Isotopic composition of nitrate-nitrogen as a marker of riparian and benthic denitrification at the scale of the whole Seine River system

Nitrogen budgets established for large river systems reveal that up to 60% of the nitrate exported from agricultural soils is eliminated, either when crossing riparian wetlands areas before even reaching surface waters, or within the rivers themselves through benthic denitrification. The study of nitrogen isotope ratios of riverine nitrates could offer an elegant means to assess the extent of denitrification and thus confirm these budgets, as it is known that denitrification results in a natural N-15 enrichment of residual nitrates. The results reported here, for the Seine river system ( France), demonstrate the feasibility of this isotopic approach at the scale of large watersheds. On the basis of in situ observations carried out in a large storage reservoir in the upstream Seine catchment (Der Lake), where intensive benthic denitrification occurs, as well as on the basis of laboratory experiments of denitrification under controlled conditions, it is shown that the isotopic discrimination associated with benthic denitrification is minimal (epsilon of NO3-N ranging from -1.5 to -3.6parts per thousand), probably because the rate-limiting step of the process consists of nitrate diffusion through the water-sediment interface. Riparian denitrification on the contrary, when it implies nitrate reduction during convective transfer through reducing environements, causes a much more significant isotopic enrichment of N-15 of residual nitrate (epsilon about -18parts per thousand). The authors report measurements of nitrogen isotopic composition of nitrate from rivers of various stream orders in the Seine river system under summer conditions. Anomalies in the data with respect to the values expected from the mixture of the various sources of nitrate are here attributed to riparian denitrification. However, the authors show that because of the patchy distribution of actively denitrifying riparian zones within the drainage network, the isotopic signature conferred to residual nitrate in river water intrinsically provides only a minimum estimate of the extent of denitrification.