water, were modelled using acetate and natural organic matter as electron donors. Acetate was chosen because it is the main intermediate in many biodegradation pathways of organic compounds, and hence it is a suitable carbon source for denitrification. To account for the spatial variability of soil parameters, the experiments were performed in triplicates. The geochemical code PHREEQC(3) was used to simulate kinetic denitrification, and equilibrium reactions of gas and mineral phases. The reactive modelling results highlighted a rapid acetate and nitrate degradation rate, a rapid production of dissolved inorganic carbon and dinitrogen, and a steady concentration of dissolved iron and sulphate, suggesting that the main pathway of nitrate attenuation is through denitrification; concomitantly excluding the occurrence of other processes leading to nitrate consumption. In the absence of acetate, the loamy soil, poor of natural organic matter, did not allow to complete the denitrification process. This modelling study investigates in detail the relationship between the denitrification process in natural soils, with excess and in limitation of organic substrates, and the occurrence and fate of dissolved dinitrogen analysed with a high precision membrane inlet mass spectrometer. Results demonstrate that modelling nitrate degradation processes as a whole, using geochemical datasets and codes, will improve the estimates of agricultural landscapes denitrification and support better nitrogen management, especially in lowland environments.