Nitrogen isotope analysis of aqueous ammonium and nitrate by membrane inlet isotope ratio mass spectrometry (MIRMS) at natural abundance levels.

RATIONALE: Existing methods for the measurement of the 15 N/14 N isotopic composition of ammonium and nitrate are either only suitable for labelled samples or require considerable sample preparation efforts (or both). Our goal was to modify an existing analytical approach to allow for natural abundance precision levels. METHODS: Published reaction protocols were used to convert ammonium into N2 by NaOBr and nitrate into N2 O by TiCl3 . A membrane inlet system was developed and coupled to an isotope ratio mass spectrometer to allow precise determination of the analytes. RESULTS: Concentrations of ≥35 µmol/L N for both ammonium or nitrate could be analysed for δ15 N values with precisions of better than 0.9 mUr. While ammonium analyses exhibited a small concentration dependency and an offset of 2.7 mUr at high ammonium concentrations irrespective of the standard isotopic composition, nitrate analysis showed no offset but a blank contribution visible at very low concentrations. CONCLUSIONS: The presented method is capable of fast measurement of δ15 N values in ammonium and nitrate from aqueous samples with reasonable accuracy at natural abundance levels. It will thus facilitate the application of isotopic methods to studies of nitrogen cycling in ecosystems.

Comparison of methods to determine triple oxygen isotope composition of N2O.

RATIONALE: The oxygen isotope anomaly, Δ(17) O, of N2 O and nitrate is useful to elucidate nitrogen oxide dynamics. A comparison of different methods for Δ(17) O measurement was performed. METHODS: For Δ(17) O measurements, N2 O was converted into O2 and N2 using microwave-induced plasma in a quartz or corundum tube reactor, respectively, or conversion was carried out in a gold wire oven. In each case, isotope ratios were measured by isotope ratio mass spectrometry. RESULTS: All the tested methods showed acceptable precision (coefficient of variation <2.4 % at 160 nmol N2 O) with high sample size but the sample size dependence was lowest when using microwave-induced plasma in a corundum tube reactor. CONCLUSIONS: The use of microwave-induced plasma in a corundum tube yields best results for Δ(17) O measurement on N2 O gas samples.

Interlaboratory assessment of nitrous oxide isotopomer analysis by isotope ratio mass spectrometry and laser spectroscopy: current status and perspectives.

RATIONALE: In recent years, research and applications of the N2O site-specific nitrogen isotope composition have advanced, reflecting awareness of the contribution of N2O to the anthropogenic greenhouse effect, and leading to significant progress in instrument development. Further dissemination of N2O isotopomer analysis, however, is hampered by a lack of internationally agreed gaseous N2O reference materials and an uncertain compatibility of different laboratories and analytical techniques. METHODS: In a first comparison approach, eleven laboratories were each provided with N2O at tropospheric mole fractions (target gas T) and two reference gases (REF1 and REF2). The laboratories analysed all gases, applying their specific analytical routines. Compatibility of laboratories was assessed based on N2O isotopocule data for T, REF1 and REF2. Results for T were then standardised using REF1 and REF2 to evaluate the potential of N2O reference materials for improving compatibility between laboratories. RESULTS: Compatibility between laboratories depended on the analytical technique: isotope ratio mass spectrometry (IRMS) results showed better compatibility for δ(15)N values, while the performance of laser spectroscopy was superior with respect to N2O site preference. This comparison, however, is restricted by the small number of participating laboratories applying laser spectroscopy. Offset and two-point calibration correction of the N2O isotopomer data significantly improved the consistency of position-dependent nitrogen isotope data while the effect on δ(15)N values was only minor. CONCLUSIONS: The study reveals that for future research on N2O isotopocules, standardisation against N2O reference material is essential to improve interlaboratory compatibility. For atmospheric monitoring activities, we suggest N2O in whole air as a unifying scale anchor.