Abstract. Nitrate loading of coastal ecosystems by rivers that drain industrialised catchments continues to be a problem in the South Eastern North Sea, in spite of significant mitigation efforts over the last 2 decades. To identify nitrate sources, sinks, and turnover in three German rivers that discharge into the German Bight, we determined δ 15N-NO3- and δ18O- NO3- in nitrate and δ 15N of particulate nitrogen for the period 2006–2009 (biweekly samples). The nitrate loads of Rhine, Weser and Ems varied seasonally in magnitude and δ 15N-NO3- (6.5–21‰), whereas the δ 18O-NO3- (-0.3–5.9‰) and δ 15N-PN (4–14‰) were less variable. Overall temporal patterns in nitrate mass fluxes and isotopic composition suggest that a combination of nitrate delivery from nitrification of soil ammonia in the catchment and assimilation of nitrate in the rivers control the isotopic composition of nitrate. Nitrification in soils as a source is indicated by low δ 18O-NO3- in winter, which traces the δ 18O of river water. Mean values of δ 18O-H2O were between –9.4‰ and –7.3‰; combined in a ratio of 2:1 with the atmospheric oxygen δ 18O of 23.5‰ agrees with the found δ 18O of nitrate in the rivers. Parallel variations of δ 15N-NO3- and δ 18O-NO3- within each individual river are caused by isotope effects associated with nitrate assimilation in the water column, the extent of which is determined by residence time in the river. Assimilation is furthermore to some extent mirrored both by the δ 15N of nitrate and particulate N. Although δ 15-NO3- observed in Rhine, Weser and Ems are reflected in high average δ 15N-PN (between 6‰ and 9‰, both are uncorrelated in the time series due to lateral and temporal mixing of PN. That a larger enrichment was consistently seen in δ 15N-NO3- relative to δ 18O-NO3- is attributed to constant additional diffuse nitrate inputs deriving from soil nitrification in the catchment area. A statistically significant inverse correlation exists between increasing δ 15N-NO3- values and decreasing NO3- concentrations. This inverse relationship – observed in each seasonal cycle – together with a robust relationship between human dominated land use and δ 15N-NO3- values demonstrates a strong influence of human activities and riverine nitrate consumption efficiency on the isotopic composition of riverine nitrate.
Carbon-13 kinetic isotope effects in the decarbonylation of liquid formic acid of natural isotopic composition initiated by phosphorus pentoxide
