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Aquifers within agricultural catchments are characterised by high spatial heterogeneity of their denitrification potential. Therefore, simple but sophisticated methods for measuring denitrification rates within the groundwater are crucial for predicting and managing N-fluxes within these anthropogenic ecosystems. Here, a newly developed automated online (15)N-tracer system is presented for measuring (N(2)+N(2)O) production due to denitrification in aquifer samples. The system consists of a self-developed sampler which automatically supplies sample aliquots to a membrane-inlet mass spectrometer. The developed system has been evaluated by a (15)N-nitrate tracer incubation experiment using samples (sulphidic and non-sulphidic) from the aquifer of the Fuhrberger Feld in northern Germany. It is shown that the membrane-inlet mass spectrometry (MIMS) system successfully enabled nearly unattended measurement of (N(2)+N(2)O) production within a range of 10 to 3300 µg N L(-1) over 7 days of incubation. The automated online approach provided results in good agreement with simultaneous measurements obtained with the well-established offline approach using isotope ratio mass spectrometry (IRMS). In addition, three different (15)N-aided mathematical approaches have been evaluated for their suitability to analyse the MIMS raw data under the given experimental conditions. Two approaches, which rely on the measurement of (28)N(2), (29)N(2) and (30)N(2), exhibit the best reliability in the case of a clear (15) N enrichment of evolved denitrification gases. The third approach, which uses only the ratio of (29)N(2)/(28)N(2), overestimates the concentration of labelled denitrification products under these conditions. By contrast, at low (15)N enrichments and low fractions of denitrified gas, the latter approach is on a par with the other two approaches. Finally, it can be concluded that the newly developed system represents a comprehensive and simply applicable tool for the determination of denitrification in aquifers.

Knowledge about the spatial variability of denitrification rates and the lifetime of denitrification in nitrate-contaminated aquifers is crucial to predict the development of groundwater quality. Therefore, regression models were derived to estimate the measured cumulative denitrification of aquifer sediments after one year of incubation from initial denitrification rates and several sediment parameters, namely total sulphur, total organic carbon, extractable sulphate, extractable dissolved organic carbon, hot water soluble organic carbon and potassium permanganate labile organic carbon. <br><br> For this purpose, we incubated aquifer material from two sandy Pleistocene aquifers in Northern Germany under anaerobic conditions in the laboratory using the ¹⁵N tracer technique. The measured amount of denitrification ranged from 0.19 to 56.2 mg N kg⁻¹ yr⁻¹. The laboratory incubations exhibited high differences between non-sulphidic and sulphidic aquifer material in both aquifers with respect to all investigated sediment parameters. Denitrification rates and the estimated lifetime of denitrification were higher in the sulphidic samples. For these samples, the cumulative denitrification measured during one year of incubation (<i>D</i>_cum(365)) exhibited distinct linear regressions with the stock of reduced compounds in the investigated aquifer samples. <i>D</i>_cum(365) was predictable from sediment variables within a range of uncertainty of 0.5 to 2 (calculated <i>D</i>_cum(365)/measured <i>D</i>_cum(365)) for aquifer material with a <i>D</i>_cum(365) > 20 mg N kg⁻¹ yr⁻¹. Predictions were poor for samples with lower <i>D</i>_cum(365), such as samples from the NO₃^&minus; bearing groundwater zone, which includes the non-sulphidic samples, from the upper part of both aquifers where denitrification is not sufficient to protect groundwater from anthropogenic NO₃^&minus; input. Calculation of <i>D</i>_cum(365) from initial denitrification rates was only successful for samples from the NO₃^&minus;-bearing zone, whereas a lag-phase of denitrification in samples from deeper zones of NO₃^&minus; free groundwater caused imprecise predictions. <br><br> In our study, <i>D</i>_cum(365) of two sandy Pleistocene aquifers was predictable using a combination of short-term incubations and analysis of sediment parameters. Moreover, the protective lifetime of denitrification sufficient to remove NO₃<sup>&mi...

An automated sample preparation unit for inorganic nitrogen (SPIN) coupled to a membrane inlet quadrupole mass spectrometer (MIMS) was developed for automated and sensitive determination of the N abundances and concentrations of nitrate, nitrite, and ammonium in aqueous solutions without any sample preparation. The minimum N concentration for an accurate determination of theN abundance is 7 μmol/L for nitrite and nitrate, with a relative standard deviation (RSD) of repeated measurements of <1%, and 70 μmol/L with an RSD < 0.4% in the case of ammonium. The SPIN-MIMS system provides a wide dynamic range (up to 3500 μmol/L) for all three N species for both isotope abundance and concentration measurements. The comparison of parallel measurements of N-labeled NH and NO from soil extracts with the denitrifier method and the SPIN-MIMS system shows a good agreement between both methods.

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