Reactive modeling of denitrification in soils with natural and depleted organic matter

Nitrogen fertilizers used in agriculture often cause nitrate leaching towards shallow groundwater, especially in lowland areas where the flat topography minimize the surface run off. In order to introduce good agricultural practices that reduce the amount of nitrate entering the groundwater system, it is important to quantify the kinetic control on nitrate attenuation capacity. With this aim, a series of anaerobic batch experiments, consisting of loamy soils and nitrate-contaminated groundwater, were carried out using acetate and natural dissolved organic matter as electron donors. Acetate was chosen because it is the main intermediate species in many biodegradation pathways of organic compounds, and it is a suitable carbon source for denitrification. Sorption of acetate was also determined, fitting a Langmuir isotherm in both natural and artificially depleted organic matter soils. Experiments were performed in quadruplicate to account for the spatial variability of soil parameters. The geochemical code PHREEQC (version 2) was used to simulate kinetic denitrification using Monod equation, equilibrium Langmuir sorption of acetate, and equilibrium reactions of gas and mineral phases (calcite). The reactive modeling results highlighted a rapid acetate and nitrate mineralization rate, suggesting that the main pathway of nitrate attenuation is through denitrification while calcite acted as a buffer for pH. However, in the absence of acetate, the natural content of organic matter did not allow to complete the denitrification process leading to nitrite accumulation. Reactive modeling is thought to be an efficient and robust tool to quantify the complex biogeochemical reactions which can take place in underground environments. © 2011 Springer Science+Business Media B.V.