Isotopic composition of nitrate in five German rivers discharging into the North Sea

We determined concentrations and isotopic composition of nitrate in five German rivers (Rhine, Elbe, Weser, Ems, and Eider) that discharge into the North Sea. Samples were obtained on a biweekly to monthly basis and chemical and isotopic analyses were conducted for the period January 2006 to March 2007 at sampling stations situated before estuarine mixing with North Sea water. We observed maximum nitrate loads in winter and fall, when both discharge and concentration of nitrate are highest. Mean annual isotope values in nitrate ranged from 8.2‰ to 11.3‰ for δ ¹⁵ N NO₃^- and 0.4‰ to 2.2‰ for δ ¹⁸ O NO₃^-. The ranges of isotope values suggest that nitrate in these rivers derives from soil nitrification, sewage, and/or manure. These and published data on other rivers in northern Europe and northern America reveal a correlation between agricultural land use (>60% in the catchment areas of rivers examined) and δ ¹⁵ N NO₃^- values. The rivers Rhine, Elbe, Weser and Ems show similar seasonal patterns of the isotopic fractionation of nitrate with increasing δ ¹⁵ N NO₃^- values and simultaneously decreasing NO₃^- concentrations during summer months, indicating that assimilation of nitrate is the main fractionation process of riverine nitrate. Isotopic signals in winter are more depleted than the mean summer isotope values, attributed to less microbial activity and assimilative processes. Load weighted nitrate δ¹⁵N of the riverine input to the German Bight Coastal Water mass before estuarine mixing and processing is between 8‰ and 12‰. The high δ¹⁵N value of river nitrate is matched by high δ¹⁵N of nitrate in surface sediments in the German Bight.